Magnetic Nanocomposite-Driven Harvesting of Chlorella vulgaris: Enhancing Microalgal Biomass Recovery Using Fe3O4 and Fe3O4@PEG Nanoparticles

This study reports on the synthesis and characterization of cobalt ferrite (CoFe2O4) nanoparticles (NPs) synthesized by chemical co-precipitation in alkaline medium at increasing temperatures in the range of 27 °C to 100 °C. High-quality samples in the size range of 5 to 10 nm were produced using very low stirring speed (250 rpm) and moderate alkaline aqueous solution concentration (4.8 mol/L). Three samples were synthesized and characterized by x–ray diffraction (XRD) and room-temperature (RT) magnetization measurements. All samples present superparamagnetic (SPM) behavior at RT and Rietveld refinements confirm the inverse cubic spinel structure (space group Fd-3m (227)) with minor detectable impurity phase. As the synthesis temperature increases, structural parameters such as lattice constant and grain size change monotonically from 8.385 to 8.383 Å and from 5.8 to 7.4 nm, respectively. Likewise, as the synthesis temperature increases the NPs’ magnetic moment and saturation magnetization increases monotonically from 2.6 ×103 to 16×103 μB and from 37 to 66 emu/g, respectively. The RT magnetization (M) versus applied field (H) curves were analyzed by the first-order Langevin function averaged out by a lognormal distribution function of magnetic moments. The excellent curve-fitting of the M versus H data is credited to a reduced particle-particle interaction due to both the SPM behavior and the existence of a surface amorphous shell layer (dead layer), the latter reducing systematically as the synthesis temperature increases.

Magnetite nanoparticles (MNPs) exhibit favorable heating responses under magnetic excitation, which makes them particularly suited for various hyperthermia applications. Herein, we report the detailed self-heating mechanisms of MNPs prepared via the Ko-precipitation Hydrolytic Basic (KHB) methodology. The as-prepared MNPs were fully characterized using various spectroscopic techniques including transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), and vibrating sample magnetometry (VSM). MNPs exhibited stable 15 nm quasi-spherical small-sized particles, pure crystalline cubic Fe3O4 phases, high saturation magnetizations (Ms = ~40 emu·g−1), and superparamagnetic behavior. In response to alternating magnetic fields (AMFs), these MNPs displayed excellent self-heating efficiencies with distinctive heating responses, even when minimal doses of MNPs were used. Heating efficacies and specific absorption rate (SAR) values as functions of concentration, frequency, and amplitude were systematically investigated. Remarkably, within only a few minutes, MNPs (2.5 mg/mL) showed a rapid dissipation of heat energy, giving a maximum intrinsic loss power (ILP) of 4.29 nHm2/kg and a SAR of 261 W/g. Hyperthermia temperatures were rapidly reached in as early as 3 min and could rise up to 80 °C. In addition, Rietveld refinement, Langevin, and linear response theory (LRT) models were studied to further assess the magnetic and heating mechanisms. The LRT model was used to determine the Néel relaxation time (τR = 5.41 × 10−7 s), which was compared to the Brownian relation time value (τB = 11 × 10−7 s), showing that both mechanisms are responsible for heat dissipated by the MNPs. Finally, the cytotoxicity assay was conducted on aqueous dispersions of MNPs, indicating their biocompatibility and low toxicity. Our results strongly suggest that the as-prepared Fe3O4 MNPs are promising vehicles for potential magnetically triggered biomedical hyperthermia applications.

Ultrasound-assisted co-precipitation has been used to prepare nano-sized Ni0.4Cu0.2Zn0.4Fe2O4 ferrite. Continuous (C-US) and pulsed (P-US) ultrasound modes are used at constant frequency = 20 kHz, reaction time = 2 h and pulse durations of 10 s on and 10 s off. All experiments were conducted at two temperatures 90 and 100°C. Samples were characterized by X-ray diffraction (XRD), Fourier transform spectroscopy (FT-IR), N2 adsorption isotherms at 77 k analysis (BET), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM) techniques. A nanocrystalline single-phase with particle size in the range 12–18 nm is obtained in both modes: continuous and pulsed ultrasound mode. FT-IR measurements show two absorption bands assigned to the tetrahedral and octahedral vibrations (ν1 and ν2) characteristics of cubic spinel ferrite. The specific surface area (SBET) is in the range of 110–140 m2 g−1 and an average pore size between 5.5 and 6.5 nm. The lowest values are obtained in pulsed mode. Finally, this work shows that the magnetic properties are affected by the ultrasound conditions, without affecting the particle shape. The saturation magnetization (Ms) values obtained for all samples are comparable. In P-US mode, the saturation magnetization (Ms) increases as temperature increases. Moreover, P-US mode opens a new avenue for synthesis of NiCuZn ferrites.

