Optimization of two-phase synthesis of Fe-hydrochar for arsenic removal from drinking water: Effect of temperature and Fe concentration.

Arsenic-contaminated water is a global concern that demands the development of cost-effective treatments to ensure a safe drinking water supply for people worldwide. In this paper, we report the optimization of a two-phase synthesis for producing a hydrochar core from olive pomace to serve as support for the deposition of Fe-hydroxide, which is the active component in As(V) removal. The operating conditions considered were the initial concentration of Fe in solution in the hydrothermal treatment (phase I) and the temperature of Fe precipitation (phase II). The obtained samples were characterized for their elemental composition, solid yield, mineral content (Fe and K), phenol release, As(V) sorption capacity, and sorbent stability. Correlation analysis revealed that higher Fe concentrations (26.8 g/L) ensured better carbonization during hydrothermal treatment, increased arsenic removal, reduced concentrations of phenols in the final liquid, and improved stability of the sorbent composite. On the other hand, the temperature during Fe precipitation (phase II) can be maintained at lower levels (25-80 °C) since higher temperatures yielded lower adsorption capacity. Regression analysis demonstrated the significance of the main effects of the parameters on sorption capacity and provided a model for selecting operating conditions (Fe concentration and phase II temperature) to obtain composite sorbents with tailored sorption properties.

Structured population balances to support microalgae-based processes: Review of the state-of-art and perspectives analysis.

Design and optimization of microalgae processes have traditionally relied on the application of unsegregated mathematical models, thus neglecting the impact of cell-to-cell heterogeneity. However, there is experimental evidence that the latter one, including but not limited to variation in mass/size, internal composition and cell cycle phase, can play a crucial role in both cultivation and downstream processes. Population balance equations (PBEs) represent a powerful approach to develop mathematical models describing the effect of cell-to-cell heterogeneity. In this work, the potential of PBEs for the analysis and design of microalgae processes are discussed. A detailed review of PBE applications to microalgae cultivation, harvesting and disruption is reported. The review is largely focused on the application of the univariate size/mass structured PBE, where the size/mass is the only internal variable used to identify the cell state. Nonetheless, the need, addressed by few studies, for additional or alternative internal variables to identify the cell cycle phase and/or provide information about the internal composition is discussed. Through the review, the limitations of previous studies are described, and areas are identified where the development of more reliable PBE models, driven by the increasing availability of single-cell experimental data, could support the understanding and purposeful exploitation of the mechanisms determining cell-to-cell heterogeneity.

A fattening factor to quantify the accumulation ability of microorganisms under N-starvation.

Many microorganisms can accumulate biomass in the form of lipids and polysaccharides, which can be used for biofuels, bioplastics, food and feed. Some innovative bioprocesses exploit the competitive advantage provided by such accumulation ability, mainly under N-starvation, to select high-accumulating strains against biological contaminants, by using uncoupled nutrient feeding. However, there is no general and easily comparable parameter available to compare biomass accumulation ability among different microbial strains, which could measure the competitive advantage. Here, a parameter termed "fattening factor" (ηx) is described to quantify such strain-specific biomass accumulation ability in bacteria, yeasts and microalgae. This parameter measures how many fold a microbial population can increase its biomass just as the result of accumulation. It is derived from considerations about the main metabolic aspects of cells' response to N-starvation, which induces variations in cell cycle, biomass production and biochemical composition. The fattening factor described here should be easily estimatable in N-starvation for every culturable microbial strain, by measuring the amount of accumulated biomass.

Two-phase synthesis of Fe-loaded hydrochar for As removal: The distinct effects of initial pH, reaction time and Fe/hydrochar ratio.

Hydrothermal carbonization (HTC) is a promising technology for producing char material (hydrochar) from waste biomass. In the present work, a two-stage process was applied and optimized to obtain a composite Fe-loaded hydrochar effective in removing arsenic from water. The first stage of carbonization of the biomass in acid conditions was followed by loading Fe3O4 in the second stage into the hydrochar by alkaline co-precipitation. The effect on the kinetics and on the final yield of HTC induced by a variation of the initial acid pH (5.6, 2.0, and 0.5) was tested. Biomass hydrolysis initially decreased the hydrochar yield and released soluble organic species, responsible for the observed pH variation. This effect was more remarkable at the lower initial pH tested. Soluble organic compounds eventually underwent polymerization, with secondary char formation, an inversion of the pH trend and an increase of hydrochar yield and C%. The final pH attained was linearly related to the hydrochar C%, O/C ratio, and initial pH. Better carbonization performances were achieved at pH = 0.5, 200 °C, and 30 min reaction time, which resulted in 53% mass yield and 72 C%. This value is larger than those previously reported for processes conducted at higher temperatures, and it shows how the addition of acid allows working at lower operative temperatures. Fe loading gave better yields at lower hydrochar concentrations, producing an adsorbent with up to 74% Fe3O4, which adsorbed 2.67 mg/g arsenic. Its adsorption capacity was remarkably affected by the stirring method used, indicating that particle-to-particle interactions considerably influence the process. This effect should be better studied for improved applications in fixed-bed columns.

