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 laboratorygenerated 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.marine aerosols | ice nucleation | clouds

Individual particles that on a mass basis consist dominantly of the components ammonium sulfate, organic material, and water are a common class of submicron particles found in today's atmosphere. Here we use (1) the organic-to-sulfate (org:sulf) mass ratio of the overall particle and (2) the oxygen-to-carbon (O:C) elemental ratio of the organic component as input variables in parameterisations that predict the critical relative humidity of several different types of particle phase transitions. These transitions include liquid-liquid phase separation (SRH), efflorescence (ERH), and deliquescence (DRH). Experiments were conducted by optical microscopy for 11 different oxygenated organic-ammonium sulfate systems covering the range 0.1 < org:sulf <12.8 and 0.29 < O:C < 1.33. These new data, in conjunction with other data already available in the literature, were used to develop the parameterisations SRH(org:sulf, O:C), ERH(org:sulf, O:C), and DRH(org:sulf, O:C). The parameterisations correctly predicted SRH within 15 % RH for 86 % of the measurements, ERH within 5 % for 86 % of the measurements, and DRH within 5 % for 95 % of the measurements. The applicability of the derived parameterisations beyond the training data set was tested against observations for organic-sulfate particles produced in an environmental chamber. The organic component consisted of secondary organic material produced by the oxidation of isoprene, α-pinene, and β-caryophyllene. The predictions of the parameterisations were also tested against data from the Southern Great Plains, Oklahoma, USA. The observed ERH and DRH values for both the chamber and field data agreed within 5 % RH with the value predicted by the parameterisations using the measured org:sulf and O:C ratios as the input variables

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23 This study addresses, through two types of experiments, the potential for the oceans to act as a 24 source of atmospheric ice-nucleating particles (INPs). The INP concentration via deposition 25 mode nucleation was measured in situ at a coastal site in British Columbia in August 2013. The 26 INP concentration at conditions relevant to cirrus clouds (i.e., -40°C and relative humidity with 27 respect to ice, RHice=139%) ranged from 0.2 L -1 to 3.3 L -1 . Correlations of the INP 28 concentrations with levels of anthropogenic tracers (i.e., CO, SO2, NOx, and black carbon) and 29 numbers of fluorescent particles do not indicate a significant influence from anthropogenic 30 sources or submicron bioaerosols, respectively. Additionally, the INPs measured in the 31 deposition mode showed a poor correlation with the concentration of particles with sizes larger 32 than 500 nm, which is in contrast with observations made in the immersion freezing mode. To 33 investigate the nature of particles that could have acted as deposition INP, laboratory 34 experiments with potential marine aerosol particles were conducted under the ice-nucleating 35 conditions used in the field. At -40°C, no deposition activity was observed with salt aerosol 36 particles (sodium chloride and two forms of commercial sea salt: Sigma-Aldrich and Instant 37 Ocean), particles composed of a commercial source of natural organic matter (Suwannee River 38 humic material), or particle mixtures of sea salt and humic material. In contrast, exudates from 39 three phytoplankton (Thalassiosira pseudonana, Nanochloris atomus, and Emiliania huxleyi) 40 and one marine bacterium (Vibrio harveyi) exhibited INP activity at low RHice values, down to 41 below 110%. This suggests that the INPs measured at the field site were of marine biological 42 origins, although we cannot rule out other sources, including mineral dust. 43 44 thank the University of Denver faculty start-up fund and PROF grant for 463 partial financial support. 464 465 References 466 Alpert, P.A., Aller, J.Y., and Knopf, D.A., 2011a. Ice nucleation from aqueous NaCl droplets with and 467 without marine diatoms, Atmos. Chem. Phys, 11, 5539-5555. 469Alpert, P. A., Aller, J. Y., and Knopf, D. A., 2011b. Initiation of the ice phase by marine biogenic surfaces 470 in supersaturated gas and supercooled aqueous phases, Phys.

