Sea-Air Transfer of Ostreopsis Phycotoxins Is Driven by the Chemical Diversity of the Particulate Fraction in the Surface Microlayer.

Blooms of Ostreopsis cf. ovata pose an emerging health threat, causing respiratory disorders in various coastal regions. This dinoflagellate produce potent phycotoxins named ovatoxins that can be transferred from the seawater to the atmosphere. However, the biotic and abiotic conditions affecting their transfer are still unknown. In this study, we investigate the sea-to-air transfer of O. cf ovata phycotoxins using a process study in an aerosol reference tank (MART) and field observations. The process study exhibited a positive correlation between the phycotoxin content in sea spray aerosol (up to 832.59 ng m-3) and the particulate phycotoxin fraction in the water column and surface microlayer. In contrast, in the natural system, aerosolized phycotoxins were only observed in one out of six air collection (total toxins 0.59 ng m-3) despite optimal wind conditions. In both the process study and the natural system, ovatoxins represented only a minor fraction of the total toxin content, which was comprised of up to 90% liguriatoxins. In seawater, while no solubilized ovatoxins were detected, the concentration in dissolved liguriatoxin-a reached up to 19.07 µg L-1. These results underscore the need for future research on the liguriatoxins, and on their toxicity to establish safe exposure thresholds for beachgoers.

Emissions from Heated Terpenoids Present in Vaporizable Cannabis Concentrates.

Vaporizable cannabis concentrates (VCCs) consumed as a liquid (vaping) or a waxy solid (dabbing) are becoming increasingly popular. However, their associated emissions and impacts have not been fully described. Mixtures containing different proportions of 12 VCC terpenoids and high MW compounds were heated at 100-500 °C inside a room-sized chamber to simulate emissions. Terpenoids, thermal degradation byproducts, and ultrafine particles (UFPs) were quantified in the chamber air. Air samples contained over 50% of emitted monoterpenes and less than 40% of released sesquiterpenes and terpene alcohols. Eleven degradation byproducts were quantified, including acrolein (1.3-3.9 µg m-3) and methacrolein (2.0 µg m-3). A large amount of UFPs were released upon heating and remained airborne for at least 3 h. The mode diameter increased from 80 nm at 100 °C to 140 nm at 500 °C, and particles smaller than 250 nm contributed to 90% of PM1.0. The presence of 0.5% of lignin, flavonoid, and triterpene additives in the heated mixtures resulted in a threefold increase in the particle formation rate and PM1.0 concentration, suggesting that these high-molecular-weight compounds enhanced aerosol inception and growth. Predicted UFP emission rates in typical consumption scenarios (6 × 1011-2 × 1013 # min-1) were higher than, or comparable with, other common indoor sources such as smoking and cooking.

Tandem Fluorescence Measurements of Organic Matter and Bacteria Released in Sea Spray Aerosols.

Biological aerosols, typically identified through their fluorescence properties, strongly influence clouds and climate. Sea spray aerosol (SSA) particles are a major source of biological aerosols, but detection in the atmosphere is challenging due to potential interference from other sources. Here, the fluorescence signature of isolated SSA, produced using laboratory-based aerosol generation methods, was analyzed and compared with two commonly used fluorescence techniques: excitation-emission matrix spectroscopy (EEMS) and the wideband integrated bioaerosol sensor (WIBS). A range of dynamic biological ocean scenarios were tested to compare EEMS and WIBS analyses of SSA. Both techniques revealed similar trends in SSA fluorescence intensity in response to changes in ocean microbiology, demonstrating the potential to use the WIBS to measure fluorescent aerosols alongside EEMS bulk solution measurements. Together, these instruments revealed a unique fluorescence signature of isolated, nascent SSA and, for the first time, a size-segregated emission of fluorescent species in SSA. Additionally, the fluorescence signature of aerosolized marine bacterial isolates was characterized and showed similar fluorescence peaks to those of SSA, suggesting that bacteria are a contributor to SSA fluorescence. Through investigation of isolated SSA, this study provides a reference for future identification of marine biological aerosols in a complex atmosphere.

Volatile aldehyde emissions from "sub-ohm" vaping devices.

