Anaerobic Biodegradability of Commercial Bioplastic Products: Systematic Bibliographic Analysis and Critical Assessment of the Latest Advances.

Bioplastics have entered everyday life as a potential sustainable substitute for commodity plastics. However, still further progress should be made to clarify their degradation behavior under controlled and uncontrolled conditions. The wide array of biopolymers and commercial blends available make predicting the biodegradation degree and kinetics quite a complex issue that requires specific knowledge of the multiple factors affecting the degradation process. This paper summarizes the main scientific literature on anaerobic digestion of biodegradable plastics through a general bibliographic analysis and a more detailed discussion of specific results from relevant experimental studies. The critical analysis of literature data initially included 275 scientific references, which were then screened for duplication/pertinence/relevance. The screened references were analyzed to derive some general features of the research profile, trends, and evolution in the field of anaerobic biodegradation of bioplastics. The second stage of the analysis involved extracting detailed results about bioplastic degradability under anaerobic conditions by screening analytical and performance data on biodegradation performance for different types of bioplastic products and different anaerobic biodegradation conditions, with a particular emphasis on the most recent data. A critical overview of existing biopolymers is presented, along with their properties and degradation mechanisms and the operating parameters influencing/enhancing the degradation process under anaerobic conditions.

Anaerobic biodegradation of disposable PLA-based products: Assessing the correlation with physical, chemical and microstructural properties.

In the present study commercial Polylactic Acid-based disposable cups and plates were selected for lab scale anaerobic degradability tests. The experiments were carried out under thermophilic conditions at different inoculum to substrate ratios and test material sizes, and the specific biogas production and associated kinetics were evaluated. Maximum biogas production was comparable for almost all the experimental runs (1620 and 1830 NmL/gTOCPLA) and a biodegradation degree in the range 86-100% was attained. Moreover, physical, chemical and microscopical analyses were used to characterize the tested materials before and after the degradation. The products composition was assessed and the presence of some additives (mainly Ca-based) was detected. Potential correlations among the process parameters and product composition were derived and a delay in process kinetics with increasing amount of additives embedded in the polymeric matrix was observed, confirming the relevant influence of the chemical blend on the biodegradation process.

Dark fermentative volatile fatty acids production from food waste: A review of the potential central role in waste biorefineries.

Volatile fatty acids (VFAs) are high-value chemicals that are increasingly demanded worldwide. Biological production via food waste (FW) dark fermentation (DF) is a promising option to achieve the sustainability and environmental benefits typical of biobased chemicals and concurrently manage large amounts of residues. DF has a great potential to play a central role in waste biorefineries due to its ability to hydrolyze and convert complex organic substrates into VFAs that can be used as building blocks for bioproducts, chemicals and fuels. Several challenges must be faced for full-scale implementation, including process optimization to achieve high and stable yields, the development of efficient techniques for selective recovery and the cost-effectiveness of the whole process. This review aims to critically discuss and statistically analyze the existing relationships between process performance and the main variables of concern. Moreover, opportunities, current challenges and perspectives of a FW-based and fermentation-centred biorefinery layout are discussed.

Valorisation of residues from municipal wastewater sieving through anaerobic (co-)digestion with biological sludge.

The Circular and Green Economy principles is inspiring new approaches to municipal wastewater treatment plants (MWWTPs) design and operation. Recently, an ever-growing interest is devoted to exploring the alternatives for switching the WWTPs from being able to 'simply' removing contaminants from water to biorefinery-like plants where energy and material can be recovered. In this perspective, both wastewater and residues from process can be valorised for recovering nutrients (N and P), producing value added products (i.e. biopolymers), energy vectors and biofuels (i.e. bio-H2, bio-CH4 and bioethanol). As an additional benefit, changing the approach for WWTPs design and operation will decrease the overall amount of landfilled residues. In this context, the present research is aimed at evaluating the CH4 production potential of MWW screening units' residues. While such a stream is typically landfilled, the expected progressive increase of biodegradable matter content due to the ban on single-use plastic along with the boost of bioplastics makes the investigation of different biochemical valorisation routes more and more interesting from an environmental and economical perspective. Thus, a full-scale data collection campaign was performed to gain information on screening residues amount and properties and to analyse the relationship with influent flowrate. The most relevant residue properties were measured, and lab-scale tests were carried out to evaluate the bio-CH4 potential.

