Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (P(3HB-co-3HV) copolymers are an attractive class of biopolymers whose properties can be tailored by changing the 3-hydroxyvalerate monomer (3HV) concentration, offering the possibility of counteracting problems related to high crystallinity, brittleness, and processability. However, there are few studies about the effects of 3HV content on the processability of copolymers. The present study aims to provide new insights into the effect of 3HV content on the processing step including common practices like compounding, addition of nucleation agents and/or amorphous polymers as plasticizers. P(3HB-co-3HV)-based films containing 3, 18, and 28 mol % 3HV were processed into films by extrusion and subsequent molding. The characterization results confirmed that increasing the 3HV content from 3 to 28 mol % resulted in a decrease in the melting point (from 175 to 100 °C) and an improvement in mechanical properties (i.e., elongation at break from 7 ± 1% to 120 ± 3%). The behavior of P(3HB-co-3HV) in the presence of additives was also investigated. It was shown that an increase in the 3HV content leads to better miscibility with amorphous polymers.

Volatile fatty acids obtained from the fermentation of the organic fraction of municipal solid waste can be used as raw materials for non-toxic ethyl ester (EE) synthesis as well as feedstock for the production of polyhydroxyalkanoates (PHAs). Taking advantage of the concept of an integrated process of a bio-refinery, in the present paper, a systematic investigation on the extraction of intracellular poly(3-hydroxybutyrate-co-3-hydroxyvalerate), produced by mixed microbial culture by using EEs was reported. Among the tested EEs, ethyl acetate (EA) was the best solvent, dissolving the copolymer at the lowest temperature. Then, extraction experiments were carried out by EA at different temperatures on two biomass samples containing PHAs with different average molecular weights. The parallel characterization of the extracted and non-extracted PHAs evidenced that at the lower temperature (100 °C) EA solubilizes preferentially the polymer fractions richer in 3HV comonomers and with the lower molecular weight. By increasing the extraction temperature from 100 °C to 125 °C, an increase of recovery from about 50 to 80 wt% and a molecular weight reduction from 48% to 65% was observed. The results highlighted that the extracted polymer purity is always above 90 wt% and that it is possible to choose the proper extraction condition to maximize the recovery yield at the expense of polymer fractionation and degradation at high temperatures or use milder conditions to maintain the original properties of a polymer.

A great research effort is involved in polyhydroxyalkanoates (PHAs) production and characterization since they are an attractive degradable polyester family that potentially could substitute oil-based polymers. This is due to two main key factors: their production is sustainable, being that they are produced by microorganisms possibly fed by organic waste-derived products, and they are degradable. Moreover, PHAs’ thermal and mechanical properties could be tuned by varying their monomeric composition through the proper selection of microorganism feedstock and bioreactor operative conditions. Hence, a rapid and facile determination of the PHA chemical structure by widely available instrumentation is useful. As an alternative to the standard gas-chromatographic method, a new procedure for the composition determination of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HBV), the most common PHA copolymer, by attenuated total reflection FTIR (ATR-FTIR) is presented. It is based on the linear dependence of selected and normalized absorption band intensity with the molar fraction of repeating units. To break free from the crystallinity variability, which affects the result reproducibility and data scattering, the polymer sample was rapidly quenched from the melt directly on the surface of the ATR internal reflection element and analyzed. The data obtained from 14 samples with a molar fraction of 3-hydroxybutyrate repeating units (X_3HB) ranging from 0.15 to 1 were analyzed. According to preliminary analyses, the normalized intensity of two absorption bands was selected to develop a calibration method able to predict X_3HB of unknown samples and to evaluate the related uncertainty through prediction intervals of inverse regression. The proposed method proves to be useful for an easy and rapid estimation of P3HBV composition.

In this work, polyhydroxy butyrate (PHB) and biochar from pine wood (PWB) are used in a mini-pilot scale biological reactor (11.3 L of geometric volume) for trichloroethylene (TCE) removal (80 mgTCE/day and 6 L/day of flow rate). The PHB-biochar reactor was realized with two sequential reactive areas to simulate a multi-reactive permeable barrier. The PHB acts as an electron donor source in the first “fermentative” area. First, the thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses were performed. The PHB-powder and pellets have different purity (96% and 93% w/w) and thermal properties. These characteristics may affect the biodegradability of the biopolymer. In the second reactive zone, the PWB works as a Dehalococcoides support and adsorption material since its affinity for chlorinated compounds and the positive effect of the “coupled adsorption and biodegradation” process has been already verified. A specific dechlorinating enriched culture has been inoculated in the PWB zone to realize a coupled adsorption and biodegradation process. Organic acids were revealed since the beginning of the test, and during the monitoring period the reductive dichlorination anaerobic pathway was observed in the first zone; no chlorinated compounds were detected in the effluent thanks to the PWB adsorption capacity.

The production of polyhydroxyalkanoates (PHAs) has been herein investigated by using an organic acid mixture originated from a pilot-scale acidogenic fermentation (AF) of reground pasta (RP) byproduct. The pilot-scale AF process was conducted either under no pH control or with the pH maintained at a value of 5.90, with the two obtained fermented mixtures termed RP-fermented 1 and RP-fermented 2, respectively. The fermented mixtures were fed to a lab-scale sequencing batch reactor (SBR), operated at short hydraulic retention time (HRT, 0.5 days) and sludge retention time (SRT, 1 day) and at two values of the applied organic loading rate (OLR) of 2.12 gCOD_ACIDS/Ld and 4.25 gCOD_ACIDS/Ld. During all of the SBR operating conditions, a high selective microbial pressure was established, as confirmed by both the microbiology analysis and the detected values of the storage yield (which reached a maximum value of 0.68 ± 0.04 COD_PHA/COD_ACIDS). A poly(hydroxybutyrate/hydroxyvalerate) copolymer and a poly(hydroxybutyrate/hydroxyvalerate/hydroxyhexanoate) terpolymer were produced with the RP-fermented 1 and RP-fermented 2 streams, respectively. When the OLR of 2.12 gCOD_ACIDS/Ld was applied to the SBR, the stored copolymer and terpolymer presented very similar molecular weights of 339 and 389 kDa, respectively.