Bioaerosols and atmospheric ice nuclei in a Mediterranean dryland: community changes related to rainfall

Certain biological particles are highly efficient ice nuclei (IN), but the actual contribution of bioparticles to the pool of atmospheric IN and their relation to precipitation are not well characterized. We investigated the composition of bioaerosols, ice nucleation activity, and the effect of rainfall by metagenomic sequencing and freezing experiments of aerosol samples collected during the INUIT 2016 campaign in a rural dryland on the eastern Mediterranean island of Cyprus. Taxonomic analysis showed community changes related to rainfall. For the rain-affected samples, we found higher read proportions of fungi, particularly of Agaricomycetes, which are a class of fungi that actively discharge their spores into the atmosphere in response to humidity changes. In contrast, the read proportions of bacteria were reduced, indicating an effective removal of bacteria by precipitation. Freezing experiments showed that the IN population in the investigated samples was influenced by both rainfall and dust events. For example, filtration and heat treatment of the samples collected during and immediately after rainfall yielded enhanced fractions of heat-sensitive IN in the size ranges larger than 5 µm and smaller than 0.1 µm, which were likely of biological origin (entire bioparticles and soluble macromolecular bio-IN). In contrast, samples collected in periods with dust events were dominated by heat-resistant IN active at lower temperatures, most likely mineral dust. The DNA analysis revealed low numbers of reads related to microorganisms that are known to be IN-active. This may reflect unknown sources of atmospheric bio-IN as well as the presence of cell-free IN macromolecules that do not contain DNA, in particular for sizes < 0.1 µm. The observed effects of rainfall on the composition of atmospheric bioaerosols and IN may influence the hydrological cycle (bioprecipitation cycle) as well as the health effects of air particulate matter (pathogens, allergens).

The effect of (NH₄)₂SO₄ on the freezing properties of non-mineral dust ice-nucleating substances of atmospheric relevance

A wide range of materials including mineral dust, soil dust, and bioaerosols have been shown to act as ice nuclei in the atmosphere. During atmospheric transport, these materials can become coated with inorganic and organic solutes which may impact their ability to nucleate ice. While a number of studies have investigated the impact of solutes at low concentrations on ice nucleation by mineral dusts, very few studies have examined their impact on non-mineral dust ice nuclei. We studied the effect of dilute (NH4)2SO4 solutions (0.05 M) on immersion freezing of a variety of non-mineral dust ice-nucleating substances (INSs) including bacteria, fungi, sea ice diatom exudates, sea surface microlayer substances, and humic substances using the droplet-freezing technique. We also studied the effect of (NH4)2SO4 solutions (0.05 M) on the immersion freezing of several types of mineral dust particles for comparison purposes. (NH4)2SO4 had no effect on the median freezing temperature (ΔT50) of 9 of the 10 non-mineral dust materials tested. There was a small but statistically significant decrease in ΔT50 (−0.43 ± 0.19 ∘C) for the bacteria Xanthomonas campestris in the presence of (NH4)2SO4 compared to pure water. Conversely, (NH4)2SO4 increased the median freezing temperature of four different mineral dusts (potassium-rich feldspar, Arizona Test Dust, kaolinite, montmorillonite) by 3 to 9 ∘C and increased the ice nucleation active site density per gram of material (nm(T)) by a factor of ∼ 10 to ∼ 30. This significant difference in the response of mineral dust and non-mineral dust ice-nucleating substances when exposed to (NH4)2SO4 suggests that they nucleate ice and/or interact with (NH4)2SO4 via different mechanisms. This difference suggests that the relative importance of mineral dust to non-mineral dust particles for ice nucleation in mixed-phase clouds could potentially increase as these particles become coated with (NH4)2SO4 in the atmosphere. This difference also suggests that the addition of (NH4)2SO4 (0.05 M) to atmospheric samples of unknown composition could potentially be used as an indicator or assay for the presence of mineral dust ice nuclei, although additional studies are still needed as a function of INS concentration to confirm the same trends are observed for different INS concentrations than those used here. A comparison with results in the literature does suggest that our results may be applicable to a range of mineral dust and non-mineral dust INS concentrations.

