Ernie R. Lewis

Production flux of sea spray aerosol

Knowledge of the size- and composition-dependent production flux of primary sea spray aerosol (SSA) particles and its dependence on environmental variables is required for modeling cloud microphysical properties and aerosol radiative influences, interpreting measurements of particulate matter in coastal areas and its relation to air quality, and evaluating rates of uptake and reactions of gases in sea spray drops. This review examines recent research pertinent to SSA production flux, which deals mainly with production of particles with r 80 (equilibrium radius at 80% relative humidity) less than 1 m and as small as 0.01 m. Production of sea spray particles and its dependence on controlling factors has been investigated in laboratory studies that have examined the dependences on water temperature, salinity, and the presence of organics and in field measurements with micrometeorological techniques that use newly developed fast optical particle sizers. Extensive measurements show that water-insoluble organic matter contributes substantially to the composition of SSA particles with r80 < 0.25 m and, in locations with high biological activity, can be the dominant constituent. Order-of-magnitude variation remains in estimates of the size-dependent production flux per white area, the quantity central to formulations of the production flux based on the whitecap method. This variation indicates that the production flux may depend on quantities such as the volume flux of air bubbles to the surface that are not accounted for in current models. Variation in estimates of the whitecap fraction as a function of wind speed contributes additional, comparable uncertainty to production flux estimates.

Direct aerosol forcing: Calculation from observables and sensitivities to inputs

[1] Understanding sources of uncertainty in aerosol direct radiative forcing (DRF), the difference in a given radiative flux component with and without aerosol, is essential to quantifying changes in Earth’s radiation budget. We examine the uncertainty in DRF owing to measurement uncertainty in the quantities on which it depends: aerosol optical depth, single scattering albedo, asymmetry parameter, solar geometry, and surface albedo. Direct radiative forcing at the top of the atmosphere and at the surface is calculated at three locations representing distinct aerosol types and radiative environments. Sensitivities, the changes in DRF in response to unit changes in individual aerosol or surface properties, are also calculated for these conditions. The uncertainty in DRF associated with a given property is computed as the product of the sensitivity and typical measurement uncertainty in the respective property. Sensitivity and uncertainty values permit estimation of total uncertainty in calculated DRF and identification of properties that most limit accuracy in estimating forcing. Absolute total uncertainties in modeled local diurnally averaged forcing range from 0.2 to 3.1 W m � 2 for the ranges of properties examined here. Relative total uncertainties range from � 20 to 80% with larger values at higher latitudes, where fluxes are low. The largest contributor to total uncertainty in DRF is single scattering albedo; however, decreasing measurement uncertainties for any property would increase accuracy in DRF. Comparison of two radiative transfer models suggests the contribution of modeling error is small compared to the total uncertainty although comparable to uncertainty arising from some individual properties.

The optimal carbonate dissociation constants for determining surface water pCO2 from alkalinity and total inorganic carbon

In many numerical ocean chemistry models, total dissolved inorganic carbon, DIC and total alkalinity, TA are transported between subsurface boxes. The partial pressure pCO2 is subsequently calculated from TA and DIC in the surface box in order to account for air–sea exchange of carbon dioxide. The conversion is commonly performed by solving the thermodynamic relationships for equilibria between carbonate, bicarbonate, and aqueous CO2 using carbonate dissociation constants. Four independent determinations of the constants have been made for seawater in the past 50 years. These results have been corrected, refit, and combined by others creating a virtual cottage industry of laboratory and field verification, and cross-checks. Here, we show that, based on field observations in three ocean basins, the calculated surface water pCO2 from TA and DIC corresponds best with the measured pCO2 if the constants proposed by Mehrbach et al. [Mehrbach, C., Culberson, C.H., Hawley, J.E., Pytkowicz, R.M., 1973. Measurement of the apparent dissociation constants of carbonic acid in seawater at atmospheric pressure. Limnology and Oceanography 18, 897–907] as refit by Dickson and Millero [Dickson, A.G., Millero, F.J., 1987. A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media. Deep-Sea Res. 34, 1733–1743] are used. This suggests that the K1/K2 ratio of Mehrbach et al. for a pCO2 range of 280–450 μatm is correct but it does not necessarily imply that the absolute values of K1 and K2 are correct or that these constants work as well at higher pCO2. An independent cross-check with pCO2 measurements made at constant temperature (20°C) is in agreement with these conclusions. The differences in calculated pCO2 can be as great as 30 μatm depending which constants are used. If the models are forced with a prescribed atmospheric pCO2 they will end up having surface concentration of TA that are up to 20 μeq kg−1 too high or DIC concentration up to 20 μmol kg−1 too low if constants other than those of Mehrbach et al. are used. This makes comparisons between observation and models problematic.

