Contribution of fungi to primary biogenic aerosols in the atmosphere: wet and dry discharged spores, carbohydrates, and inorganic ions

Biogenic aerosols play important roles in atmospheric chemistry physics, the biosphere, climate, and public health. Here, we show that fungi which actively discharge their spores with liquids into the air, in particular actively wet spore discharging Ascomycota (AAM) and actively wet spore discharging Basidiomycota (ABM), are a major source of primary biogenic aerosol particles and components. We present the first estimates for the global average emission rates of fungal spores.

Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the spores of AAM and ABM may account for a large proportion of coarse particulate matter in tropical rainforest regions during the wet season (0.7–2.3 μg m⁻³). For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively wet discharged basidiospores (ABS). ABM emissions seem to account for most of the atmospheric abundance of mannitol (10–68 ng m⁻³), and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter (7–49 ng m⁻³), but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season (17–43 ng m⁻³), and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations.

Based on the average abundance of mannitol reported for extratropical continental boundary layer air (~25 ng m⁻³), we have also calculated a value of ~17 Tg yr⁻¹ as a first estimate for the global average emission rate of ABS over land surfaces, which is consistent with the typically observed concentrations of ABS (~10³–10⁴ m⁻³; ~0.1^–1 μg m⁻³). The global average atmospheric abundance and emission rate of total fungal spores, including wet and dry discharged species, are estimated to be higher by a factor of about three, i.e. 1 μg m⁻³ and ~50 Tg yr⁻¹. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr⁻¹ of anthropogenic primary organic aerosol; 12–70 Tg yr⁻¹ of secondary organic aerosol) indicate that emissions from fungi should be taken into account as a significant global source of organic aerosol. The effects of fungal spores and related chemical components might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10⁻⁴ to 10⁻³ S cm⁻¹ at room temperature. Gelation was found to cause little change in the ⁷Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids.

A new Lewis-base ionic liquid comprising a mono-charged diamine structure : a highly stable electrolyte for lithium electrochemistry

A new Lewis-base ionic liquid (IL) based on mono-charged 1,4-diazabicyclo[2.2.2]octane (dabco) was synthesized and its thermal and electrochemical behaviour was characterized. The dabco-based IL with bis(trifluoromethanesulfonyl)amide (TFSA) anion melts at 76 °C when the N-substituted alkyl chain length is 2. The dabco-based IL showed a wide electrochemical window of over 4 V ranging from −3.5 to +1.5 V vs. Fc/Fc⁺ and was able to deposit and strip lithium from a nickel substrate at reasonable efficiency.

Release of allergens in respirable aerosols : a link between grass pollen and asthma

Background: Asthma incidence has long been linked to pollen, even though pollen grains are too large to penetrate into the airways where asthmatic responses originate. Pollen allergens found in small, respirable particles have been implicated in a number of asthma epidemics, particularly ones following rainfall or thunderstorms.

Objective: The aim of this study was to determine how pollen allergens form the respirable aerosols necessary for triggering asthma.

Methods: Flowering grasses were humidified and then dried in a controlled-environment chamber connected to a cascade impactor and an aerosol particle counter. Particles shed from the flowers were analyzed with high-resolution microscopy and immunolabeled with rabbit anti-Phl p 1 antibody, which is specific for group 1 pollen allergens.

Results: Contrary to what has been reported in other published accounts, most of the pollen in this investigation remained on the open anthers of wind pollinated plants unless disturbed—eg, by wind. Increasing humidity caused anthers to close. After a cycle of wetting and drying followed by wind disturbance, grasses flowering within a chamber produced an aerosol of particles that were collected in a cascade impactor. These particles consisted of fragmented pollen cytoplasm in the size range 0.12 to 4.67 μm; they were loaded with group 1 allergens.

Conclusion: Here we provide the first direct observations of the release of grass pollen allergens as respirable aerosols. They can emanate directly from the flower after a moisture-drying cycle. This could explain asthmatic responses associated with grass pollination, particularly after moist weather conditions.

