Abstract. The second phase of the Fifth International Ice Nucleation Workshop (FIN-02) involved the gathering of a large number of researchers at the Karlsruhe Institute of Technology's Aerosol Interactions and Dynamics of the Atmosphere (AIDA) facility to promote characterization and understanding of ice nucleation measurements made by a variety of methods used worldwide. Compared to the previous workshop in 2007, participation was doubled, reflecting a vibrant research area. Experimental methods involved sampling of aerosol particles by direct processing ice nucleation measuring systems from the same volume of air in separate experiments using different ice nucleating particle (INP) types, and collections of aerosol particle samples onto filters or into liquid for sharing amongst measurement techniques that post-process these samples. In this manner, any errors introduced by differences in generation methods when samples are shared across laboratories were mitigated. Furthermore, as much as possible, aerosol particle size distribution was controlled so that the size limitations of different methods were minimized. The results presented here use data from the workshop to assess the comparability of immersion freezing measurement methods activating INPs in bulk suspensions, methods that activate INPs in condensation and/or immersion freezing modes as single particles on a substrate, continuous flow diffusion chambers (CFDCs) directly sampling and processing particles well above water saturation to maximize immersion and subsequent freezing of aerosol particles, and expansion cloud chamber simulations in which liquid cloud droplets were first activated on aerosol particles prior to freezing. The AIDA expansion chamber measurements are expected to be the closest representation to INP activation in atmospheric cloud parcels in these comparisons, due to exposing particles freely to adiabatic cooling. The different particle types used as INPs included the minerals illite NX and potassium feldspar (K-feldspar), two natural soil dusts representative of arable sandy loam (Argentina) and highly erodible sandy dryland (Tunisia) soils, respectively, and a bacterial INP (Snomax®). Considered together, the agreement among post-processed immersion freezing measurements of the numbers and fractions of particles active at different temperatures following bulk collection of particles into liquid was excellent, with possible temperature uncertainties inferred to be a key factor in determining INP uncertainties. Collection onto filters for rinsing versus directly into liquid in impingers made little difference. For methods that activated collected single particles on a substrate at a controlled humidity at or above water saturation, agreement with immersion freezing methods was good in most cases, but was biased low in a few others for reasons that have not been resolved, but could relate to water vapor competition effects. Amongst CFDC-style instruments, various factors requiring (variable) higher supersaturations to achieve equivalent immersion freezing activation dominate the uncertainty between these measurements, and for comparison with bulk immersion freezing methods. When operated above water saturation to include assessment of immersion freezing, CFDC measurements often measured at or above the upper bound of immersion freezing device measurements, but often underestimated INP concentration in comparison to an immersion freezing method that first activates all particles into liquid droplets prior to cooling (the PIMCA-PINC device, or Portable Immersion Mode Cooling chAmber–Portable Ice Nucleation Chamber), and typically slightly underestimated INP number concentrations in comparison to cloud parcel expansions in the AIDA chamber; this can be largely mitigated when it is possible to raise the relative humidity to sufficiently high values in the CFDCs, although this is not always possible operationally. Correspondence of measurements of INPs among direct sampling and post-processing systems varied depending on the INP type. Agreement was best for Snomax® particles in the temperature regime colder than −10 ∘C, where their ice nucleation activity is nearly maximized and changes very little with temperature. At temperatures warmer than −10 ∘C, Snomax® INP measurements (all via freezing of suspensions) demonstrated discrepancies consistent with previous reports of the instability of its protein aggregates that appear to make it less suitable as a calibration INP at these temperatures. For Argentinian soil dust particles, there was excellent agreement across all measurement methods; measures ranged within 1 order of magnitude for INP number concentrations, active fractions and calculated active site densities over a 25 to 30 ∘C range and 5 to 8 orders of corresponding magnitude change in number concentrations. This was also the case for all temperatures warmer than −25 ∘C in Tunisian dust experiments. In contrast, discrepancies in measurements of INP concentrations or active site densities that exceeded 2 orders of magnitude across a broad range of temperature measurements found at temperatures warmer than −25 ∘C in a previous study were replicated for illite NX. Discrepancies also exceeded 2 orders of magnitude at temperatures of −20 to −25 ∘C for potassium feldspar (K-feldspar), but these coincided with the range of temperatures at which INP concentrations increase rapidly at approximately an order of magnitude per 2 ∘C cooling for K-feldspar. These few discrepancies did not outweigh the overall positive outcomes of the workshop activity, nor the future utility of this data set or future similar efforts for resolving remaining measurement issues. Measurements of the same materials were repeatable over the time of the workshop and demonstrated strong consistency with prior studies, as reflected by agreement of data broadly with parameterizations of different specific or general (e.g., soil dust) aerosol types. The divergent measurements of the INP activity of illite NX by direct versus post-processing methods were not repeated for other particle types, and the Snomax® data demonstrated that, at least for a biological INP type, there is no expected measurement bias between bulk collection and direct immediately processed freezing methods to as warm as −10 ∘C. Since particle size ranges were limited for this workshop, it can be expected that for atmospheric populations of INPs, measurement discrepancies will appear due to the different capabilities of methods for sampling the full aerosol size distribution, or due to limitations on achieving sufficient water supersaturations to fully capture immersion freezing in direct processing instruments. Overall, this workshop presents an improved picture of present capabilities for measuring INPs than in past workshops, and provides direction toward addressing remaining measurement issues.