Sea spray aerosol as a unique source of ice nucleating particles

Ice nucleating particles (INPs) are vital for ice initiation in, and precipitation from, mixed-phase clouds. A source of INPs from oceans within sea spray aerosol (SSA) emissions has been suggested in previous studies but remained unconfirmed. Here, we show that INPs are emitted using real wave breaking in a laboratory flume to produce SSA. The number concentrations of INPs from laboratory-generated SSA, when normalized to typical total aerosol number concentrations in the marine boundary layer, agree well with measurements from diverse regions over the oceans. Data in the present study are also in accord with previously published INP measurements made over remote ocean regions. INP number concentrations active within liquid water droplets increase exponentially in number with a decrease in temperature below 0 °C, averaging an order of magnitude increase per 5 °C interval. The plausibility of a strong increase in SSA INP emissions in association with phytoplankton blooms is also shown in laboratory simulations. Nevertheless, INP number concentrations, or active site densities approximated using “dry” geometric SSA surface areas, are a few orders of magnitude lower than corresponding concentrations or site densities in the surface boundary layer over continental regions. These findings have important implications for cloud radiative forcing and precipitation within low-level and midlevel marine clouds unaffected by continental INP sources, such as may occur over the Southern Ocean.

Determination of and evidence for non‐core‐shell structure of particles containing black carbon using the Single‐Particle Soot Photometer (SP2)

[1] The large uncertainty associated with black carbon (BC) direct forcing is due, in part, to the dependence of light absorption of BC-containing particles on the position of the BC within the particle. It is predicted that this absorption will be greatest for an idealized core-shell configuration in which the BC is a sphere at the center of the particle whereas much less absorption should be observed for particles in which the BC is located near or on the surface. Such microphysical information on BC-containing particles has previously been provided only by labor-intensive microscopy techniques, thus often requiring that climate modelers make assumptions about the location of the BC within the particle that are based more on mathematical simplicity than physical reality. The present paper describes a novel analysis method that utilizes the temporal behavior of the scattering and incandescence signals from individual particles containing

Clouds, Precipitation, and Marine Boundary Layer Structure during the MAGIC Field Campaign

The recent ship-based Marine ARM GCSS Pacific Cross-Section Intercomparison (GPCI) Investigation of Clouds (MAGIC) field campaign with the marine-capable Second ARM Mobile Facility (AMF2) deployed on the Horizon Lines cargo container M/V Spirit provided nearly 200 days of intraseasonal high-resolution observations of clouds, precipitation, and marine boundary layer (MBL) structure on multiple legs between Los Angeles, California, and Honolulu, Hawaii. During the deployment, MBL clouds exhibited a much higherfrequencyofoccurrencethanothercloudtypesandoccurredmoreofteninthewarmseasonthaninthe cold season. MBL clouds demonstrated a propensity to produce precipitation, which often evaporated before reaching the ocean surface. The formation of stratocumulus is strongly correlated to a shallow MBL with a strong inversion and a weak transition, while cumulus formation is associated with a much weaker inversion and stronger transition. The estimated inversion strength is shown to depend seasonally on the potential temperature at 700hPa. The location of the commencement of systematic MBL decoupling always occurred eastward of the locations of cloud breakup, and the systematic decoupling showed a strong moisture stratification.Theentrainment ofthedrywarmairabovetheinversionappearstobethedominantfactortriggering the systematic decoupling, while surface latent heat flux, precipitation, and diurnal circulation did not play major roles. MBL clouds broke up over a short spatial region due to the changes in the synoptic conditions, implying that in real atmospheric conditions the MBL clouds do not have enough time to evolve as in the idealized models.

Assessment of the quality of the shipboard measurements of total alkalinity on the WOCE Hydrographic Program Indian Ocean CO2 survey cruises 1994–1996

In 1995, we participated in a number of WOCE Hydrographic Program cruises in the Indian Ocean as part of the Joint Global Ocean Flux Study (JGOFS) CO2 Survey sponsored by the Department of Energy (DOE). Two titration systems were used throughout this study to determine the pH, total alkalinity (TA) and total inorganic carbon dioxide (TCO2) of the samples collected during these cruises. The performance of these systems was monitored by making closed cell titration measurements on Certified Reference Materials (CRMs). A total of 962 titrations were made on six batches of CRMs during the cruises. The reproducibility calculated from these titrations was ±0.007 in pH, ±4.2 μmol kg−1 in TA, and ±4.1 μmol kg−1 in TCO2. The at-sea measurements on the CRMs were in reasonable agreement with laboratory measurements made on the same batches. These results demonstrate that the CRMs can be used as a reference standard for TA and to monitor the performance of titration systems at sea. Measurements made on the various legs of the cruise agreed to within 6 μmol kg−1 at the 15 crossover points. The overall mean and standard deviation of the differences at all the crossovers are 2.1±2.1 μmol kg−1. These crossover results are quite consistent with the overall reproducibility of the CRM analyses for TA (±4 μmol kg−1) over the duration of the entire survey. The TA results for the Indian Ocean cruises provide a reliable data set that when combined with TCO2 data can completely characterize the carbonate system.

