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Environmental observation networks, such as AmeriFlux, are foundational for monitoring ecosystem response to climate change, management practices, and natural disturbances; however, their effectiveness depends on their representativeness for the regions or continents. We proposed an empirical, time series approach to quantify the similarity of ecosystem fluxes across AmeriFlux sites. We extracted the diel and seasonal characteristics (i.e., amplitudes, phases) from carbon dioxide, water vapor, energy, and momentum fluxes, which reflect the effects of climate, plant phenology, and ecophysiology on the observations, and explored the potential aggregations of AmeriFlux sites through hierarchical clustering. While net radiation and temperature showed latitudinal clustering as expected, flux variables revealed a more uneven clustering with many small (number of sites < 5), unique groups and a few large (> 100) to intermediate (15–70) groups, highlighting the significant ecological regulations of ecosystem fluxes. Many identified unique groups were from under-sampled ecoregions and biome types of the International Geosphere-Biosphere Programme (IGBP), with distinct flux dynamics compared to the rest of the network. At the finer spatial scale, local topography, disturbance, management, edaphic, and hydrological regimes further enlarge the difference in flux dynamics within the groups. Nonetheless, our clustering approach is a data-driven method to interpret the AmeriFlux network, informing future cross-site syntheses, upscaling, and model-data benchmarking research. Finally, we highlighted the unique and underrepresented sites in the AmeriFlux network, which were found mainly in Hawaii and Latin America, mountains, and at under- sampled IGBP types (e.g., urban, open water), motivating the incorporation of new/unregistered sites from these groups. 

Volcanic ash nucleates ice when immersed in supercooled water droplets, giving it the potential to influence weather and climate from local to global scales. This ice nucleation activity (INA) is likely derived from a subset of the crystalline mineral phases in the ash. The INA of other mineral-based dusts can change when exposed to various gaseous and aqueous chemical species, many of which also interact with volcanic ash in the eruption plume and atmosphere. However, the effects of aqueous chemical aging on the INA of volcanic ash have not been explored. We show that the INA of two mineralogically distinct ash samples from Fuego and Astroni volcanoes is variably reduced following immersion in water or aqueous sulfuric acid for minutes to days. Aging in water decreases the INA of both ash samples by up to two orders of magnitude, possibly due to a reduction in surface crystallinity and cation availability accompanying leaching. Aging in sulfuric acid leads to minimal loss of INA for Fuego ash, which is proposed to reflect a quasi-equilibrium between leaching that removes ice-active sites and dissolution that reveals or creates new sites on the pyroxene phases present. Conversely, exposure to sulfuric acid reduces the INA of Astroni ash by one to two orders of magnitude, potentially through selective dissolution of ice-active sites associated with surface microtextures on some K-feldspar phases. Analysis of dissolved element concentrations in the aged ash leachates shows supersaturation of certain mineral species which could have precipitated and altered the INA of the ash. These results highlight the key role that leaching, dissolution, and precipitation likely play in the aqueous aging of volcanic ash with respect to its INA. Finally, we discuss the implications for understanding the nature and reactivity of ice-active sites on volcanic ash and its role in influencing cloud properties in the atmosphere. 

Ice-nucleating particles (INPs) in biomass-burning aerosol (BBA) that affect cloud glaciation, microphysics, precipitation, and radiative forcing were recently found to be driven by the production of mineral phases. BBA experiences extensive chemical aging as the smoke plume dilutes, and we explored how this alters the ice activity of the smoke using simulated atmospheric aging of authentic BBA in a chamber reactor. Unexpectedly, atmospheric aging enhanced the ice activity for most types of fuels and aging schemes. The removal of organic carbon particle coatings that conceal the mineral-based ice-active sites by evaporation or oxidation then dissolution can increase the ice activity by greater than an order of magnitude. This represents a different framework for the evolution of INPs from biomass burning where BBA becomes more ice active as it dilutes and ages, making a larger contribution to the INP budget, resulting cloud microphysics, and climate forcing than is currently considered. 

We examined the reactive uptake of dinitrogen pentoxide (N 2 O 5 ) to authentic biomass-burning aerosol (BBA) using a small chamber reservoir in combination with an entrained aerosol flow tube. BBA was generated from four different fuel types and the reactivity of N 2 O 5 was probed from 30 to 70% relative humidity (RH). The N 2 O 5 reactive uptake coefficient, γ (N 2 O 5 ), depended upon RH, fuel type, and to a lesser degree on aerosol chloride mass fractions. The γ (N 2 O 5 ) ranged from 2.0 (±0.4) ×10 −3 on black needlerush derived BBA at 30% RH to 6.0 (±0.6) ×10 −3 on wiregrass derived BBA at 65% RH. Major N 2 O 5 reaction products were observed including gaseous ClNO 2 and HNO 3 and particulate nitrate, and used to create a reactive nitrogen budget. Black needlerush BBA had the most particulate chloride, and the only measured ClNO 2 yield > 1%. The ClNO 2 yield on black needlerush decayed from an initial value of ∼100% to ∼30% over the course of the burn experiment, suggesting a depletion of BBA chloride over time. Black needlerush was also the only fuel for which the reactive nitrogen budget indicated other N-containing products were generated. Generally, the results suggest limited chloride availability for heterogeneous reaction for BBA in the RH range probed here, including BBA with chloride mass fractions on the higher end of previously reported values (∼17–34%). Though less than fresh sea spray aerosol, ∼50%. We use these measured quantities to discuss the implications for nocturnal aerosol nitrate formation, the chemical fate of N 2 O 5 (g), and the availability of particulate chloride for activation in biomass burning plumes. 

We present a new algorithm for the analysis of whispering gallery modes (WGMs) found in the cavity enhanced Raman spectra retrieved from optically tweezed droplets. Our algorithm improves the computational scaling when analyzing core–shell droplets ( i.e. phase-separated or biphasic droplets) in the aerosol optical tweezers (AOT), making it computationally practical to analyze spectra collected at a few Hz over hours-long experiments. This enables the determination of the size and refractive index of both the core and shell phases with high accuracy, at 0.5 Hz time resolution. Phase-separated core–shell droplets are common morphologies in a wide variety of biophysical, colloidal, and aerosolized chemical systems, and have recently become a major focus in understanding the atmospheric chemistry of particulate matter. Our new approach reduces the number of parameters directly searched for, decreasing computational demands. We assess the accuracy of the diameters and refractive indices retrieved from a homogeneous or core–shell droplet. We demonstrate the performance of the new algorithm using experimental data from a droplet of aqueous glycerol coated by squalane. We demonstrate that a shell formation causes adjacent WGMs to split from each other in their wavenumber position through the addition of a secondary organic aerosol shell around a NaCl(aq) droplet. Our new algorithm paves the way for more in-depth physiochemical experiments into liquid–liquid phase separation and their consequences for interfacial chemistry—a topic with growing experimental needs for understanding the dynamics and chemistry of atmospheric aerosol particles, and in biochemical systems.