Sea spray is the largest aerosol source on Earth. Bubble bursting mechanisms at the ocean surface create smaller film burst and larger jet drop particles. This study quantified the effects of particle chemistry on the depositional ice nucleation efficiency of laboratory-generated sea spray aerosols under the cirrus-relevant conditions. Cultures of Prochlorococcus, the most abundant phytoplankton species in the global ocean, were used as a model source of organic sea spray aerosols. We showed that smaller particles generated from lysed Prochlorococcus cultures are organically enriched and nucleate more effectively than larger particles generated from the same cultures. We then quantified the ice nucleation efficiency of single component organic molecules that mimic Prochlorococcus proteins, lipids, and saccharides. Amylopectin, agarose, and aspartic acid exhibited similar critical ice saturations, fractional activations, and ice nucleation active site number densities to particles generated from Prochlorococcus cultures. These findings indicate that saccharides and proteins with numerous and well-ordered hydrophilic functional groups may determine the ice nucleation abilities of organic sea spray aerosols.

Oceanic oxygen deficient zones (ODZs) influence global biogeochemical cycles in a variety of ways, most notably by acting as a sink for fixed nitrogen (Codispoti et al. 2001). Optimum multiparameter analysis of data from two cruises in the Eastern Tropical North Pacific (ETNP) was implemented to develop a water mass analysis for the large ODZ in this region. This analysis reveals that the most pronounced oxygen deficient conditions are within the 13 C water (13CW) mass, which is distributed via subsurface mesoscale features such as eddies branching from the California Undercurrent. Nitrite accumulates within these eddies and slightly below the core of the 13CW. This water mass analysis also reveals that the 13CW and deeper Northern Equatorial Pacific Intermediate Water (NEPIW) act as the two Pacific Equatorial source waters to the California Current System. The Equatorial Subsurface Water and Subtropical Subsurface Water are synonymous with the 13CW and this study refers to this water mass as the 13CW based on its history. Since the 13CW has been found to dominate the most pronounced oxygen deficient conditions within the Eastern Tropical South Pacific ODZ and the Peru-Chile Undercurrent, the 13CW and the NEPIW define boundaries for oxygen minimum conditions across the entire eastern Pacific Ocean.