A novel view on the mechanism of biological activity of antifreeze proteins

The adaptation of organisms to sub-zero temperatures is an intriguing problem in biology and biotechnology. The ice-binding antifreeze proteins are known to be responsible for the adaptation, but the mechanism of their action is still far from being clear. Here we show that: (i) in contrast to common belief, ice-binding proteins do not reduce the water freezing temperature and even raise the ice melting point; (ii) at sub-zero temperatures (to −30°C), ice can be formed only on ice-binding surfaces, but, for kinetic reasons, not in bulk water; (iii) living cells have some large surfaces, which can bind the antifreeze proteins. These facts allow suggesting that the task of antifreeze proteins is not to bind to the ice crystals already formed in the cell and stop their growth or rearrangement, but to bind to those cell surfaces where the ice nuclei can form, and thus to prevent ice formation completely.

Effect of Graphene on Ice Polymorph

Recently, ice with stacking disorder structure, consisting of random sequences of cubic ice (Ic) and hexagonal ice (Ih) layers, was reported to be more stable than pure Ih/Ic. Due to a much lower free energy barrier of heterogeneous nucleation, in practice, the freezing process of water is controlled by heterogeneous nucleation triggered by an external medium. Therefore, we carry out molecular dynamic simulations to explore how ice polymorphism depends on the lattice structure of the crystalline substrates on which the ice is grown, focusing on the primary source of atmospheric aerosols, carbon materials. It turns out that, during the nucleation stage, the polymorph of ice nuclei is strongly affected by graphene substrates. For ice nucleation on graphene, we find Ih is the dominant polymorph. This can be attributed to structural similarities between graphene and basal face of Ih. Our results also suggest that the substrate only affects the polymorph of ice close to the graphene surface, with the preference for Ih diminishing as the ice layer grows.

Bioaerosols and atmospheric ice nuclei in a Mediterranean dryland: Community changes related to rainfall

Certain biological particles are highly efficient ice nuclei (IN), but the actual contribution of bioparticles to the pool of atmospheric IN and their relation to precipitation are not well characterized. We investigated the composition of bioaerosols, ice nucleation activity, and the effect of rainfall by metagenomic sequencing and freezing experiments of aerosol samples collected during the INUIT 2016 campaign in a rural dryland on the Eastern Mediterranean island Cyprus. Taxonomic analysis showed community changes related to rainfall. For the rain-affected samples, we found higher read proportions of fungi, in particular of Agaricomycetes, which are a class of fungi actively discharging their spores into the atmosphere in response to humidity changes. In contrast, the read proportions of bacteria were reduced, indicating an effective removal of bacteria by precipitation. Freezing experiments showed that the IN population in the investigated samples was influenced by both rainfall and dust events. For example, filtration and heat treatment of the samples collected during and immediately after rainfall yielded enhanced fractions of heat-sensitive IN in the size ranges larger than 5 μm and smaller than 0.1 μm, which were likely of biological origin (entire bioparticles and soluble macromolecular bio-IN). In contrast, samples collected in periods with dust events were dominated by heat-resistant IN active at lower temperatures, most likely mineral dust. The DNA analysis revealed low numbers of reads related to microorganisms that are known to be IN-active. This may reflect unknown sources of atmospheric bio-IN as well as the presence of cell-free IN macromolecules that do not contain DNA, in particular for sizes < 0.1 μm. The observed effects of rainfall on the composition of atmospheric bioaerosols and IN may influence the hydrological cycle (bioprecipitation cycle) as well as the health effects of air particulate matter (pathogens, allergens).

Estimating the potential cooling effect of cirrus thinning achieved via the seeding approach

Cirrus thinning is a newly emerging geoengineering approach to mitigate global warming. To sufficiently exploit the potential cooling effect of cirrus thinning with the seeding approach, a flexible seeding method is used to calculate the optimal seeding number concentration, which is just enough to prevent homogeneous ice nucleation from occurring. A simulation using the Community Atmosphere Model version 5 (CAM5) with the flexible seeding method shows a global cooling effect of -1.36±0.18 W m−2, which is approximately two-thirds of that from artificially turning off homogeneous nucleation (-1.98±0.26 W m−2). However, simulations with fixed seeding ice nuclei particle number concentrations of 20 and 200 L−1 show a weak cooling effect of -0.27±0.26 W m−2 and warming effect of 0.35±0.28 W m−2, respectively. Further analysis shows that cirrus seeding leads to a significant warming effect of liquid and mixed-phase clouds, which counteracts the cooling effect of cirrus clouds. This counteraction is more prominent at low latitudes and leads to a pronounced net warming effect over some low-latitude regions. The sensitivity experiment shows that cirrus seeding carried out at latitudes with solar noon zenith angles greater than 12∘ could yield a stronger global cooling effect of −2.00 ± 0.25 W m−2. Overall, the potential cooling effect of cirrus thinning is considerable, and the flexible seeding method is essential.

