Laboratory and field studies of ice-nucleating particles from open-lot livestock facilities in Texas

In this work, an abundance of ice-nucleating particles (INPs) from livestock facilities was studied through laboratory measurements from cloud-simulation chamber experiments and field investigation in the Texas Panhandle. Surface materials from two livestock facilities, one in the Texas Panhandle and another from McGregor, Texas, were selected as dust proxies for laboratory analyses. These two samples possessed different chemical and biological properties. A combination of aerosol interaction and dynamics in the atmosphere (AIDA) measurements and offline ice spectrometry was used to assess the immersion freezing mode ice nucleation ability and efficiency of these proxy samples at temperatures above −29 ∘C. A dynamic filter processing chamber was also used to complement the freezing efficiencies of submicron and supermicron particles collected from the AIDA chamber. For the field survey, periodic ambient particle sampling took place at four commercial livestock facilities from July 2017 to July 2019. INP concentrations of collected particles were measured using an offline freezing test system, and the data were acquired for temperatures between −5 and −25 ∘C. Our AIDA laboratory results showed that the freezing spectra of two livestock dust proxies exhibited higher freezing efficiency than previously studied soil dust samples at temperatures below −25 ∘C. Despite their differences in composition, the freezing efficiencies of both proxy livestock dust samples were comparable to each other. Our dynamic filter processing chamber results showed on average approximately 50 % supermicron size dominance in the INPs of both dust proxies. Thus, our laboratory findings suggest the importance of particle size in immersion freezing for these samples and that the size might be a more important factor for immersion freezing of livestock dust than the composition. From a 3-year field survey, we measured a high concentration of ambient INPs of 1171.6 ± 691.6 L−1 (average ± standard error) at −25 ∘C for aerosol particles collected at the downwind edges of livestock facilities. An obvious seasonal variation in INP concentration, peaking in summer, was observed, with the maximum at the same temperature exceeding 10 000 L−1 on 23 July 2018. The observed high INP concentrations suggest that a livestock facility is a substantial source of INPs. The INP concentration values from our field survey showed a strong correlation with measured particulate matter mass concentration, which supports the importance of size in ice nucleation of particles from livestock facilities.</p

The Ny-Ålesund Aerosol Cloud Experiment (NASCENT): Overview and First Results

The Arctic is warming at more than twice the rate of the global average. This warming is influenced by clouds, which modulate the solar and terrestrial radiative fluxes and, thus, determine the surface energy budget. However, the interactions among clouds, aerosols, and radiative fluxes in the Arctic are still poorly understood. To address these uncertainties, the Ny-Ålesund Aerosol Cloud Experiment (NASCENT) study was conducted from September 2019 to August 2020 in Ny-Ålesund, Svalbard. The campaign’s primary goal was to elucidate the life cycle of aerosols in the Arctic and to determine how they modulate cloud properties throughout the year. In situ and remote sensing observations were taken on the ground at sea level, at a mountaintop station, and with a tethered balloon system. An overview of the meteorological and the main aerosol seasonality encountered during the NASCENT year is introduced, followed by a presentation of first scientific highlights. In particular, we present new findings on aerosol physicochemical and molecular properties. Further, the role of cloud droplet activation and ice crystal nucleation in the formation and persistence of mixed-phase clouds, and the occurrence of secondary ice processes, are discussed and compared to the representation of cloud processes within the regional Weather Research and Forecasting Model. The paper concludes with research questions that are to be addressed in upcoming NASCENT publications

A comprehensive characterization of ice nucleation by three different types of cellulose particles immersed in water

