Uniform nanoparticles by flame-assisted spray pyrolysis (FASP) of low cost precursors

A new flame-assisted spray pyrolysis (FASP) reactor design is presented, which allows the use of inexpensive precursors and solvents (e.g., ethanol) for synthesis of nanoparticles (10-20nm) with uniform characteristics. In this reactor design, a gas-assisted atomizer generates the precursor solution spray that is mixed and combusted with externally fed inexpensive fuel gases (acetylene or methane) at a defined height above the atomizing nozzle. The gaseous fuel feed can be varied to control the combustion enthalpy content of the flame and onset of particle formation. This way, the enthalpy density of the flame is decoupled from the precursor solution composition. Low enthalpy content precursor solutions are prone to synthesis of non-uniform particles (e.g., bimodal particle size distribution) by standard flame spray pyrolysis (FSP) processes. For example, metal nitrates in ethanol typically produce nanosized particles by gas-to-particle conversion along with larger particles by droplet-to-particle conversion. The present FASP design facilitates the use of such low enthalpy precursor solutions for synthesis of homogeneous nanopowders by increasing the combustion enthalpy density of the flame with low-cost, gaseous fuels. The effect of flame enthalpy density on product properties in the FASP configuration is explored by the example of Bi2O3 nanoparticles produced from bismuth nitrate in ethanol. Product powders were characterized by nitrogen adsorption, X-ray diffraction, X-ray disk centrifuge, and transmission electron microscopy. Homogeneous Bi2O3 nanopowders were produced both by increasing the gaseous fuel content and, most notably, by cutting the air entrainment prior to ignition of the spra

Marine turf of an invasive alga expels lugworms from the lower shore

Bare sandy flats at and below low tide level of the Wadden Sea (eastern North Sea, European Atlantic) were observed in 2020 to have been invaded by an introduced grass-like alga, Vaucheria cf. velutina (Xanthophyceae). A dense algal turf accumulated and stabilized mud, where resident seniors of the lugworm Arenicola marina had reworked rippled sand. Algae and worms were incompatible. Initially, rising patches with algal turf alternated with bare pits where lugworms crowded. Their bioturbation inhibited young algae, while the felt of established algal rhizoids clogged feeding funnels of worm bur- rows. Eventually, a mosaic pattern of competitors gave way to a coherent algal turf without lugworms. Concomitantly, a rich small-sized benthic fauna took advantage of the novel algal turf. This exotic Vaucheria may have the potential for drastically altering the ecological web at the lower shore

Invasion trajectory of Pacific oysters in the northern Wadden Sea

Invasion trajectories of introduced alien species usually begin with a long establishment phase of low abundance, often followed by exponential expansion and subsequent adjustment phases. We review the first 26 years of feral Pacific oysters Crassostrea gigas around the island of Sylt in the Wadden Sea (North Sea, NE Atlantic), and reveal causal conditions for the invasion phases. Sea-based oyster farming with repeated introductions made establishment of feral oysters almost inevitable. Beds of mussels Mytilus edulis on mud flats offered firm substrate for attachment and ideal growth conditions around low tide level. C. gigas mapped on to the spatial pattern of mussel beds. During the 1990s, cold summers often hampered recruitment and abundances remained low but oyster longevity secured persistence. Since the 2000s, summers were often warmer and recruitment more regular. Young oysters attached to adult oysters and abundances of >1000 m−2 were achieved. However, peak abundance was followed by recruitment failure. The population declined and then was also struck by ice winters causing high mortality. Recovery was fast (>2000 m−2) but then recruitment failed again. We expect adjustment phase will proceed with mean abundance of about 1000 m−2 but density-dependent (e.g., diseases) and density-independent (e.g., weather anomalies) events causing strong fluctuations. With continued global warming, feral C. gigas at the current invasion fronts in British estuaries and Scandinavian fjords may show similar adjustment trajectories as observed in the northern Wadden Sea, and also other marine introductions may follow the invasion trajectory of Pacific oysters

Manila clams Ruditapes philippinarum spreading north and establishing in the European Wadden Sea

