First Characterization of Ostreopsis cf. ovata (Dinophyceae) and Detection of Ovatoxins during a Multispecific and Toxic Ostreopsis Bloom on French Atlantic Coast.

Blooms of the benthic toxic dinoflagellate genus Ostreopsis have been recorded more frequently during the last two decades, particularly in warm temperate areas such as the Mediterranean Sea. The proliferation of Ostreopsis species may cause deleterious effects on ecosystems and can impact human health through skin contact or aerosol inhalation. In the eastern Atlantic Ocean, the toxic O. cf. ovata has not yet been reported to the north of Portugal, and the only species present further north was O. cf. siamensis, for which the toxic risk is considered low. During summer blooms of unidentified Ostreopsis species on the French Basque coast (Atlantic) in 2020 and 2021, people suffered from irritations and respiratory disorders, and the number of analyzed cases reached 674 in 2021. In order to investigate the causes, sampling was carried out during summer 2021 to (i) taxonomically identify Ostreopsis species present using a molecular approach, (ii) isolate strains from the bloom and culture them, and (iii) characterize the presence of known toxins which may be involved. For the first time, this study reports the presence of both O. cf. siamensis and O. cf. ovata, for which the French Basque coast is a new upper distribution limit. Furthermore, the presence of ovatoxins a, b, c, and d in the environmental sample and in a cultivated strain in culture confirmed the toxic nature of the bloom and allowed identifying O. cf. ovata as the producer. The present data identify a new health risk in the area and highlight the extended distribution of some harmful dinoflagellates, presumably in relation to climate change.

Cements in the 21st Century: Challenges, Perspectives, and Opportunities.

In a book published in 1906, Richard Meade outlined the history of portland cement up to that point1. Since then there has been great progress in portland cement-based construction materials technologies brought about by advances in the materials science of composites and the development of chemical additives (admixtures) for applications. The resulting functionalities, together with its economy and the sheer abundance of its raw materials, have elevated ordinary portland cement (OPC) concrete to the status of most used synthetic material on Earth. While the 20th century was characterized by the emergence of computer technology, computational science and engineering, and instrumental analysis, the fundamental composition of portland cement has remained surprisingly constant. And, although our understanding of ordinary portland cement (OPC) chemistry has grown tremendously, the intermediate steps in hydration and the nature of calcium silicate hydrate (C-S-H), the major product of OPC hydration, remain clouded in uncertainty. Nonetheless, the century also witnessed great advances in the materials technology of cement despite the uncertain understanding of its most fundamental components. Unfortunately, OPC also has a tremendous consumption-based environmental impact, and concrete made from OPC has a poor strength-to-weight ratio. If these challenges are not addressed, the dominance of OPC could wane over the next 100 years. With this in mind, this paper envisions what the 21st century holds in store for OPC in terms of the driving forces that will shape our continued use of this material. Will a new material replace OPC, and concrete as we know it today, as the preeminent infrastructure construction material?

Adsorption of aqueous insensitive munitions compounds by graphene nanoplatelets.

Mitigation strategies for potential environmental impacts of insensitive munition (IM) compounds, including 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), nitroguanidine (NQ), and methylnitroguanidine, (MeNQ) are being considered to enhance sustainability of current or potential IM formulations. Graphene nanoplatelets (GnPs) were investigated for adsorptive removal of each compound. GnPs were characterized to determine surface areas, along with particle size and zeta potential at different pH and ionic strength conditions. Adsorption kinetics and isotherm studies were conducted, comparing results against granular activated carbon (GAC). Ionic strength, pH, and temperature were adjusted to inform impacts on adsorptive behaviors and performance. The results indicated that GnPs adsorbed IM compounds more rapidly than GAC. Additionally, GnPs removed DNAN with greater capacity compared to GAC, likely due to π-π interactions. GnPs removed other compounds via van der Waals forces, while GAC exhibited greater adsorption capacities due to higher surface area. Although negative charges associated with GnPs and dissociated NTO species hindered adsorption, pH and ionic strength did not impact other compounds. Moreover, this study reports the first environmental treatment technique for MeNQ. Overall, these findings suggest that GnPs are a promising treatment technology for IM-laden waters, particularly those with compounds like DNAN where specific interactions enhance removal efficiency.

Effect of Carbon Nanofiber Clustering on the Micromechanical Properties of a Cement Paste.

