The role of biomass elemental composition and ion-exchange in metal sorption by algae.

The use of macroalgae, microalgae and cyanobacteria for metal sorption has been widely reported. Still, there are no studies allowing a direct comparison of the performance of these biomasses, especially while evaluating metal competition. The simultaneous sorption of Co2+, Cu2+, Ni2+ and Zn2+ present in a multi-elemental solution by six macroalgae, two microalgae and three cyanobacteria was evaluated. Brown macroalgae were shown to be the most promising biosorbent, with Undaria pinnatifida having a total metal sorption capacity of 0.6 mmol g-1. Overall, macroalgae performed better than microalgae, followed by cyanobacteria. Carboxyl groups were identified as being the main functional groups involved in metal sorption, and all biomass samples were found to be selective to Cu2+. This was linked not only to its higher complexation constant value with relevant functional groups when compared to the remaining metals, but also the Irving-Williams series. The release of K+ and Ca2+ to the aqueous solution during the metal sorption was followed. The obtained results suggest they are readily exchanged with metals in the solution, indicating the occurrence of an ion-exchange mechanism in metal sorption by most biomass. Red macroalgae are an exception to the reported trends, suggesting that their metal sorption mechanism may differ from the other biomass types.

Recovery of bacterioruberin and proteins using aqueous solutions of surface-active compounds.

Haloarchaea microorganisms are little explored marine resources that can be a promising source of valuable compounds with unique characteristics, due to their adaptation to extreme environments. In this work, the extraction of bacterioruberin and proteins from Haloferax mediterranei ATCC 33500 was investigated using aqueous solutions of ionic liquids and surfactants, which were further compared with ethanol. Despite the good performance of ethanol in the extraction of bacterioruberin, the use of aqueous solutions of surface-active compounds allowed the simultaneous release of bacterioruberin and proteins in a multi-product process, with the non-ionic surfactants being identified as the most promising. The optimum operational conditions allowed a maximum extraction yield of 0.37 ± 0.01 mgbacterioruberin gwet biomass -1 and 352 ± 9 mgprotein gwet biomass -1 with an aqueous solution of Tween® 20 (at 182.4 mM) as the extraction solvent. In addition, high purities of bacterioruberin were obtained, after performing a simple induced precipitation using ethanol as an antisolvent to recover the proteins present in the initial extract. Finally, a step for polishing the bacterioruberin was performed, to enable solvent recycling, further closing the process to maximize its circularity.

Cyanobacteria as Candidates to Support Mars Colonization: Growth and Biofertilization Potential Using Mars Regolith as a Resource.

Cyanobacteria are indicated as organisms that can possibly support Mars colonization, contributing to the production of oxygen and other commodities therein. In this general context, the aim of this work was to evaluate the ability of three species of cyanobacteria (Anabaena cylindrica, Nostoc muscorum, and Arthrospira platensis) and a green microalga (Chlorella vulgaris) to grow using only the resources existing in Mars, i.e., water and Martian regolith stimulant (MGS-1), under an Earth-like atmosphere. A Martian regolith extract was produced and used as a culture medium to grow these species. Their growth was assessed during a period of 25 days, using optical density and fluorometric parameters. After this period, the possible contribution of end-of-life cyanobacteria/microalga as biofertilizing agents was also assessed, using the macrophyte Lemna minor as a vegetable model. Among the three species, N. muscorum showed the best growth performance when compared to the other species, while A. platensis and C. vulgaris were not able to thrive on Mars regolith extract. Therefore, N. muscorum should be the target of future studies not only due to their role in oxygen production but also due to their possible use as a food source, as many members of the Nostoc genus. Cyanobacteria and microalgae (A. platensis and C. vulgaris) showed good abilities as biofertilizing agents, i.e., they stimulated biomass (i.e., dry weight) production at levels comparable to the plants that grew on standard synthetic medium. The highest yield was reached with A. platensis, while the lowest was achieved using the media with N. muscorum. FTIR-ATR (Fourier transform infrared with attenuated total reflectance) spectroscopy showed that the differences between the plants grown on media with or without Martian regolith seem to be related mainly to polysaccharides.

Bio-Based Solar Energy Harvesting for Onsite Mobile Optical Temperature Sensing in Smart Cities.

The Internet of Things (IoT) fosters the development of smart city systems for sustainable living and increases comfort for people. One of the current challenges for sustainable buildings is the optimization of energy management. Temperature monitoring in buildings is of prime importance, as heating account for a great part of the total energy consumption. Here, a solar optical temperature sensor is presented with a thermal sensitivity of up to 1.23% °C-1 based on sustainable aqueous solutions of enhanced green fluorescent protein and C-phycocyanin from biological feedstocks. These photonic sensors are presented under the configuration of luminescent solar concentrators widely proposed as a solution to integrate energy-generating devices in buildings, as windows or façades. The developed mobile sensor is inserted in IoT context through the development of a self-powered system able to measure, record, and send data to a user-friendly website.

Glycine-betaine-derived ionic liquids: Synthesis, characterization and ecotoxicological evaluation.