In an era of accelerating biological globalization and climatic warming, it is vital to understand how introduced species integrate. Pacific Manila clams Ruditapes philippinarum were introduced for aquaculture to Europe in the 1970s, spread and became harvested from the Mediterranean Sea to British coasts. From the Dutch Rhine Delta, Manila clams immigrated stepwise into the southern Wadden Sea, and by long distance jump dispersal they arrived in the northern Wadden Sea in the 2010s. Encounters remained few until 2021, when live clams were often found in intertidal seagrass beds and around mixed beds of Pacific oysters with native mussels. Shell lengths reached up to 74 mm with a longevity of 7–8 years. Adult abundances remained low (<10 clams m−2), although larval numbers substantially increased in 2022 and 2023. Strong predation on spat may constitute ecological resistance to the immigrant. Haplotype diversity at mtDNA COI gene fragments is high and its composition is mixed from dominant haplotypes of other European sites, suggesting multiple introductions or an unknown source with an already mixed population. Currently, this is the most northern (55◦ N) population of R. philippinarum in continental Europe, but with the rapid expansion of this genetically variable population, further northward spread can be expected

The Role of Nebulizer Gas Flow in Electrosonic Spray Ionization (ESSI)

In this work, we investigated the role of the nebulizer gas flow in electrosonic spray ionization (ESSI), by systematically studying the relation between the flow and the ion signals of proteins, such as cytochrome c and holomyoglobin using ESSI-mass spectrometry (MS). When a neutral solution was delivered with a small sample flow rate (≤5μL/min), no obvious transition from electrospray ionization (ESI) to ESSI was found as the gas velocity varies from subsonic to supersonic speed. Droplets mostly experienced acceleration instead of breakup by the high-speed nebulizer gas. On the contrary, using particular experimental conditions, such as an acidic solution or high sample flow rate (≥200μL/min), more folded protein ions appear to be kept in droplets of diminishing size due to breakup by the high-speed nebulizer gas in ESSI compared with ESI. Theoretical analyses and numerical simulations were also performed to explain the observed phenomena. These systematic studies clarify the ionization mechanism of ESSI and provide valuable insight for optimizing ESSI and other popular pneumatically assisted electrospray ionization methods for future application

On the mechanism of extractive electrospray ionization (EESI) in the dual-spray configuration

Dual-spray extractive electrospray ionization (EESI) mass spectrometry as a versatile analytical technique has attracted much interest due to its advantages over conventional electrospray ionization (ESI). The crucial difference between EESI and ESI is that in the EESI process, the analytes are introduced in nebulized form via a neutral spray and ionized by collisions with the charged droplets from an ESI source formed by spraying pure solvent. However, the mechanism of the droplet-droplet interactions in the EESI process is still not well understood. For example, it is unclear which type of droplet-droplet interaction is dominant: bounce, coalescence, disruption, or fragmentation? In this work, droplet-droplet interaction was investigated in detail based on a theoretical model. Phase Doppler anemometry (PDA) was employed to investigate the droplet behavior in the EESI plume and provide the experimental data (droplet size and velocity) necessary for theoretical analysis. Furthermore, numerical simulations were performed to clarify the influence of the sheath gas flow on the EESI process. No coalescence between the droplets in the ESI spray and the droplets in the sample spray was observed using various geometries and sample flow rates. Theoretical analysis, together with the PDA results, suggests that droplet fragmentation may be the dominant type of droplet-droplet interaction in the EESI. The interaction time between the ESI droplet and the sample droplet was estimated to be <5μs. This work gives a clear picture of droplet-droplet interactions in the dual-spray EESI process and detailed information for the optimization of this method for future applications that require higher sensitivit

Spread of the invasive shell-boring annelid Polydora websteri (Polychaeta, Spionidae) into naturalised oyster reefs in the European Wadden Sea

With globally growing aquaculture activities, the co-introduction of parasites alongside large-scale movements of commercial species poses an increasing risk for marine ecosystems. Here, we present the first record of the shell-boring polychaete Polydora websteri Hartman in Loosanoff and Engle, 1943 in invasive Pacific oysters Crassostrea (Magallana) gigas (Thunberg, 1793) in the European Atlantic Ocean. In October 2014, mud blisters in the shells of wild Pacific oysters and specimens of a spionid polychaete were observed in close proximity to a commercial oyster farm at the island of Sylt (Germany) in the European Wadden Sea. Subsequent investigations indicated that these blisters only occurred near the farm and that no other mollusc species were affected. Morphological and molecular analysis identified the polychaete as Polydora websteri, a species that nowadays widely occurs around the globe, but likely is native to the Asian Pacific. Later sampling activities detected P. websteri also at other locations around Sylt as well as in the Dutch part of the Wadden Sea at the island of Texel. The number of polychaetes in the oysters was, however, relatively low and mostly below 10 individuals per oyster. Together, this evidence suggests that P. websteri is currently extending its range. As the introduction of P. websteri may have severe ecological and economic implications, this study aims to alert others to look for P. websteri at Western European coasts within farmed or wild Pacific oysters to further document its spread