Metal-based flocculation to harvest microalgae: a look beyond separation efficiency

Metal-based flocculants are commonly used for biomass harvesting in microalgae-based bio-refineries. Besides the high separation efficiency, additional aspects should be considered, related to the toxicity of metals for the algal biomass. Partitioning tests for commonly used flocculants (i.e., FeCl₃ and Al₂(SO₄)₃) showed that metals were mostly transferred to the solid phase with more than 95% of dosed metal ending up into the biomass, and low metal concentrations in the liquid effluent (lower than 0.4 mg L^-1 for both metals), thus allowing for water reuse. Photosynthesis inhibition was tested on microalgae and microalgae-bacteria cultures, using a standardized photo-respirometry protocol in which typical concentrations used during coagulation-flocculation were assessed. Modelling dose-response curves, concentrations corresponding to 50% inhibition (IC₅₀) were obtained, describing short-term effects. The obtained IC₅₀ ranged from 13.7 to 28.3 mg Al L^-1 for Al, and from 127.9 to 195.8 mg Fe L^-1 for Fe, showing a higher toxicity for the Al-based flocculant. The recovery of photosynthesis inhibition was also quantified, to evaluate the possibility of reusing/recycling the harvested biomass. The results highlighted that the residual photosynthetic activities, evaluated after 1 h and 24 h of exposure to metals were partially recovered, especially for Al, passing from 67.3% to 94.6% activity, respectively, while long-term Fe effects were stronger (passing from 64.9% to 77.6% activity). A non-toxic flocculant (cationic starch) was finally tested, excluding potential effects due to biomass aggregation, as the reduction of photosynthetic activity only reached 3.4%, compared to control. Relevant modifications to the light availability and the optical properties of algal suspensions were assessed, identifying a strong effect of iron which caused an increase of the light absorbance up to approximately 40% at high Fe concentrations. Possible implications of dosing metallic flocculants in MBWWT processes are discussed, and suggestions are given to perform inhibition tests on flocculating chemicals.