Environmental life cycle assessment of polyhydroxyalkanoates production from cheese whey.

Cheese whey (CW) is the main by-product of the dairy industry and is often considered one of the main agro-industrial biowaste streams to handle, especially within the European Union, where the diary activities play an essential role in the agrarian economy. In the paper, Life Cycle Assessment (LCA) is used to analyse the feasibility of producing polyhydroxyalkanoates (PHA) as the main output of an innovative CW valorisation route which is benchmarked against a conventional anaerobic digestion (AD) process. To this aim, the LCA inventory data are derived from lab-scale PHA accumulation tests performed on real CW, while data from the literature of concern are used for modelling both the PHA extraction from the accumulating biomass and for the alternative CW valorisation through AD. The comparison shows that AD would have better environmental performances than the baseline PHA production scenario. For example, the climate change indicator values result 44.8 and -35.7 kg CO2 eq./t CW for the baseline PHA recovery and AD, respectively. LCA proved to be a useful tool to highlight the weak points of innovative processes and suggest proper improvements. Once improved and again analysed through the LCA, the PHA production process from CW shows that environmental performance comparable to AD may be achieved. With reference, again, to the climate change indicator the value can be reduced to -50.3 kg CO2 eq./t CW for the improved PHA production process.

Effect of ultrasonic post-treatment on anaerobic digestion of lignocellulosic waste.

This paper evaluates the effects of ultrasonication (US) applied, individually or in combination with a mechanical treatment, to the effluent of anaerobic digestion (AD) of lignocellulosic waste, on methane (CH4) production. US of the substrate downstream of AD is a relatively novel concept aimed at improving the degradation of recalcitrant components in order to enhance the overall energy efficiency of the process. US tests were carried out on real digestate samples at different energies (500-50,000 kJ/kg total solids (TS), corresponding to sonication densities of 0.08-0.45 W/ml). AD tests were performed on mixtures of sonicated (Sus) and untreated (S) substrate at two different Sus: S ratios (25:75 and 75:25 w/w), simulating post-sonicated material recycling to the biological process. The US effect was estimated through the solubilization degree of organic matter, as well as the CH4 production yield and kinetics, which were all found to be enhanced by the treatment. At Sus: S = 75:25 and Es ≥ 20,000 kJ/kg TS (0.25 W/ml), CH4 production improved by 20% and the values of the kinetic parameters increased by 64-82%.

The dairy biorefinery: Integrating treatment processes for cheese whey valorisation.

With an estimated worldwide production of 190 billion kg per year, and due to its high organic load, cheese whey represents a huge opportunity for bioenergy and biochemicals production. Several physical, chemical and biological processes have been proposed to valorise cheese whey by producing biofuels (methane, hydrogen, and ethanol), electric energy, and/or chemical commodities (carboxylic acids, proteins, and biopolymers). A biorefinery concept, in which several value-added products are obtained from cheese whey through a cascade of biotechnological processes, is an opportunity for increasing the product spectrum of dairy industries while allowing for sustainable management of the residual streams and reducing disposal costs for the final residues. This review critically analyses the different treatment options available for energy and materials recovery from cheese whey, their combinations and perspectives for implementation. Thus, instead of focusing on a specific valorisation platform, in the present review the most relevant aspects of each strategy are analysed to support the integration of different routes, in order to identify the most appropriate treatment train.

Organic waste biorefineries: Looking towards implementation.