Abstract. This study investigates the measurement of ice nucleating particle (INP) concentrations and sizing of crystals using continuous flow diffusion chambers (CFDCs). CFDCs have been deployed for decades to measure the formation of INPs under controlled humidity and temperature conditions in laboratory studies and by ambient aerosol populations. These measurements have, in turn, been used to construct parameterizations for use in models by relating the formation of ice crystals to state variables such as temperature and humidity as well as aerosol particle properties such as composition and number. We show here that assumptions of ideal instrument behavior are not supported by measurements made with a commercially available CFDC, the SPectrometer for Ice Nucleation (SPIN), and the instrument on which it is based, the Zurich Ice Nucleation Chamber (ZINC). Non-ideal instrument behavior, which is likely inherent to varying degrees in all CFDCs, is caused by exposure of particles to different humidities and/or temperatures than predicated from instrument theory of operation. This can result in a systematic, and variable, underestimation of reported INP concentrations. We find here variable correction factors from 1.5 to 9.5, consistent with previous literature values. We use a machine learning approach to show that non-ideality is most likely due to small-scale flow features where the aerosols are combined with sheath flows. Machine learning is also used to minimize the uncertainty in measured INP concentrations. We suggest that detailed measurement, on an instrument-byinstrument basis, be performed to characterize this uncertainty.

Abstract. Soot and black carbon (BC) particles are generated in the incomplete combustion of fossil fuels, biomass, and biofuels. These airborne particles affect air quality, human health, aerosol–cloud interactions, precipitation formation, and climate. At present, the climate effects of BC particles are not well understood. Their role in cloud formation is obscured by their chemical and physical variability and by the internal mixing states of these particles with other compounds. Ice nucleation in field studies is often difficult to interpret. Nonetheless, most field studies seem to suggest that BC particles are not efficient ice-nucleating particles (INPs). On the other hand, laboratory measurements show that in some cases, BC particles can be highly active INPs under certain conditions. By working with well-characterized BC particles, our aim is to systematically establish the factors that govern the ice nucleation activity of BC. The current study focuses on laboratory measurements of the effectiveness of BC-containing aerosol in the formation of ice crystals in temperature and ice supersaturation conditions relevant to cirrus clouds. We examine ice nucleation on BC particles under water-subsaturated cirrus cloud conditions, commonly understood as deposition-mode ice nucleation. We study a series of well-characterized commercial carbon black particles with varying morphologies and surface chemistries as well as ethylene flame-generated combustion soot. The carbon black particles used in this study are proxies for atmospherically relevant BC aerosols. These samples were characterized by electron microscopy, mass spectrometry, and optical scattering measurements. Ice nucleation activity was systematically examined in temperature and saturation conditions in the ranges of 217≤T≤235 K and 1.0≤Sice≤1.5 and 0.59≤Swater≤0.98, respectively, using a SPectrometer for Ice Nuclei (SPIN) instrument, which is a continuous-flow diffusion chamber coupled with instrumentation to measure light scattering and polarization. To study the effect of coatings on INPs, the BC-containing particles were coated with organic acids found in the atmosphere, namely stearic acid, cis-pinonic acid, and oxalic acid. The results show significant variations in ice nucleation activity as a function of size, morphology, and surface chemistry of the BC particles. The measured ice nucleation activity dependencies on temperature, supersaturation conditions, and the physicochemical properties of the BC particles are consistent with an ice nucleation mechanism of pore condensation followed by freezing. Coatings and surface oxidation modify the initial formation efficiency of pristine ice crystals on BC-containing aerosol. Depending on the BC material and the coating, both inhibition and enhancement in INP activity were observed. Our measurements at low temperatures complement published data and highlight the capability of some BC particles to nucleate ice under low ice supersaturation conditions. These results are expected to help refine theories relating to soot INP activation in the atmosphere.

Atmospheric ice nucleating particles (INPs) influence global climate by altering cloud formation, lifetime, and precipitation efficiency. The role of secondary organic aerosol (SOA) material as a source of INPs in the ambient atmosphere has not been well defined. Here, we demonstrate the potential for biogenic SOA to activate as depositional INPs in the upper troposphere by combining field measurements with laboratory experiments. Ambient INPs were measured in a remote mountaintop location at –46 °C and an ice supersaturation of 30% with concentrations ranging from 0.1 to 70 L–1. Concentrations of depositional INPs were positively correlated with the mass fractions and loadings of isoprene-derived secondary organic aerosols. Compositional analysis of ice residuals showed that ambient particles with isoprene-derived SOA material can act as depositional ice nuclei. Laboratory experiments further demonstrated the ability of isoprene-derived SOA to nucleate ice under a range of atmospheric conditions. We further show that ambient concentrations of isoprene-derived SOA can be competitive with other INP sources. This demonstrates that isoprene and potentially other biogenically-derived SOA materials could influence cirrus formation and properties.

