Synergistic Ozone-Ultrasonication Pretreatment for Enhanced Algal Bioresource Recovery: Optimization and Detoxification

Although algae possess a high capacity for carbon sequestration, the recalcitrant multilayered cell wall structure and residual microcystin toxicity associated with Microcystis aeruginosa significantly hinder the efficient recovery of algal biomass resources. This study developed a synergistic ozone-ultrasonication (O3-US) pretreatment strategy, systematically comparing its cell-disruption efficacy with standalone O3 or US, using harvested algal biomass from natural aquatic systems dominated by Microcystis aeruginosa. The synergistic effects revealed were: (1) O3-mediated oxidation of extracellular polymeric substances and cell wall matrices, (2) the release of ultrasound-induced cavitation-enhancing intracellular components, and (3) an improvement in the O3 mass transfer by hydrodynamic shear forces. Through response surface methodology optimization, the O3-US process achieved maximal performance at 0.14 gO3/gTSS, with a 4 W/mL ultrasonic intensity, and a 20 min duration. Remarkably, the released protein was 289.2 mg/gTSS, which was 4.3-fold and 1.9-fold, respectively, more than that released in O3 pretreatment and US pretreatment, while the polysaccharide was 87.5 mg/gTSS, increased by 2.4-fold and 3.1-fold respectively, compared to O3 alone and US alone. The released solubilized chemical oxygen demand (SCOD) was 1037.1 mg/gTSS, increased by 43.3% and 216.1%, respectively, relative to O3 alone and US alone. DNA quantification further validated the synergistic cell disruption caused by O3-US. Fluorescence excitation-emission matrix (EEM) spectroscopy identified biodegradable aromatic proteins (Regions I-II) and soluble microbial byproducts (Region IV) as dominant organic fractions, demonstrating enhanced bioavailability. The hybrid process reduced energy consumption by 33.3% in ultrasonic intensity and 60% in duration versus US alone, while achieving 94.5% microcystin-LR (MC-LR) degradation, which showed a 96.6% risk reduction compared to ultrasonic treatment. This work establishes an efficient, low-energy, and safe pretreatment technology for algal resource recovery, synergistically enhancing intracellular resource release while mitigating cyanotoxin hazards in algal biomass valorization.