Soil nutrient availability is a key constraint on tropical forest growth. On highly weathered soils, intact forests' carbon-nutrient cycles have developed over pedogenic time scales, leading to tight nutrient cycling of some depleted elements, such as phosphorus. Ecosystem nutrient recycling and plant nutrient limitation are predominant in lowland Amazonia, controlling the forests' response to disturbance and climate change. Deforestation, biomass removal, and fire lead to the loss of carbon and nutrients previously stored in vegetation, potentially enforcing nutrient limitation and reducing carbon storage in regrowing forests.   Here, we employ the process-based terrestrial biosphere model QUINCY (Thum et al., 2019), coupled with the microbial-explicit soil model JSM (Yu et al., 2020) to simulate carbon and nutrient cycling rates at intact Amazonian forest sites, which span a natural gradient of 30 to 727 mg phosphorus g dry soil-1, and from 2 to 81% clay. The model QUINCY-JSM accounts for dynamic plant carbon investment in growth and nutrient acquisition, and microbial-explicit growth, turnover, and nutrient cycling. We confront the ecosystems with historical changes in atmospheric CO2 and climate, and simulate an experimental harvest of the entire forest stand to assess the consequences of that nutrient loss on the regrowing forest stand. Simulations of the Amazon forest sites are in good agreement with forest census data on vegetation carbon dynamics. Biologically-driven nutrient mineralization represents the main source of nutrients for plants, with negligible contribution of inorganic nutrient cycling in highly weathered sites. After experimental deforestation, we find that the inorganic nutrient supply is insufficient and restricts forest growth, leading to lower vegetation biomass equilibrium after deforestation. Our simulations suggest that forest degradation may occur through biomass removal in tropical forests.Thum, T., Caldararu, S., Engel, J., Kern, M., Pallandt, M., Schnur, R., et al. (2019). A new model of the coupled carbon, nitrogen, and phosphorus cycles in the terrestrial biosphere (QUINCY v1.0; revision 1996). Geoscientific Model Development, 12(11), 4781–4802. https://doi.org/10.5194/gmd-12-4781-2019Yu, L., Ahrens, B., Wutzler, T., Schrumpf, M., & Zaehle, S. (2020). Jena Soil Model (JSM v1.0; Revision 1934): A microbial soil organic carbon model integrated with nitrogen and phosphorus processes. Geoscientific Model Development, 13(2), 783–803. https://doi.org/10.5194/gmd-13-783-202

Microalgae are considered as one promising source of third-generation biofuels due to their fast growth rates, potentially higher yield rates and wide ranges of growth conditions. However, the extremely low biomass concentration in microalgae cultures presents a great challenge to the harvesting of microalgae because a large volume of water needs to be removed to obtain dry microalgal cells for the subsequent oil extraction process. In this study, the fresh water microalgae Chlorella vulgaris (C. vulgaris) was effectively harvested using both low molecular weight (MW) and high MW chitosan flocculants. The flocculation efficiency was evaluated by physical appearance, supernatant absorbance, zeta potential and solids content after centrifugal dewatering. High flocculation efficiency of 98.0-99.0% was achieved at the optimal dosage of 30-40 mg/g with formation of large microalgae flocs. This study suggests that the polymer bridging mechanism was governing the flocculation behaviour of C. vulgaris using high MW chitosan. Besides, charge patch neutralisation mechanism prevailed at low MW chitosan where lower dosage was sufficient to reach near-zero zeta potential compared with the high MW chitosan. The amount of chitosan polymer present in the culture may also affect the mechanism of flocculation.

Sanitizing effect of ethanol on a Yersinia enterocolitica biofilm was evaluated in terms of biomass removal and bactericidal activity. We found that 40% ethanol was most effective for biofilm biomass removal; however, no significant difference was observed in bactericidal activity between treatment with 40 and 70% ethanol. This unexpected low ethanol concentration requirement for biomass removal was confirmed using biofilms of two additional pathogenic bacteria, Aeromonas hydrophila and Xanthomonas oryzae. Although only three pathogenic Gram-negative bacteria were tested and the biofilm in nature was different from the biofilm in this study, the results in this study suggested the possible re-evaluation of the effective sanitizing ethanol concentration 70%, which is the concentration commonly employed for sanitization, on bacteria in a biofilm.