"Sub-ohm" atomizers with reduced resistance can deliver more power than conventional electronic cigarettes. Typical battery outputs are 100 W or more. These devices are particularly popular among young users, and can be a significant source of volatile carbonyls in the indoor environment. Emissions from next-generation sub-ohm vaping products were characterized by determining e-liquid consumption and volatile aldehydes emissions for several combinations of popular high-power configurations. Tests explored the effect of dilution air flow (air vent opening), puffing volume, and coil assembly configuration. The mass of liquid consumed per puff increased as the puff volume increased from 50 to 100 mL, then remained relatively constant for larger puff volumes up to 500 mL. This is likely due to mass transfer limitations at the wick and coil assembly, which reduced the vaporization rate at higher puff volumes. Carbonyl emission rates were systematically evaluated using a 0.15 Ω dual coil atomizer as a function of the puffing volume and dilution air flow, adjusted by setting the air vents to either 100% (fully open), 50%, 25%, or 0% (closed). The highest formaldehyde emissions were observed for the lowest puff volume (50 mL) when the vents were closed (48 ng mg-1), opened at 25% (39 ng mg-1) and at 50% (32 ng mg-1). By contrast, 50-mL puffs with 100% open vents, and puff volumes >100 mL for any vent aperture, generated formaldehyde yields of 20 ng mg-1 or lower, suggesting that a significant cooling effect resulted in limited carbonyl formation. Considering the effect of the coil resistance when operated at a voltage of 3.8 V, the amount of liquid evaporated per puff decreased as the resistance increased, in the order of 0.15 Ω > 0.25 Ω > 0.6 Ω, consistent with decreasing aerosol temperatures measured at the mouthpiece. Three different configurations of 0.15 Ω coils (dual, quadruple and octuple) were evaluated, observing significant variability. No clear trend was found between carbonyl emission rates and coil resistance or configuration, with highest emissions corresponding to a 0.25 Ω dual coil atomizer. Carbonyl emission rates were compared with those determined using the same methodology for conventional e-cigarettes (lower power tank systems), observing overall lower yields for the sub-ohm devices.

Heated Tobacco Products: Volatile Emissions and Their Predicted Impact on Indoor Air Quality.

This study characterized emissions from IQOS, a heated tobacco product promoted as a less harmful alternative to cigarettes. Consumable tobacco plugs were analyzed by headspace GC/MS to assess the influence of heating temperature on the emission profile. Yields of major chemical constituents increased from 4.1 mg per unit at 180 °C to 6.2 mg at 200 °C, and 10.5 mg at 220 °C. The Health Canada Intense smoking regime was used to operate IQOS in an environmental chamber, quantifying 33 volatile organic compounds in mainstream and sidestream emissions. Aldehydes, nitrogenated species, and aromatic species were found, along with other harmful and potentially harmful compounds. Compared with combustion cigarettes, IQOS yields were in most cases 1-2 orders of magnitude lower. However, yields were closer to, and sometimes higher than electronic cigarettes. Predicted users' daily average intake of benzene, formaldehyde, acetaldehyde and acrolein were 39 µg, 32 µg, 2.2 mg and 71 µg, respectively. Indoor air concentrations were estimated for commonly encountered scenarios, with acrolein levels of concern (over 0.35 µg m-3) derived from IQOS used in homes and public spaces. Heated tobacco products are a weaker indoor pollution source than conventional cigarettes, but their impacts are neither negligible nor yet fully understood.

Non-targeted tandem mass spectrometry enables the visualization of organic matter chemotype shifts in coastal seawater.