Desert dust interactions with the atmospheric environment

Κατά τη διάρκεια των τελευταίων δεκαετιών, η επίδραση των αιωρούμενων σωματιδίων στο κλίμα και στον καιρό έχουν μελετηθεί μέσα από πλήθος εργασιών της διεθνούς επιστημονικής κοινότητας. Η αλληλεπίδραση των αιωρούμενων σωματιδίων με το ατμοσφαιρικό περιβάλλον σχετίζεται άμεσα με πλήθος μηχανισμών μέσα στην ατμόσφαιρα, οι οποίοι καθιστούν την πρόγνωση του καιρού και τις κλιματικές προσομοιώσεις ιδιαίτερα πολύπλοκες. Πιο συγκεκριμένα, τα αιωρούμενα σωματίδια μεταβάλλουν άμεσα το ισοζύγιο της ακτινοβολίας στην ατμόσφαιρα (direct effect), επιδρούν στο βιοχημικό κύκλο των θαλάσσιων και χερσαίων οικοσυστημάτων και επηρεάζουν την ανθρώπινη υγεία. Επιπλέον, επηρεάζουν τον υδρολογικό κύκλο το σχηματισμό των νεφών (indirect effect) και την κατανομή του υετού.Σκοπός της παρούσας διδακτορικής διατριβής είναι η μελέτη της έμμεσης επίδρασης των σωματιδίων της ερημικής σκόνης στο σχηματισμό των νεφών και του υετού, μέσω του πλήρως συζευγμένου μετεωρολογικού – χημικού μοντέλου Weather Research and Forecasting/Chemistry (WRF/Chem). Ως πρώτο βήμα, αξιολογήθηκαν τα τρία σχήματα εκπομπής σκόνης του πακέτου Goddard Global Ozone Chemistry Aerosol Radiation and Transport – GOCART μέσω μιας μελέτης περίπτωσης αμμοθύελλας που εκδηλώθηκε στην περιοχή της Μεσογείου. Το συγκεκριμένο φαινόμενο σχετίζεται με σημαντικές συνθήκες αστάθειας και αγεωστροφικότητας στις περιοχές που θεωρούνται πηγές σκόνης. Πάνω από τις συγκεκριμένες περιοχές παρατηρήθηκε σύγκλιση του πολικού (Polar Jetstream – PJ) και υποτροπικού αεροχειμάρρου (Subtropical Jetstream – STJ), αλλά και αναδίπλωση της τροπόσφαιρας. Τα σχήματα σκόνης τα οποία αξιολογήθηκαν είναι το πρωτότυπο GOCART, το ανανεωμένο GOCART – AFWA από την υπηρεσία καιρού της πολεμικής αεροπορίας των Ηνωμένων Πολιτειών (Air Force Weather Agency - AFWA) και το ανανεωμένο GOCART – UoC από το Πανεπιστήμιο της Κολωνίας (University of Cologne – UoC). Η απόκριση των παραπάνω σχημάτων στα παραπάνω φαινόμενα αξιολογήθηκε μέσω σύγκρισης των αποτελεσμάτων των προσομοιώσεων. To GOCART – AFWA παρουσίασε τους καλύτερους στατιστικούς δείκτες ενώ είχε και την πιο ικανοποιητική χωροχρονική απεικόνιση των συγκεντρώσεων της μεταφερόμενης σκόνης. Επομένως, το GOCART – AFWA είναι και το σχήμα που χρησιμοποιήθηκε περαιτέρω στην εξέλιξη της παρούσας διδακτορικής διατριβής. Επιπλέον, η μελέτη των μηχανισμών της υγρής εναπόθεσης κυρίως μέσα στην περιοχή των νεφών αποτέλεσε ένα επιπλέον προπαρασκευαστικό βήμα. Το GOCART – AFWA στην πρωτότυπή του μορφή δεν υποστηρίζει κάποιο σχήμα υγρής εναπόθεσης. Επομένως το σχήμα υγρής εναπόθεσης των Seinfeld & Pandis (1998), εισήχθη στο εν λόγω σχήμα, για την περιοχή εντός του νέφους όσο και για την περιοχή κάτω από αυτό. Η υγρή εναπόθεση εντός του νέφους έχει ιδιαίτερη σημασία και λαμβάνει χώρα σε ύψη από 3.5 km και πάνω όπου κυρίως