Cultivation processes to select microorganisms with high accumulation ability.

The microbial ability to accumulate biomolecules is fundamental for different biotechnological applications aiming at the production of biofuels, food and bioplastics. However, high accumulation is a selective advantage only under certain stressful conditions, such as nutrient depletion, characterized by lower growth rate. Conventional bioprocesses maintain an optimal and stable environment for large part of the cultivation, that doesn't reward cells for their accumulation ability, raising the risk of selection of contaminant strains with higher growth rate, but lower accumulation of products. Here in this work the physiological responses of different microorganisms (microalgae, bacteria, yeasts) under N-starvation and energy starvation are reviewed, with the aim to furnish relevant insights exploitable to develop tailored bioprocesses to select specific strains for their higher accumulation ability. Microorganism responses to starvation are reviewed focusing on cell cycle, biomass production and variations in biochemical composition. Then, the work describes different innovative bioprocess configurations exploiting uncoupled nutrient feeding strategies (feast-famine), tailored to maintain a selective pressure to reward the strains with higher accumulation ability in mixed microbial populations. Finally, the main models developed in recent studies to describe and predict microbial growth and intracellular accumulation upon N-starvation and feast-famine conditions have been reviewed.

Extracellular and intracellular phenol production by microalgae during photoautotrophic batch cultivation.

Understanding the mechanisms of phenol production by microalgae can contribute to the development of microalgal biorefinery processes with higher economic and environmental sustainability. However, little is known about how phenols are produced and accumulate during microalgal cultivation. In this study, both extracellular and intracellular phenol production by two microalgal strains (Tetradesmus obliquus and Chlorella sp.) were investigated throughout a conventional photoautotrophic batch cultivation. The highest intracellular phenol content (10-25 mg g-1) and productivity (12-18 mg L-1 d-1) were attained for both strains in the first part of the batch, indicating a positive relation with nutrient availability and biomass productivity. Extracellular phenol production was 2-20 fold lower than intracellular phenols, but reached up to 27 mg L-1 for T. obliquus and 13 mg L-1 for Chlorella sp. The latter finding highlights relevant issues about the management of the exhausted culture medium, due to likely antimicrobial effects.

Sustainable Bioactive Packaging Based on Thermoplastic Starch and Microalgae.

This study combines the use of corn starch and Tetradesmus obliquus microalgae for the production of antioxidant starch films as flexible packaging material. Starch was plasticized with glycerol and blended with 1 w% polyallylamine chosen as an agent to modify the film physical properties. The addition of polyallylamine improved film water stability and water vapor transmission rate as well as mechanical stiffness and tenacity. The dried Tetradesmus obliquus microalgae, which showed an EC50 value of 2.8 mg/mg DPPH (2.2-Diphenyl-1-picrylhydrazyl radical), was then used as antioxidant filler. The addition of microalgae provided the films with good antioxidant activity, which increased with microalgae content increasing. To our knowledge, this is the first study reporting the development of sustainable bioactive packaging films composed of almost 100% starch, and follows the European union's goals on plastics strategy concerning the promotion of bio-based, compostable plastics and the setting up of approaches to prevent food waste with a simple plastic packaging.

Production of an iron-coated adsorbent for arsenic removal by hydrothermal carbonization of olive pomace: Effect of the feedwater pH.

The removal of arsenic from water by adsorption is currently hindered by the elevated cost of conventional adsorbent materials. To overcome this limit, an innovative iron-coated adsorbent was produced by hydrothermal carbonization (170 °C, 30 min) of olive pomace, an inexpensive byproduct of the olive oil production. Hydrothermal carbonization experiments were performed starting from olive pomace dispersions in solutions with acidic, neutral and alkaline pH, in presence and absence of FeCl3. Acidic conditions improved the carbonization, ensuring reduced H/C and O/C ratios, and increased the adsorbent stability. However, acidic pH yielded unsatisfactory iron coating, with only 32% of the iron dissolved in the initial solution transferred to the produced hydrochar. Under alkaline pH, 96% of the iron in the feedwater was, in contrast, stably dispersed over the hydrochar surface, giving the highest maximum arsenic adsorption capacity (4.1 mg/g). However, alkaline pH promoted biomass hydrolysis, causing the loss of 60% and 87% of the total C and N, respectively, and reducing the stability of the produced hydrochar. A two-stage process was tested to overcome these issues, including hydrothermal carbonization under acidic pH with FeCl3, followed by the addition of NaOH. This process prevented biomass hydrolysis yielding a stable hydrochar. However, as compared to the one-stage alkaline synthesis, the two-stage process produced an hydrochar with reduced arsenic adsorption capacity (1.4 mg/g), indicating that biomass hydrolysis could positively influence hydrochar adsorption characteristics, possibly by increasing the specific surface area. Indications are then provided on how to optimize the two-stage process in order to produce a hydrochar with both satisfactory stability and arsenic adsorption capacity.