Urbanization along coastlines alters marine ecosystems including contributing molecules of anthropogenic origin to the coastal dissolved organic matter (DOM) pool. A broad assessment of the nature and extent of anthropogenic impacts on coastal ecosystems is urgently needed to inform regulatory guidelines and ecosystem management. Recently, non-targeted tandem mass spectrometry approaches are gaining momentum for the analysis of global organic matter composition (chemotypes) including a wide array of natural and anthropogenic compounds. In line with these efforts, we developed a non-targeted liquid chromatography tandem mass spectrometry (LC-MS/MS) workflow that utilizes advanced data analysis approaches such as feature-based molecular networking and repository-scale spectrum searches. This workflow allows the scalable comparison and mapping of seawater chemotypes from large-scale spatial surveys as well as molecular family level annotation of unknown compounds. As a case study, we visualized organic matter chemotype shifts in coastal environments in northern San Diego, USA, after notable rain fall in winter 2017/2018 and highlight potential anthropogenic impacts. The observed seawater chemotype, consisting of 4384 LC-MS/MS features, shifted significantly after a major rain event. Molecular drivers of this shift could be attributed to multiple anthropogenic compounds, including pesticides (Imazapyr and Isoxaben), cleaning products (Benzyl-tetradecyl-dimethylammonium) and chemical additives (Hexa (methoxymethyl)melamine) and potential degradation products. By expanding the search of identified xenobiotics to other public tandem mass spectrometry datasets, we further contextualized their possible origin and show their importance in other ecosystems. The mass spectrometry and data analysis pipelines applied here offer a scalable framework for future molecular mapping and monitoring of marine ecosystems, which will contribute to a deliberate assessment of how chemical pollution impacts our oceans.

Effect of different gases on the sonochemical Cr(VI) reduction in the presence of citric acid.

The sonochemical (850 kHz) Cr(VI) reduction (0.30 mM, pH 2) in the presence of citric acid (Cit, 2 mM) was analyzed under different working atmospheres: reactor open to air without sparging (ROAWS), and Ar, O2, air and N2 sparging. Hydrogen peroxide formation in pure water at pH 2 and KI dosimetry were also measured. Zero-order kinetics was observed in all cases. A complete Cr(VI) reduction after 180 min insonation was obtained with the ROAWS and under Ar, while a lower Cr(VI) reduction efficiency was achieved under the other conditions. The Cr(VI) reduction and H2O2 formation rates followed the order ROAWS â‰… Ar > air â‰… O2 ≫ N2, while for KI dosimetry the order was ROAWS â‰« O2 â‰… air > Ar â‰« N2. This indicates that H2O2 formation rate is a better measure of the system reactivity for Cr(VI) reduction. For air, O2 and N2, once the sparging was stopped, Cr(VI) reduction rate increased up to approximately the same value obtained for the ROAWS, suggesting that the sparging decreased the generation of reactive species and, thus, the Cr(VI) reduction rate. Nitrate production was measured at low concentrations (micromolar range) in the ROAWS, air and N2 systems. Formic and acetic acids were detected as Cit degradation products. Reaction mechanisms were proposed. It can be concluded that the best condition for Cr(VI) removal is with the ROAWS because of a higher Cr(VI) reduction rate, no atmosphere control is required, and it is a less expensive system.

Sonochemical reduction of Cr(VI) in air in the presence of organic additives: What are the involved mechanistic pathways?

The sonochemical (850 kHz) reduction of Cr(VI) (0.3 mM, pH 2, reactor open to air) was analyzed in the presence of different additives. The effects on Cr(VI) reduction efficiency of added formic acid (FA, 10 mM), citric acid (Cit, 2 mM), ethylenediaminetetraacetic acid (EDTA, 1 mM), methanol (MeOH, 0.1 M), ethanol (EtOH, 0.1 M), 2-propanol (2-PrOH, 0.1 M), tert-butanol (t-BuOH, 0.1 M), phenol (PhOH, 2 mM) and sodium lauryl sulfate (SLS, 1 mM) have been evaluated in comparison with the system in the absence of additives. Complete Cr(VI) reduction was obtained only when using EDTA (at 120 min) and Cit (at 180 min). Cr(III) complexes with these compounds or with their degradation products were detected as final products. For EDTA, Cit, t-BuOH, FA and SLS, the Cr(VI) decay could be adjusted to a zero-order kinetics; in the cases of MeOH, EtOH and 2-PrOH, there was a deviation from the zero-order kinetics. The Cr(VI) conversion increased in the order SLS (very low) < no additive ≅ MeOH ≅ EtOH ≅ 2-PrOH < FA < t-BuOH < PhOH < Cit < EDTA. The role of EDTA and Cit in stabilizing intermediate Cr(V) peroxo compounds and enhancing their direct transformation into different Cr(III) species is considered a major factor in the acceleration of Cr(VI) reduction processes. Mechanistic pathways are proposed.