σάρωση των μικρότερων σωματιδίων πραγματοποιείται. Η εισαγωγή ενός σχήματος υγρής εναπόθεσης έχει ιδιαίτερη σημασία κυρίως για την περιοχή εντός του νέφους, αφού τροποποιεί σημαντικά τη συγκέντρωση των σωματιδίων σκόνης που θα δράσουν σαν επιπλέον πυρήνες συμπύκνωσης (Cloud Condensation Nuclei – CCN) στην εν λόγω περιοχή. Η σύγκριση των αποτελεσμάτων των προσομοιώσεων με δεδομένα παρατηρήσεων έδειξαν ότι το παραπάνω σχήμα υγρής εναπόθεσης βελτιώνει τη γενικότερη προγνωστική ικανότητα του μοντέλου καθώς περιορίζεται η υπερεκτίμηση στον υπολογισμό των συγκεντρώσεων σκόνης. Η επίδραση των σωματιδίων της σκόνης που δρουν ως πυρήνες συμπύκνωσης (Cloud Condensation Nuclei – CCN) μελετήθηκε μέσω της εισαγωγής του σχήματος πυρηνοποίησης των Fountoukis & Nenes (2005) σε ένα double moment σχήμα μικροφυσικής του WRF/Chem. Ομοίως με τους μηχανισμούς υγρής εναπόθεσης, το GOCART – AFWA δεν υποστηρίζει κάποιο σχήμα πυρηνοποίησης των προσομοιωμένων σωματιδίων σκόνης. Αντ’ αυτού, μια σταθερή αρχική συγκέντρωση CCN χρησιμοποιείται για την περαιτέρω χωροχρονική των CCN. Επιπλέον, η επίδραση των προσομοιωμένων CCN μέσω του σχήματος Fountoukis & Nenes (2005) σε μηχανισμούς ανωμεταφοράς (convection) έχει επίσης ληφθεί υπόψιν. Η παραπάνω επίδραση έχει εξεταστεί ακόμα και σε χωρικές αναλύσεις που ανήκουν στη λεγόμενη «γκρίζα ζώνη» (6 – 10 km). Σε ό,τι αφορά στην ανωτέρω «γκρίζα ζώνη», υπάρχει μια διχογνωμία στη διεθνή επιστημονική κοινότητα για το αν οι μηχανισμοί ανωμεταφοράς θα πρέπει να είναι ενεργοποιημένοι, καθώς υπάρχουν νεότερες μελέτες οι στις οποίες οι παραπάνω μηχανισμοί λαμβάνονται υπόψιν. Ωστόσο, δεν έχει συμπεριληφθεί μέχρι στιγμής η επίδραση των CCN που υπολογίζονται με δυναμικό τρόπο στους παραπάνω μηχανισμούς. Συγκρίσεις των προϊόντων του μοντέλου με παρατηρήσεις έδειξαν ότι η προγνωστική ικανότητα του μοντέλου σχετικά με την κατανομή του υετού βελτιώνεται σημαντικά. Αξιοσημείωτη είναι η θετική επίδραση του παραπάνω σχήματος πυρηνοποίησης ακόμα και ημέρες μετά την εκδήλωση της μεταφοράς σκόνης όπου η βροχόπτωση εμφανίζεται ενισχυμένη. Ενίσχυση βροχόπτωσης παρατηρείται και σε περιοχές μακριά από την εκδήλωση των φαινομένων σκόνης. Αντιθέτως, η βροχόπτωση περιορίζεται σε περιοχές και χρονικές περιόδους που δεν απέχουν σημαντικά από τα φαινόμενα μεταφοράς σκόνης. Επιπλέον, παρόλο που στη συγκεκριμένη διατριβή τα σωματίδια σκόνης δεν συμμετέχουν σε παραμετροποιήσεις πυρήνων πάγου (ice nuclei – IN), το εν λόγω σχήμα πυρηνοποίησης συμβάλλει σε μια ικανοποιητική απόκριση μεταξύ αναλογίας μείγματος νεφοσταγόνων και πάγου. Επιπλέον, σε ό,τι αφορά στις οπτικές ιδιότητες των σωματιδίων σκόνης, το σχήμα πυρηνοποίησης περιορίζει συστηματικά και μέσα τεταραγωνικά σφάλματα. Τέλος, οι συγκρίσεις των συγκεντρώσεων των CCN με μετρήσεις, έδειξαν ικανοποιητικότερους συντελεστές συσχέτισης μετά την εισαγωγή του σχήματος πυρηνοποίησης.

