Although the organic fraction of municipal solid waste (OFMSW) and sewage sludge (SS) originate from the same urban area and contain similar organic matter, they are collected separately and handled with different technologies. In this work, a combined treatment of OFMSW−SS mixture was investigated at pilot scale, by using a three-step mixed microbial culture (MMC) process in order to produce polyhydroxyalkanoate (PHA) as final high value biobased product. Biomass selection efficiency was quantified by PHAspecific storage rate that was 258 mg COD PHA /g COD Xa /h under the optimized process condition. In fed-batch tests, PHA-storing MMC was able to accumulate up to 46 wt % PHA. In the perspective of a full-scale application and taking into account the mass flows in each process step, an overall yield of 65 g PHA/kg TVS was estimated.
The present study reports on the production and characterization of a new biopackaging material made of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from municipal biowaste (MBW) and produced by the mixed bacterial culture technology. After purification and extraction, the MBW-derived PHBV was processed by electrospinning to yield defect-free ultrathin fibers, which were thermally post-treated. Annealing at 130 °C, well below the biopolymer's melting temperature (Tm), successfully yielded a continuous film resulting from coalescence of the electrospun fibrillar morphology, the so-called biopaper, exhibiting enhanced optical and color properties compared to traditional melt compounding routes. The crystallinity and crystalline morphology were comprehensively studied as a function of temperature by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and combined time-resolved synchrotron small-and wide-angle X-ray scattering (SAXS and WAXS) experiments, which clearly indicated that the molecular order within the copolyester was improved up to a maximum at 130 °C, and then it decreased at the biopolymer's Tm. It was hypothesized that by annealing at the temperature at which the thermally induced molecular order is maximized, the fibers generated sufficient mobility to align alongside, hence reducing surface energy and porosity. The data suggest that this material shows a good balance between enhanced mechanical and improved barrier properties to vapors and gases in comparison to traditional paper and other currently used petroleum-derived polymers, thus presenting significant potential to be part of innovative food biopackaging designs for the protection and preservation of foods in a circular bioeconomy scenario.
The utilization of food waste and sewage sludge as organic substrate from urban context for the synthesis of microbial polyhydroxyalkanoates (PHAs) has been only recently investigated at pilot scale. Within this context, two stabilization methods have been found for preserving the amount of PHA intracellularly produced by open mixed microbial culture (MMC): thermal drying and wet acidification of the biomass at the end of PHA accumulation process. The extracted PHA from the two differently stabilized biomasses was then characterized with regard to chemical composition, molecular weight, and thermal properties. The polymer contained two types of monomers, namely 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) at a relative percentage of 93.0–79.8 and 7.0–20.2 w/w, respectively. PHA extracted from wet-acidified biomass had higher average molecular weights (Mw) of 370–424 kDa while PHA recovered from thermally stabilized dried biomass had a 3-fold lower Mw (on average). The PHA decomposition temperatures Td10% and Tdmax were in the range 260–268 °C and 269–303 °C, respectively, not dependent on the monomeric composition or molecular weight. Thermal properties such as melting temperature (Tm1 132–150 °C; Tm2 155–167 °C) and melting enthalpy (26–70 J/g) were quantified in a relatively broad range according to the different stabilization-extraction method and obtained composition.
Polyhydroxyalkanoates (PHAs) production at pilot scale has been recently investigated and carried out exploiting different process configurations and organic wastes. More in detail, three pilot platforms, in Treviso (North-East of Italy), Carbonera (North-East of Italy) and Lisbon, produced PHAs by open mixed microbial cultures (MMCs) and different organic waste streams: organic fraction of municipal solid waste and sewage sludge (OFMSW-WAS), cellulosic primary sludge (CPS), and fruit waste (FW), respectively. In this context, two stabilization methods have been applied, and compared, for preserving the amount of PHA inside the cells: thermal drying and wet acidification of the biomass at the end of PHA accumulation process. Afterward, polymer has been extracted following an optimized method based on aqueous-phase inorganic reagents. Several PHA samples were then characterized to determine PHA purity, chemical composition, molecular weight, and thermal properties. The polymer contained two types of monomers, namely 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) at a relative percentage of 92.6–79.8 and 7.4–20.2 w/w, respectively, for Treviso and Lisbon plants. On the other hand, an opposite range was found for 3HB and 3HV monomers of PHA from Carbonera, which is 44.0–13.0 and 56.0–87.0 w/w, respectively. PHA extracted from wet-acidified biomass had generally higher viscosity average molecular weights (Mv) (on average 424.8 ± 20.6 and 224.9 ± 21.9 KDa, respectively, for Treviso and Lisbon) while PHA recovered from thermally stabilized dried biomass had a three-fold lower Mv.
In this study, the performance of the selection process for polyhydroxyalkanoate (PHA) production from mixed microbial cultures (MMCs) at pilot scale was deeply investigated with the solid retention time (SRT) to cycle length (CL) ratio as main affecting parameter. Four different runs were tested by varying the SRT/CL ratio maintaining the same organic loading rate (OLR). The pilot-scale selection and accumulation reactors were fed with a fermented mixture of source-selected organic fraction of municipal solid waste (OFMSW) and waste activated sludge (WAS), refined with a centrifuge and membrane unit for the coarse solid removal. The selected biomass obtained in the most performing run was characterized by a specific storage rate of 375 mg COD P /g COD Xa h and a storage yield of 0.46 COD P /COD SOL . Accumulations performed with the same biomass were characterized by a storage yield of 0.62 COD P /COD VFA . The microbiome composition was assessed. In the most performing run, putative PHA-storing bacteria affiliated with Paracoccus genus were found at high abundance (36.8%), in contrast to all other runs. An overall PHA yield of 110 g PHA/kg VS was estimated for the best scenario, revealing an interesting perspective for biorefinery technology chains based on the three-stage process for PHA production.
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.
Groundwater remediation is one of the main objectives to minimize environmental impacts and health risks. Chlorinated aliphatic hydrocarbons contamination is prevalent and presents particularly challenging scenarios to manage with a single strategy. Different technologies can manage contamination sources and plumes, although they are usually energy-intensive processes. Interesting alternatives involve in-situ bioremediation strategies, which allow the chlorinated contaminant to be converted into non-toxic compounds by indigenous microbial activity. Despite several advantages offered by the bioremediation approaches, some limitations, like the relatively low reaction rates and the difficulty in the management and control of the microbial activity, can affect the effectiveness of a bioremediation approach. However, those issues can be addressed through coupling different strategies to increase the efficiency of the bioremediation strategy. This mini review describes different strategies to induce the reduction dechlorination reaction by the utilization of innovative strategies, which include the increase or the reduction of contaminant mobility as well as the use of innovative strategies of the reductive power supply. Subsequently, three future approaches for a greener and more sustainable intervention are proposed. In particular, two bio-based materials from renewable resources are intended as alternative, long-lasting electron-donor sources (e.g., polyhydroxyalkanoates from mixed microbial cultures) and a low-cost adsorbent (e.g., biochar from bio-waste). Finally, attention is drawn to novel bio-electrochemical systems that use electric current to stimulate biological reactions.
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