The use of carbon nanofibers (CNFs) in cement systems has received significant interest over the last decade due to their nanoscale reinforcing potential. However, despite many reports on the formation of localized CNF clusters, their effect on the cement paste micromechanical properties and relation to the mechanical response at the macroscopic scale are still not fully understood. In this study, grid nanoindentation coupled with scanning electron microscopy and energy dispersive spectroscopy was used to determine the local elastic indentation modulus and hardness of a portland cement paste containing 0.2% CNFs with sub-micro and microscale CNF clusters. The presence of low stiffness and porous assemblage of phases (modulus of 15-25 GPa) was identified in the cement paste with CNFs and was attributed primarily to the interfacial zone surrounding the CNF clusters. The CNFs favored the formation of higher modulus C-S-H phases (>30 GPa) in the bulk paste at the expense of the lower stiffness C-S-H. Nanoindentation results combined with a microscale-macroscale upscaling homogenization method further revealed an elastic modulus of the CNF clusters in the range from 18 to 21 GPa, indicating that the CNF clusters acted as compliant inclusions relative to the cement paste.

Evaluating the fate of metals in air pollution control residues from coal-fired power plants.

Changes in emissions control at U.S. coal-fired power plants will shift metals content from the flue gas to the air pollution control (APC) residues. To determine the potential fate of metals that are captured through use of enhanced APC practices, the leaching behavior of 73 APC residues was characterized following the approach of the Leaching Environmental Assessment Framework. Materials were tested over pH conditions and liquid-solid ratios expected during management via land disposal or beneficial use. Leachate concentrations for most metals were highly variable over a range of coal rank, facility configurations, and APC residue types. Liquid-solid partitioning (equilibrium) as a function of pH showed significantly different leaching behavior for similar residue types and facility configurations. Within a facility, the leaching behavior of blended residues was shown to follow one of four characteristic patterns. Variability in metals leaching was greater than the variability in totals concentrations by several orders of magnitude, inferring that total content is not predictive of leaching behavior. The complex leaching behavior and lack of correlation to total contents indicates that release evaluation under likely field conditions is a better descriptor of environmental performance than totals content or linear partitioning approaches.

Effect of indigenous bacterial activity on arsenic mobilization under anaerobic conditions.

Batch biochemical leaching tests were carried out to investigate the mobility of arsenic from a contaminated soil collected from a French gold mining site. The specific objective of this research was to examine the effect of indigenous bacterial activity on arsenic mobilization under anaerobic conditions. In a first step, physical and chemical characterizations were performed to provide data concerning the liquid-solid partitioning and mobility of arsenic and other inorganic constituents. In a second step, batch bioleaching tests were conducted in shaker flasks to determine the effect of indigenous bacterial activity under different anaerobic conditions (i.e., addition of mineral nutrients and carbon sources) on arsenic mobilization. Results indicated that arsenic release during contact with deionized water was limited by its very low solubility in the interstitial solution and by the stability of the different arsenic compounds formed with the amorphous solid phases of the soil (mainly iron (oxy)hydroxides). However, an increased mobilization potential was observed over the long term under anaerobic conditions with indigenous bacterial activity enhanced by the addition of carbon sources.

Effect of experimentally induced reducing conditions on the mobility of arsenic from a mining soil.

A method for estimating the release of contaminants from contaminated sites under reducing conditions is proposed. The ability of two chemical reducing agents, sodium ascorbate and sodium borohydride, to produce different redox environments in a gold mining soil contaminated with arsenic was investigated. Liquid-solid partitioning experiments were carried out in the presence of each of the reducing agents at different pH conditions. Both the effect of varying concentrations of the reducing agent and the effect of varying pH in the presence of a constant concentration of the reducing agent were studied. Concentrations of sodium ascorbate ranging from 0.0075 to 0.046 mol L(-1) and concentrations of sodium borohydride ranging from 0.0075 to 0.075 mol L(-1) were examined. The addition of varying concentrations of sodium borohydride provided greater reducing conditions (ranging from -500 to +140 mV versus NHE) than that obtained using sodium ascorbate (ranging from -7 to +345 mV versus NHE). The solubilization of arsenic and iron was significantly increased by the addition of sodium ascorbate for all concentrations examined and pH tested, compared to that obtained under oxidizing conditions (as much as three orders of magnitude and four orders of magnitude, respectively, for the addition of 0.046 mol L(-1) of sodium ascorbate). In contrast, the alkaline and highly reduced soil conditions obtained with sodium borohydride lead to a lower effect on arsenic solubilization (as much as one order of magnitude for pH values between ca. 7 and 10 and no effect for pH values between ca. 10 and 12) and no effect on iron solubilization for all concentrations examined and pH tested. At similar ORP-pH conditions the results of extraction for arsenic and iron were different for the two reagents used.