Extraction of Carotenoids and Fat-Soluble Vitamins from Tetradesmus Obliquus Microalgae: An Optimized Approach by Using Supercritical CO2.

In recent years, great attention has been focused on rapid, selective, and environmentally friendly extraction methods to recover pigments and antioxidants from microalgae. Among these, supercritical fluid extraction (SFE) represents one of the most important alternatives to traditional extraction methods carried out with the use of organic solvents. In this study, the influence of parameters such as pressure, temperature, and the addition of a polar co-solvent in the SFE yields of carotenoids and fat-soluble vitamins from T. obliquus biomass were evaluated. The highest extraction of alpha-tocopherol, gamma-tocopherol, and retinol was achieved at a pressure of 30 MPa and a temperature of 40 °C. It was observed that overall, the extraction yield increased considerably when a preliminary step of sample pre-treatment, based on a matrix solid phase dispersion, was applied using diatomaceous earth as a dispersing agent. The use of ethanol as a co-solvent, under certain conditions of pressure and temperature, resulted in selectively increasing the yields of only some compounds. In particular, a remarkable selectivity was observed if the extraction was carried out in the presence of ethanol at 10 MPa and 40 °C: under these conditions, it was possible to isolate menaquinone-7, a homologous of vitamin K2, which, otherwise, cannot not recovered by using traditional extraction procedures.

Quantification of Tetradesmus obliquus (Chlorophyceae) cell size and lipid content heterogeneity at single-cell level.

Much of our current knowledge of microbial growth is obtained from studies at a population level. Driven by the realization that processes that operate within a population might influence a population's behavior, we sought to better understand Tetradesmus obliquus (formerly Scenedesmus obliquus) physiology at the cellular level. In this work, an accurate pretreatment method to quantitatively obtain single cells of T. obliquus, a coenobia-forming alga, is described. These single cells were examined by flow cytometry for triacylglycerol (TAG), chlorophyll, and protein content, and their cell sizes were recorded by coulter counter. We quantified heterogeneity of size and TAG content at single-cell level for a population of T. obliquus during a controlled standard batch cultivation. Unexpectedly, variability of TAG content per cell within the population increased throughout the batch run, up to 400 times in the final stage of the batch run, with values ranging from 0.25 to 99 pg · cell-1 . Two subpopulations, classified as having low or high TAG content per cell, were identified. Cell size also increased during batch growth with average values from 36 to 70 µm3  · cell-1 ; yet cell size variability increased only up to 16 times. Cell size and cellular TAG content were not correlated at the single-cell level. Our data show clearly that TAG production is affected by cell-to-cell variation, which suggests that its control and better understanding of the underlying processes may improve the productivity of T. obliquus for industrial processes such as biodiesel production.

Effect of Ca2+ concentration on Scenedesmus sp. growth in heterotrophic and photoautotrophic cultivation.

The influence of Ca2+ concentration on the growth of the microalga Scenedesmus sp. in heterotrophic and photoautotrophic cultivations was investigated. Heterotrophic growth was induced by the addition of olive mill wastewaters (9% v·v-1) to the culture. Variations in the calcium concentration affected differently biomass production depending on whether microalgae were cultivated under heterotrophic or photoautotrophic regime. In photoautotrophic regime, increasing the calcium concentration from 20 to 230mg⋅L-1 decreased maximum cell concentration and growth rate. In heterotrophic cultivation, cell concentration and growth rate decreased with Ca2+ concentration increasing from 20 to 80mg⋅L-1 but then increased with Ca2+ concentration increasing to 230mg⋅L-1. Increasing calcium concentration invariably promoted cell aggregation. The precipitation of calcium phosphates can explain the decreasing growth rate and cell concentration attained with increasing calcium concentration, while the influence of Ca2+ concentration on the adsorption of phenols on suspended solids can explain the enhanced growth attained at large Ca2+ concentration under heterotrophic regime. Implications of the illustrated results for industrial scale application of microalgae are thoroughly discussed.