Experiments demonstrating that cytochrome (cyt) b5 inhibits the activity of cytochrome P450 2B4 (cyt P450 2B4) at higher concentrations suggested that cyt b5 was occupying the cyt P450 reductase-binding site on cyt P450 2B4 and preventing the reduction of ferric cyt P450 (Zhang, H., Im, S.-C., and Waskell, L. (2007) J. Biol. Chem. 282, 29766-29776). In this work experiments were undertaken with manganese-containing cyt b5 (Mn-cyt b5) to test this hypothesis. Because Mn-cyt b5 does not undergo oxidation state changes under our experimental conditions, interpretation of the experimental results was unambiguous. The rate of electron transfer from cyt P450 reductase to ferric cyt P450 2B4 was decreased by Mn-cyt b5 in a concentration-dependent manner. Moreover, reduction of cyt P450 2B4 by cyt P450 reductase was incomplete in the presence of Mn-cyt b5. At a Mn-cyt b(5):cyt P450 2B4:cyt P450 reductase molar ratio of 5:1:1, the rate of reduction of ferric cyt P450 was decreased by 10-fold, and only 30% of the cyt P450 was reduced, whereas 70% remained oxidized. It could be demonstrated that Mn-cyt b5 had its effect by acting on cyt P450, not the reductase, because the reduction of cyt c by cyt P450 reductase in the presence of Mn-cyt b5 was not effected. Furthermore, under steady-state conditions in the cyt P450 reconstituted system, Mn-cyt b5, which lacks the ability to reduce oxyferrous cyt P450 2B4, was unable to stimulate the activity of cyt P450. Mn-cyt b5 only inhibited the cyt P450 2B4 activity. In conjunction with site-directed mutagenesis studies and experiments that strongly suggested that cyt b5 competed with cyt P450 reductase for binding to cyt P450, the current investigation demonstrates unequivocally that cyt b5 inhibits the activity of cyt P450 2B4 by preventing cyt P450 reductase from binding to cyt P450, a prerequisite for electron transfer from cyt P450 reductase to cyt P450 and catalysis.

The presence of pharmaceutical residues in aquatic systems poses a growing environmental concern, necessitating the development of sustainable and efficient sensing materials. In this study, haloalkaliphilic archaea were employed as green biocatalysts for the synthesis of magnetite (Fe₃O₄) nanoparticles and their application in the electrochemical detection of ibuprofen under saline conditions. Two archaeal strains produced Fe₃O₄ nanoparticles with well-defined inverse spinel crystal structures, nanoscale dimensions, and superparamagnetic behavior, while exhibiting distinct surface chemistry and magnetic properties. Strain-dependent differences in crystallinity and surface functionalization were found to strongly influence electrochemical performance. RA5-derived nanoparticles exhibited higher crystallinity and enhanced charge-transfer efficiency, achieving a sensitivity of 2.105 µA mg L⁻¹ and a limit of detection of 0.927 mg L⁻¹. In contrast, A6-derived nanoparticles featured a richer organic surface corona that promoted analyte adsorption, resulting in a sensitivity of 2.2186 µA mg L⁻¹ and a detection limit of 1.05 mg L⁻¹. Both modified electrodes enabled reliable ibuprofen detection over a wide linear concentration range of 0–100 mg L⁻¹. These results demonstrate that haloalkaliphilic archaea can function as sustainable nano-factories for producing functional magnetic nanomaterials, offering an eco-friendly strategy for electrochemical monitoring of pharmaceutical contaminants in complex aquatic environments.

Toxicity of cobalt ferrite (CoFe2O4) nanobeads in Chlorella vulgaris: Interaction, adaptation and oxidative stress

Bacteria associated with seaweeds can both harm and benefit their hosts. Many seaweed species are known to produce compounds that inhibit growth of bacterial isolates, but the ecological role of seaweed metabolites for the associated bacterial community structure is not well understood. In this study the response of a colonizing bacterial community to the secondary metabolite (1,1,3,3-tetrabromo-2-heptanone) from the red alga Bonnemaisonia hamifera was investigated by using field panels coated with the metabolite at a range of concentrations covering those measured at the algal surface. The seaweed metabolite has previously been shown to have antibacterial effects. The metabolite significantly affected the natural fouling community by (i) altering the composition, (ii) altering the diversity by increasing the evenness and (iii) decreasing the density, as measured by terminal restriction fragment length polymorphism in conjunction with clone libraries of the 16S rRNA genes and by bacterial enumeration. No single major bacterial taxon (phylum, class) was particularly affected by the metabolite. Instead changes in community composition were observed at a more detailed phylogenetic level. This indicates a broad specificity of the seaweed metabolite against bacterial colonization, which is supported by the observation that the bacterial density was significantly affected at a lower concentration (0.02 μg cm−2) than the composition (1–2.5 μg cm−2) and the evenness (5 μg cm−2) of the bacterial communities. Altogether, the results emphasize the role of secondary metabolites for control of the density and structure of seaweed-associated bacterial communities.