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The hygroscopic phase transitions of ammonium sulfate mixed with isoprene-derived secondary organic material were investigated in aerosol experiments. The organic material was produced by isoprene photo-oxidation at 40% relative humidity. The low volatility fraction of the photo-oxidation products condensed onto ammonium sulfate particles. The particle-phase organic material had oxygen-to-carbon ratios of 0.67 to 0.74 for mass concentrations of 20 to 30 μg m^&minus;3. The deliquescence, efflorescence, and phase miscibility of the mixed particles were investigated using a dual arm tandem differential mobility analyzer. The isoprene photo-oxidation products induced deviations in behavior relative to pure ammonium sulfate. Compared to an efflorescence relative humidity (ERH) of 30 to 35% for pure ammonium sulfate, efflorescence was eliminated for mixed aqueous particles having organic volume fractions ε of approximately 0.6 and greater. Compared to a deliquescence relative humidity (DRH) of 80% for pure ammonium sulfate, the DRH steadily decreased for increasing ε, approaching a DRH of 40% for ε of 0.9. Parameterizations of the DRH(ε) and ERH(ε) curves were as follows: DRH(ε)= &Sigma; _<i>i</i> <i>c_i,d xⁱ</i> valid for 0 ≤ ε ≤ 0.86 and ERH(ε)= &Sigma; _<i>i</i> <i>c_i,e xⁱ</i> valid for 0 ≤ ε ≤ 0.55 for the coefficients <i>c_0,d</i>= 80.67, <i>c_0,e</i> = 28.35, <i>c_1,d</i>= &minus;11.45, <i>c_1,e</i> = &minus;13.66, <i>c_2,d</i> = 0, <i>c_2,e</i> = 0, <i>c_3,d</i> = 57.99, <i>c_3,e</i> = &minus;83.80, <i>c_4,d</i> = &minus;106.80, and <i>c_4,d</i> = 0. The molecular description that is thermodynamically implied by these strongly sloped DRH(ε) and ERH(ε) curves is that the organic isoprene photo-oxidation products, the inorganic ammonium sulfate, and water form a miscible liquid phase even at low relative humidity. This phase miscibility is in contrast to the liquid-liquid separation that occurs for some other types of secondary organic material. These differences in liquid-liquid separation are consistent with a prediction recently presented in the literature that the bifurcation between liquid-liquid phase separation versus mixing depends on the oxygen-to-carbon ratio of the organic material. The conclusions are that the influence of secondary organic material on the hygroscopic properties of ammonium sulfate varies with organic composition and that the degree of oxygenation of the organic material, which is a measurable characteristic of complex orga...

Diatoms are encased within sophisticated stable lightweight silica cell walls. These frustules have the potential to protect the algal cell against the feeding tools of their most abundant metazoan predators, the copepods. We examined the mechanical strengths of the 3 North Sea diatom species Actinoptychus senarius, Thalassiosira punctigera and Coscinodiscus wailesii and their effect on feeding efficiency of copepods. (1) We determined the stability of the diatoms by means of 'micro-crush-tests' performed in the laboratory with calibrated microneedles. (2) In feeding experiments, we compared the ability and efficiency of the 3 North Sea copepod species Temora longicornis, Centropages hamatus and Acartia clausi to crush frustules. The results showed a remarkable correlation between mechanical properties and size of diatom frustules and feeding success of the copepods. The weakly silicified diatom T. punctigera was the least stable and best fed upon, whilst having the highest growth rate. The diatoms having the most complex frustule, A. senarius, exhibited the greatest stability, whilst being fed upon least. The largest diatom, C. wailesii, was partially protected by its size, but was nonetheless suitable as prey for the large copepods that, in the case of C. hamatus, seem to have developed special feeding techniques to overcome the size-mediated protection.

Recent atmospheric measurements show that biological particles are important ice nuclei. Types of biological particles that may be good ice nuclei include bacteria, pollen and fungal spores. We studied the ice nucleation properties of water droplets containing fungal spores from the genus <i>Cladosporium</i>, one of the most abundant types of spores found in the atmosphere. For water droplets containing a <i>Cladosporium</i> spore surface area of ~217 μm² (equivalent to ~5 spores with average diameters of 3.2 μm), 1% of the droplets froze by &minus;28.5 &deg;C and 10% froze by &minus;30.1 &deg;C. However, there was a strong dependence on freezing temperature with the spore surface area of <i>Cladosporium</i> within a given droplet. As such, freezing temperatures for droplets containing 1–5 spores are expected to be approximately &minus;35.1&plusmn;2.3 &deg;C (1&sigma; S.D.). Atmospheric ice nucleation on spores of <i>Cladosporium</i> sp., or other spores with similar surface properties, do not appear to explain recent atmospheric measurements showing that biological particles are important ice nuclei. The poor ice nucleation ability of <i>Cladosporium</i> sp. spores may be attributed to the surface which is coated with hydrophobins (a class of hydrophobic proteins that appear to be widespread in filamentous fungi). Given the ubiquity of hydrophobins on spore surfaces, the current study may be applicable to many fungal species of atmospheric importance