The Dynamic Shape Factor of Sodium Chloride Nanoparticles as Regulated by Drying Rate

The influence of drying rate on the dynamic shape factor χ of NaCl particles was investigated. The drying rate at the efflorescence relative humidity (ERH) of 45% was controlled in a laminar flow tube and varied from 5.5 ± 0.9 to 101 ± 3 RH s–1 at ERH, where RH represents one percent unit of relative humidity. Dry particles having mobility diameters of 23–84 nm were studied, corresponding to aqueous particles of 37–129 nm at the RH (57%) prior to drying. At each mobility diameter and drying rate, the critical supersaturation of cloud-condensation activation was also measured. The mobility diameter and the critical supersaturation were combined in an analysis to determine the value of χ. The measured values varied from 1.02 to 1.26. For fixed particle diameter the χ value decreased with increasing drying rate. For fixed drying rate, a maximum occurred in χ between 35- and 40-nm dry mobility diameter, with a lower χ for both smaller and larger particles. The results of this study, in conjunction with the introduced apparatus for obtaining quantified drying rates, can allow the continued development of a more detailed understanding of the morphology of submicron salt particles, with the potential for the follow-on development of quantitative modeling of evaporation and crystal growth at these dimensions.

Reversible uptake of water on NaCl nanoparticles at relative humidity below deliquescence point observed by noncontact environmental atomic force microscopy.

The behavior of NaCl nanoparticles as a function of relative humidity (RH) has been characterized using non-contact environmental atomic force microscopy (e-AFM) to measure the heights of particles deposited on a prepared hydrophobic surface. Cubic NaCl nanoparticles with sides of 35 and 80 nm were found to take up water reversibly with increasing RH well below the bulk deliquescence relative humidity (DRH) of 75% at 23(∘)C, and to form a liquid-like surface layer of thickness 2 to 5 nm, with measurable uptake (>2 nm increase in particle height) beginning at 70% RH. The maximum thickness of the layer increased with increasing RH and increasing particle size over the range studied. The liquid-like behavior of the layer was indicated by a reversible rounding at the upper surface of the particles, fit to a parabolic cross-section, where the ratio of particle height to maximum radius of curvature increases from zero (flat top) at 68% RH to 0.7 ± 0.3 at 74% RH. These observations, which are consistent with a reorganization of mass on the solid NaCl nanocrystal at RH below the DRH, suggest that the deliquescence of NaCl nanoparticles is more complex than an abrupt first-order phase transition. The height measurements are consistent with a phenomenological model that assumes favorable contributions to the free energy of formation of a liquid layer on solid NaCl due both to van der Waals interactions, which depend partly upon the Hamaker constant, A(film), of the interaction between the thin liquid film and the solid NaCl, and to a longer-range electrostatic interaction over a characteristic length of persistence, ξ; the best fit to the data corresponded to A(film)= 1 kT and ξ = 2.33 nm.

Deliquescence and efflorescence of small particles

We examine size-dependent deliquescence/efflorescence phase transformation for particles down to several nanometers in size. Thermodynamic properties of inorganic salt particles, coated with aqueous solution layers of varying thickness and surrounded by vapor, are analyzed. A thin layer criterion (TLC) is introduced to define a limiting deliquescence relative humidity (RH(D)) for small particles. This requires: (1) equality of chemical potentials between salt in an undissolved core, and thin adsorbed solution layer, and (2) equality of chemical potentials between water in the thin layer and vapor phase. The usual bulk deliquescence conditions are recovered in the limit of large dry particle size. Nanosize particles are found to deliquesce at relative humidity just below the RH(D) on crossing a nucleation barrier, located at a critical solution layer thickness. This barrier vanishes precisely at the RH(D) defined by the TLC. Concepts and methods from nucleation theory including the kinetic potential, self-consistent nucleation theory, nucleation theorems, and the Gibbs dividing surface provide theoretical foundation and point to unifying features of small particle deliquescence/efflorescence processes. These include common thermodynamic area constructions, useful for interpretation of small particle water uptake measurements, and a common free-energy surface, with constant RH cross sections describing deliquescence and efflorescence related through the nucleation theorem.