Ionic Liquids (ILs) are generically regarded as environmentally "harmless" and thus, assumed as "non-toxic". However, due to the endless design possibilities, their ecotoxicological profile is still poorly known. An accurate knowledge on the toxicity of a substance is required, under the scope of environmental regulation worldwide, before their application and commercialization. Knowledge on the relationship between the chemical structure and toxic effects is essential for the future design of more biocompatible solvents. Focusing on the use of ILs as base lubricants, lubricant additives, or even as potential working fluids for absorption heat pumps, the knowledge on its environmental impact is of great importance, due to the possibility of spills. In this specific context, four analogues of glycine-betaine-based ILs (AGB-ILs) and four glycine-betaine based ILs (GB-ILs) were synthesized and characterized. Their ecotoxicity was assessed using representatives of two trophic levels in aquatic ecosystems, the bacteria Allivibrio fischeri (commonly used as a screening test organism) and the microalgae Raphidocelis subcapitata (as an alternative test organism that has been proven very sensitive to several IL families). The microalgae were more sensitive than the bacteria, hence, following a precautionary principle, we recommend considering the toxicity towards microalgae as an indicator in future studies regarding the focused ILs. Although four of the studied ILs were derived from a natural amino acid, all were considered hazardous for the aquatic environment, disproving the primary theory that all ILs derived from natural compounds are benign. Furthermore, the modification in the structure of anion and the cation can lead to the increase of toxicity.

The antagonist and synergist potential of cholinium-based deep eutectic solvents.

The design of environmentally friendlier solvents has gained increasing relevance in the last decade. Deep eutectic solvents (DES) have recently emerged, with advantages like low-cost and putative lower environmental impact. However, information about DES toxicity is still scarce. This work aims to contribute to profiling the ecotoxicity of DES based on cholinium chloride ([Chol]Cl). Six DES were addressed, combining [Chol]Cl (as hydrogen bond acceptor - HBA) with ethylene glycol, glycerol, 1,2-propanediol, propionic acid, 1-propanol, and urea as hydrogen bond donors (HBD), in different molar ratios. The Microtox® Acute Toxicity Test, was used for assessing their toxicity towards the marine bacteria Allivibrio fischeri . Because the dissociation of DES in water is expected, analysis appraising the mixtures toxicity theory should be considered, which is a step forward in this field. This analysis suggested that [Chol]Cl and all HBD with the exception of propionic acid:[Chol]Cl 1:2 and 4:1 behave antagonistically, which is contrary to what has been suggested previously. The most extreme cases are Urea:[Chol]Cl and 1-Propanol:[Chol]Cl, with EC50 values higher than their starting materials dosed singly, configuring very promising and biocompatible alternative solvents. Toxicity was found to be dependent on DES composition, as well as on molar proportions of the starting materials.

Unraveling the ecotoxicity of deep eutectic solvents using the mixture toxicity theory.

The interest on deep eutectic solvents (DES) has been increasing. However, the ecotoxicological profile of DES is scarcely known. Also, despite previous studies showed that DES components dissociate in water, none assessed DES toxicity using the classical and adequate models for mixture toxicity prediction - concentration addition (CA) and independent action (IA). This study evaluates the ecotoxicological profile of DES based on [N1111]Cl, [N2222]Cl and [N3333]Cl as hydrogen bond acceptors (HBA) combined with hydrogen-bond donors (HBD) vis. ethylene glycol and 1-propanol, through the Microtox® Acute Toxicity Test. CA and IA with deviations describing synergism/antagonism, dose-ratio and dose-level effects were fitted to the toxicity data. Neither the starting materials nor DES were found hazardous to Aliivibrio fischeri, in this specific case agreeing with the claimed "green character" of DES. Among the starting materials, ethylene glycol was the least toxic, whereas [N3333]Cl was the most toxic (30 min-EC50 = 96.49 g L-1 and 0.5456 g L-1, respectively). DES toxicity followed the same trend as observed for the salts: [N1111]Cl-based DES < [N2222]Cl-based DES < [N3333]Cl-based DES. The IA model, with specific deviations, adjusted better in 5 out of 6 DES. Antagonism was observed for [N1111]Cl-based DES, and synergism for [N3333]Cl-based DES and for 1-propanol:[N2222]Cl. The application of the mixture toxicity models represents a breakthrough in the problematic of assessing the toxicity of the countless number of DES that can be created with the same starting materials, since they provide the expected toxicity of any virtual combination between HBA and HBD.

Correction to: Stepwise strategy for monitoring toxic cyanobacterial blooms in lentic water bodies.

Unfortunately, the name of the third author was incorrectly captured in the published online paper.

Stepwise strategy for monitoring toxic cyanobacterial blooms in lentic water bodies.

Climate change has been causing the increase in frequency, severity, and duration of harmful algal blooms, which makes the establishment of water management strategies indispensable. For cyanobacteria, several methods are currently used in monitoring programs. However, these methods are time-consuming and require specialists, and results are usually not provided within an adequate timeframe for taking timely mitigation actions. This work proposes a strategy for a faster, easier, and more cost-effective monitoring of cyanobacterial blooms, using a stepwise approach based on fluorometric determination of phycocyanin at an early stage. Complementary parameters (chlorophyll a, enumeration of dominant cyanobacterial species and cyanotoxin potential and quantification) are determined when necessary, thus progressively allocating human and financial resources within the monitoring program. This strategy was applied and validated using nine lentic eutrophic freshwater bodies prone to the occurrence of cyanobacterial blooms. Samples were sequentially evaluated, and the study ended up with two samples that showed high health risks. However, according to WHO guidelines, eight of the nine samples would be classified as having "moderate risk of adverse health effects" and could lead to preventive measures that would have an important regional economic impact. Therefore, the present approach proved to be a promising alternative to increase the effectiveness and accuracy of the risk assessment process in water bodies where cyanobacterial blooms occur.