We present the laboratory results of immersion freezing efficiencies of cellulose particles at supercooled temperature (T) conditions. Three types of chemically homogeneous cellulose samples are used as surrogates that represent supermicron and submicron ice-nucleating plant structural polymers. These samples include microcrystalline cellulose (MCC), fibrous cellulose (FC) and nanocrystalline cellulose (NCC). Our immersion freezing dataset includes data from various ice nucleation measurement techniques available at 17 different institutions, including nine dry dispersion and 11 aqueous suspension techniques. With a total of 20 methods, we performed systematic accuracy and precision analysis of measurements from all 20 measurement techniques by evaluating T-binned (1 ∘C) data over a wide T range (−36 ∘C <T<−4 ∘C). Specifically, we intercompared the geometric surface area-based ice nucleation active surface site (INAS) density data derived from our measurements as a function of T, ns,geo(T). Additionally, we also compared the ns,geo(T) values and the freezing spectral slope parameter (Δlog(ns,geo)/ΔT) from our measurements to previous literature results. Results show all three cellulose materials are reasonably ice active. The freezing efficiencies of NCC samples agree reasonably well, whereas the diversity for the other two samples spans ≈ 10 ∘C. Despite given uncertainties within each instrument technique, the overall trend of the ns,geo(T) spectrum traced by the T-binned average of measurements suggests that predominantly supermicron-sized cellulose particles (MCC and FC) generally act as more efficient ice-nucleating particles (INPs) than NCC with about 1 order of magnitude higher ns,geo(T)

The Fifth International Workshop on Ice Nucleation phase 2 (FIN-02): laboratory intercomparison of ice nucleation measurements

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

Unexpected formation of a copper(II) 12-metallacrown-4 with (S)-glutamic-g-hydroxamic acid: a thermodynamic and spectroscopic study in aqueous solution

The equilibria of copper(II) with (S)-glutamic-gamma-hydroxamic acid (H2L) were investigated in aqueous solution by different techniques: glass electrode potentiometry; calorimetry; VIS and CD spectrophotometry; and ES-MS. An unexpected pentacopper(II) 12-metallacrown-4 [Cu5L4H-4](2-) was detected, analogous to those well known formed by alpha- and beta-aminohydroxamic acids, but of lower stability Another five species were found: [CuLH](+); [CuL2H2]; [Cu2L2]; [CuL2H](-); and [CuL2](2-). Their structures are proposed based on both spectroscopic and calorimetric data

Copper Binding to the Neurotoxic Peptide PrP106-126. Thermodynamic and Structural Studies

The human prion protein fragment PrP106-126 is a highly fibrillogenic peptide, resistant to proteinases and toxic to neurons; it derives from the normal prion protein (PrPC), with which it can interact, thus inhibiting its superoxide dismutase-like activity. The same properties are also shown by the abnormal isoform of the prion protein (PrPSc), and this similarity makes PrP106-126 an interesting model for the neurotoxic action of PrPSc. A role for copper in PrP106-126 aggregation and toxicity has recently been evidenced, and the interaction of terminal Lys, His and Met residues with the copper ion at neutral pH has been suggested. In order to shed more light on the the complex-formation equilibria of PrP106-126 with the copper ion, a thorough investigation has been carried out by means of several experimental techniques: potentiometry, solution calorimetry, VIS spectrophotometry, circular dichroism, EPR and NMR spectroscopy. A shorter and more soluble fragment-PrP106-113, which lacks the hydrophobic C-terminal domain of PrP106-126 but contains all the potential donor groups-has also been considered for the sake of comparison. The involvement of terminal amino, imidazolic and amido nitrogens in complex formation has been confirmed, while no evidence was found for the interaction of side chains of Met and Lys residues with the copper ion. Solution structures for the main complexes are suggested

Copper Binding to the Neurotoxic Peptide PrP106-126. Thermodynamic and structural studies

The human prion protein fragment PrP106-126 is a highly fibrillogenic peptide, resistant to proteinases and toxicto neurons; it derives from the normal prion protein (PrPC), with which it can interact, thus inhibiting its superoxide dismutase-like activity. The same properties are also shown by the abnormal isoform of the prion protein (PrPSc), and this similarity makes PrP106-126 an interesting model for the neurotoxicac tion of PrPSc. A role for copper in PrP106-126 aggregation and toxicity has recently been evidenced, and the interaction of terminal Lys, His and Met residues with the copper ion at neutral pH has been suggested. In order to shed more light on the complex-formation equilibria of PrP106-126 with the copper ion, a thorough investigation has been carried out by means of several experimental techniques: potentiometry, solution calorimetry, VIS spectrophotometry, circular dichroism, EPR and NMR spectroscopy. A shorter and more soluble fragment –PrP106-113 , which lacks the hydrophobic C-terminal domain of PrP106-126 but contains all the potential donor groups–has also been considered for the sake of comparison. The involvement of terminal amino, imidazolicand amido nitrogens in complex formation has been confirmed, while no evidence was found for the interaction of side chains of Met and Lys residues with the copper ion