Nitrification, the oxidation of ammonium to nitrite and then nitrate, is often discounted as a source of nitrate in euphotic zone waters due to photoinhibition of nitrifying microorganisms and/or competition for ammonium with phytoplankton. However, there have also been counterarguments that nitrification represents a significant “regenerated” nitrate source to phytoplankton, augmenting the “new” nitrate supplied via physical processes. If nitrification is an appreciable nitrate source in the euphotic zone, then the assumption of a balance between nitrate uptake and organic matter export will overestimate export production. We investigated the relative importance of nitrification and nitrate uptake in the subarctic North Atlantic in late spring and late summer. The rates and vertical distributions of primary production, nitrogen uptake, and ammonium and nitrite oxidation were determined through isotope tracer experiments and the distributions of the nitrogen and oxygen isotopes of nitrate. In surface waters, ammonium and nitrite oxidation rates were low, representing an average of 5.2% and 2.5% of total euphotic zone nitrate uptake, respectively. The nitrogen and oxygen isotopes of nitrate confirmed that nitrification was not significant within the euphotic zone. Comparison of the rates of nitrogen uptake and primary production showed that while springtime phytoplankton growth could be fully supported by new nitrate and recycled ammonium, up to 50% of summertime productivity was likely fueled by dissolved organic nitrogen (DON). Uptake of DON implies that the fraction of primary production exported from surface waters in the late summer was significantly lower than the measured nitrate and ammonium uptake rates suggest.

Abstract. There is evidence that black carbon (BC) particles may affect cirrus formation and, hence, global climate by acting as potential ice nucleating particles (INPs) in the troposphere. Nevertheless, the ice nucleation (IN) ability of bare BC and BC coated with secondary organic aerosol (SOA) material remains uncertain. We have systematically examined the IN ability of 100–400 nm size-selected BC particles with different morphologies and different SOA coatings representative of anthropogenic (toluene and n-dodecane) and biogenic (β-caryophyllene) sources in the cirrus regime (−46 to −38 ∘C). Several BC proxies were selected to represent different particle morphologies and oxidation levels. Atmospheric aging was further replicated with the exposure of SOA-coated BC to OH. The results demonstrate that the 400 nm hydrophobic BC types nucleate ice only at or near the homogeneous freezing threshold. Ice formation at cirrus temperatures below homogeneous freezing thresholds, as opposed to purely homogeneous freezing, was observed to occur for some BC types between 100 and 200 nm within the investigated temperature range. More fractal BC particles did not consistently act as superior INPs over more spherical ones. SOA coating generated by oxidizing β-caryophyllene with O3 did not seem to affect BC IN ability, probably due to an SOA-phase state transition. However, SOA coatings generated from OH oxidation of various organic species did exhibit higher IN-onset supersaturation ratio with respect to ice (SSi), compared with bare BC particles, with the toluene-SOA coating showing an increase in SSi of 0.1–0.15 while still below the homogeneous freezing threshold. Slightly oxidized toluene SOA coating seemed to have a stronger deactivation effect on BC IN ability than highly oxidized toluene SOA, which might be caused by oligomer formation and the phase state transition of toluene SOA under different oxidation levels. n-dodecane and β-caryophyllene-derived SOA-coated BC only froze in the homogeneous regime. We attribute the inhibition of IN ability to the filling of the pores on the BC surface by the SOA material coating. OH exposure levels of n-dodecane and β-caryophyllene SOA coating experiments, from an equivalent atmospheric exposure time from 10 to 90 d, did not render significant differences in the IN potential. Our study of selected BC types and sizes suggests that increases in diameter, compactness, and/or surface oxidation of BC particles lead to more efficient IN via the pore condensation freezing (PCF) pathway, and that coatings of common SOA materials can inhibit the formation of ice.