Development of the drop Freezing Ice Nuclei Counter (FINC), intercomparison of droplet freezing techniques, and use of soluble lignin as an atmospheric ice nucleation standard

Aerosol–cloud interactions, including the ice nucleation of supercooled liquid water droplets caused by ice-nucleating particles (INPs) and macromolecules (INMs), are a source of uncertainty in predicting future climate. Because INPs and INMs have spatial and temporal heterogeneity in source, number, and composition, predicting their concentration and distribution is a challenge requiring apt analytical instrumentation. Here, we present the development of our drop Freezing Ice Nuclei Counter (FINC) for the estimation of INP and INM concentrations in the immersion freezing mode. FINC's design builds upon previous droplet freezing techniques (DFTs) and uses an ethanol bath to cool sample aliquots while detecting freezing using a camera. Specifically, FINC uses 288 sample wells of 5–60 µL volume, has a limit of detection of −25.4 ± 0.2 ∘C with 5 µL, and has an instrument temperature uncertainty of ± 0.5 ∘C. We further conducted freezing control experiments to quantify the nonhomogeneous behavior of our developed DFT, including the consideration of eight different sources of contamination. As part of the validation of FINC, an intercomparison campaign was conducted using an NX-illite suspension and an ambient aerosol sample from two other drop freezing instruments: ETH's DRoplet Ice Nuclei Counter Zurich (DRINCZ) and the University of Basel's LED-based Ice Nucleation Detection Apparatus (LINDA). We also tabulated an exhaustive list of peer-reviewed DFTs, to which we added our characterized and validated FINC. In addition, we propose herein the use of a water-soluble biopolymer, lignin, as a suitable ice-nucleating standard. An ideal INM standard should be inexpensive, accessible, reproducible, unaffected by sample preparation, and consistent across techniques. First, we compared lignin's freezing temperature across different drop freezing instruments, including on DRINCZ and LINDA, and then determined an empirical fit parameter for future drop freezing validations. Subsequently, we showed that commercial lignin has consistent ice-nucleating activity across product batches and demonstrated that the ice-nucleating ability of aqueous lignin solutions is stable over time. With these findings, we present lignin as a good immersion freezing standard for future DFT intercomparisons in the research field of atmospheric ice nucleation.

Studying the Bulk and Contour Ice Nucleation of Water Droplets via Quartz Crystal Microbalances

Due to the stochastic and time-dependent character of the ice embryo formation and growth (i.e., a process that can be analyzed statistically, but cannot be predicted precisely), the heterogeneous ice nucleation on atmospheric aerosols or macroscopic solid surfaces is still shrouded in mystery, regardless of the extremely active research and exponential progress within this scientific field. For instance, whether the icing appears from outside-in or inside-out is a subject of intense controversy, with practicability in designing passive icephobic coatings or improving the effectiveness of the cryopreservation technologies. Here, we propose an artful technique for quantitative analysis of the different modes of water freezing using super-nonwettable soot-coated quartz crystal microbalances (QCMs). To achieve this goal, a set of 5 MHz QCMs are loaded one at a time with a 50 μL droplet, whose bulk or contour solidification is detected in real-time. The obtained experimental results show that our sensor devices recognize explicitly if the ice nuclei form predominantly at the liquid–solid interface or spread along the droplet’s entire outer shell by triggering individual reproducible responses in terms of the direction of signal evolution in time. Our results may serve as a foundation for the future incorporation of QCM devices in different freezing assays, where gaining information about the ice adhesion forces and ice layer’s thickness is mandatory.