The marine macroalga, Ulva lactuca, has been exposed for 48h to different concentrations of Ag added as either silver nanoparticles (AgNP) or aqueous metal (AgNO(3)) and the resulting toxicity, estimated from reductions in quenching of chlorophyll-a fluorescence, and accumulation of Ag measured. Aqueous Ag was toxic at available concentrations as low as about 2.5μgl(-1) and exhibited considerable accumulation that could be defined by the Langmuir equation. AgNP were not phytotoxic to the macroalga at available Ag concentrations up to at least 15μgl(-1) and metal measured in U. lactuca was attributed to a physical association of nanoparticles at the algal surface. At higher AgNP concentrations, a dose-response relationship was observed that was similar to that for aqueous Ag recorded at much lower concentrations. These findings suggest that AgNP are only indirectly toxic to marine algae through the dissolution of Ag(+) ions into bulk sea water, albeit at concentrations orders of magnitude greater than those predicted in the environment.

The soluble selenium oxyanion, selenite (Se(IV)) is toxic and it bioaccumulates at low concentrations which is why its presence in aquatic systems has to be regulated. Pseudomonas stutzeri NT-I is one of the numerous microorganisms capable of reducing Se(IV) into the relatively less toxic Se(0). Previous studies using strain NT-I have mainly focused on Se(IV) reduction occurring in the presence of bacterial biomass for the entirety of the reaction. However, it has been reported that some pseudomonas strains are capable of secreting biomolecules or metabolites into their surrounding environments which aid Se(IV) reduction. In this study, aerobic batch reduction of 2 mM Se(IV) was carried out in two stages, that is, firstly in the presence of bacterial biomass for 1 h (in order to initiate the reaction) and secondly in the absence of biomass by use of the bacterial supernatant (cell-free extract), post biomass removal. This was done to investigate the selenium reducing capabilities of the cell-free extracts. Obtained results showed that the total Se(IV) reduction within the first hour prior to biomass removal was rapid, translating to an average reduction rate of 0.45 mmol.h-1 and a 22 % reduction in the Se(IV) concentration. However, Se(IV) reduction still occurred post biomass removal by use of the cell-free extract, albeit at a slower rate. The average reduction rate was 0.01 mmol.h-1 and the Se(IV) removal was 58 %. From these results, it was concluded that the bacterial biomass likely secreted metabolites which remained in the medium after the removal of biomass. It is these secreted metabolites which are thought to possess selenite reducing capabilities.

Interactions between bacteriophages (phages) and biofilms are poorly understood despite their broad ecological and water quality implications. Here, we report that biofilm exposure to lytic polyvalent phages at low concentrations (i.e., 102-104 phages/mL) can counterintuitively promote biofilm growth and densification (corroborated by confocal laser scanning microscopy (CLSM)). Such exposure hormetically upregulated quorum sensing genes (by 4.1- to 24.9-fold), polysaccharide production genes (by 3.7- to 9.3-fold), and curli synthesis genes (by 4.5- to 6.5-fold) in the biofilm-dwelling bacterial hosts (i.e., Escherichia coli and Pseudomonas aeruginosa) relative to unexposed controls. Accordingly, the biofilm matrix increased its polysaccharide and extracellular DNA content relative to unexposed controls (by 41.8 ± 2.3 and 81.4 ± 2.2%, respectively), which decreased biofilm permeability and increased structural integrity. This contributed to enhanced resistance to disinfection with chlorine (bacteria half-lives were 6.08 ± 0.05 vs 3.91 ± 0.03 min for unexposed controls) and to subsequent phage infection (biomass removal was 18.2 ± 1.2 vs 32.3 ± 1.2% for unexposed controls), apparently by mitigating diffusion of these antibacterial agents through the biofilm. Overall, low concentrations of phages reaching a biofilm may result in unintended biofilm stimulation, which might accelerate biofouling, biocorrosion, or other biofilm-related water quality problems.

In a previous paper (J. Mater. Chem., 1996, 6, 573), we reported that colloidal silver dispersions can be synthezised by the polyol process, using an ethylene glycol–polyvinylpyrolidone (PVP) solution to reduce silver nitrate under precise temperature conditions. Quasi-spherical particles with a narrow size distribution were obtained. Low precursor and PVP concentrations, in contrast to high silver nitrate concentrations, were found to yield monodisperse systems with an average particle size of 15 to 21 nm. To understand the particle formation mechanism, the evolution of particle size and shape during the reaction was monitored by TEM and UV absorption spectroscopy techniques. An Ostwald ripening mechanism is proposed to account for the formation of the silver particles, even though the variation of temperature with time is not ideal for a complete mechanistic understanding.

Biofilm removal efficacy using direct electric current in cross-flow ultrafiltration processes for water treatment