Birch pollen rupture and the release of aerosols of respirable allergens

Backgound Birch pollen allergens have been implicated as asthma triggers; however, pollen grains are too large to reach the lower airways where asthmatic reactions occur. Respirable-sized particles containing birch pollen allergens have been detected in air filters, especially after rainfall but the source of these particles has remained speculative.

Objective To determine the processes by which birch pollen allergens become airborne particles of respirable size with the potential to contribute to airways inflammation.

Methods Branches with attached male catkins were harvested and placed in a controlled emission chamber. Filtered dry air was passed through the chamber until the anthers opened, then they were humidified for 5 h and air-dried again. Flowers were disturbed by wind generated from a small electric fan. Released particles were counted, measured and collected for immuno-labelling and high-resolution microscopy.

Results Birch pollen remains on the dehisced anther and can rupture in high humidity and moisture. Fresh pollen takes as long as 3 h to rupture in water. Drying winds released an aerosol of particles from catkins. These were fragments of pollen cytoplasm that ranged in size from 30 nm to 4 μm and contained Bet v 1 allergens.

Conclusion When highly allergenic birch trees are flowering and exposed to moisture followed by drying winds they can produce particulate aerosols containing pollen allergens. These particles are small enough to deposit in the peripheral airways and have the potential to induce an inflammatory response.

Contribution of fungi to primary biogenic aerosols in the atmosphere : active discharge of spores, carbohydrates, and inorganic ions by Asco- and Basidiomycota

Spores and related chemical compounds from actively spore-discharging Ascomycota (AAM) and actively spore-discharging Basidiomycota (ABM) are primary biogenic components of air particulate matter (characteristic size range 1–10 μm). Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the forcible discharge of fungal spores may account for a large proportion of coarse air particulate matter in tropical rainforest regions during the wet season. For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol, mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively discharged basidiospores (ABS), and that the literature-derived emission ratio of about 5 pg per ABS may be taken as a representative average. ABM emissions may account for most of the atmospheric abundance of mannitol, and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter, but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season, and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations.

Based on the average abundance of mannitol in particulate matter, which is consistent with the above emission ratio and the observed abundance of ABS, we have also calculated a value of ~17 Tg yr−1 as a first estimate for the global average emission rate of ABS over land surfaces. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr−1 of anthropogenic primary organic aerosol; 12–70 Tg yr−1 of secondary organic aerosol) indicate that emissions from actively spore-discharging fungi should be taken into account as a significant source of organic aerosol. Their effects might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

Measurement of aqueous film thickness between charged mercury and mica surfaces : a direct experimental probe of the Poisson-Boltzmann distribution

A stable aqueous electrolyte film is formed between a mercury drop and a flat mica surface due to electrical double-layer repulsion when a negative potential is applied to the mercury. Film thickness has been measured as a function of applied potential while keeping the film pressure constant. By making measurements in this way, it is possible to map the data directly according to the Poisson-Boltzmann equation. An excellent fit to the data is obtained, providing direct evidence for this classical equation and its use as the basis of the Gouy-Chapman model of the diffuse double layer in electrolyte solutions.

Binding affinities of amino acid analogues at the charged aqueous titania interface : implications for titania-binding peptides

Despite the extensive utilization of biomolecule-titania interfaces, biomolecular recognition and interactions at the aqueous titania interface remain far from being fully understood. Here, atomistic molecular dynamics simulations, in partnership with metadynamics, are used to calculate the free energy of adsorption of different amino acid side chain analogues at the negatively-charged aqueous rutile TiO2 (110) interface, under conditions corresponding with neutral pH. Our calculations predict that charged amino acid analogues have a relatively high affinity to the titania surface, with the arginine analogue predicted to be the strongest binder. Interactions between uncharged amino acid analogues and titania are found to be repulsive or weak at best. All of the residues that bound to the negatively-charged interface show a relatively stronger adsorption compared with the charge-neutral interface, including the negatively-charged analogue. Of the analogues that are found to bind to the titania surface, the rank ordering of the binding affinities is predicted to be "arginine" > "lysine" ≈ aspartic acid > "serine". This is the same ordering as was found previously for the charge-neutral aqueous titania interface. Our results show very good agreement with available experimental data and can provide a baseline for the interpretation of peptide-TiO2 adsorption data.