The concept of biorefinery expands the possibilities to extract value from organic matter in form of either bespoke crops or organic waste. The viability of biorefinery schemes depends on the recovery of higher-value chemicals with potential for a wide distribution and an untapped marketability. The feasibility of biorefining organic waste is enhanced by the fact that the biorefinery will typically receive a waste management fee for accepting organic waste. The development and implementation of waste biorefinery concepts can open up a wide array of possibilities to shift waste management towards higher sustainability. However, barriers encompassing environmental, technical, economic, logistic, social and legislative aspects need to be overcome. For instance, waste biorefineries are likely to be complex systems due to the variability, heterogeneity and low purity of waste materials as opposed to dedicated biomasses. This article discusses the drivers that can make the biorefinery concept applicable to waste management and the possibilities for its development to full scale. Technological, strategic and market constraints affect the successful implementations of these systems. Fluctuations in waste characteristics, the level of contamination in the organic waste fraction, the proximity of the organic waste resource, the markets for the biorefinery products, the potential for integration with other industrial processes and disposal of final residues are all critical aspects requiring detailed analysis. Furthermore, interventions from policy makers are necessary to foster sustainable bio-based solutions for waste management.

Influence of the pH control strategy and reactor volume on batch fermentative hydrogen production from the organic fraction of municipal solid waste.

Three different experimental sets of runs involving batch fermentation assays were performed to evaluate the influence of the experimental conditions on biological hydrogen production from the source-separated organic fraction of municipal solid waste collected through a door-to-door system. The fermentation process was operated with and without automatic pH control, at a pH of 5.5 and 6.5, food-to-microorganism ratios of 1/3 and 1/1 (wet weight basis) and with different working volumes (0.5 and 3 L). The experimental results showed that the pH control strategy and the reactor volume did not affect the final hydrogen production yield but played an important role in determining the time evolution of the process. Indeed, although the different experimental conditions tested yielded comparable hydrogen productions (with maximum average values ranging from 68.5 to 88.5 NLH2 (kgTVSOF)-1), the automatic pH control strategy improved the process from the kinetic viewpoint resulting in a t95 reduction from an average of 34.9 h without automatic pH control to an average of 19.5 h.

A parametric response surface study of fermentative hydrogen production from cheese whey.

Batch factorial experiments were performed on cheese whey+wastewater sludge mixtures to evaluate the influence of pH and the inoculum-to-substrate ratio (ISR) on fermentative H2 production and build a related predictive model. ISR and pH affected H2 potential and rate, and the fermentation pathways. The specific H2 yield varied from 61 (ISR=0, pH=7.0) to 371L H2/kg TOCwhey (ISR=1.44gVS/g TOC, pH=5.5). The process duration range was 5.3 (ISR=1.44gVS/g TOC, pH=7.5) - 183h (ISR=0, pH=5.5). The metabolic products included mainly acetate and butyrate followed by ethanol, while propionate was only observed once H2 production had significantly decreased. The multiple metabolic products suggested that the process was governed by several fermentation pathways, presumably overlapping and mutually competing, reducing the conversion yield into H2 compared to that expected with clostridial fermentation.

Energy recovery from one- and two-stage anaerobic digestion of food waste.

One- and two-stage anaerobic digestion of food waste aimed at recovering methane (CH4) and hydrogen and methane (H2+CH4), respectively, were compared in order to assess the potential benefits from the two-stage process in terms of overall energy recovery. Results suggest that a two-stage process where the first reactor is properly operated in order to achieve a significant net hydrogen production, may display a 20% comparatively higher energy recovery yield as a result, mainly, of enhanced methane production as well as of the associated hydrogen production. The highest methane production of the two-stage process was due to improved hydrolysis and fermentation of food waste, with increased amounts of volatile fatty acids being readily available to methanogenesis.

Effect of alkaline pretreatment on anaerobic digestion of olive mill solid waste.

The present study evaluates the influence of alkaline (NaOH) pretreatment on anaerobic digestion of olive pomace. Batch hydrolysis experiments with different NaOH dosages, process durations and temperatures were conducted, in which the variation of olive pomace solubilization in the liquid phase was investigated. The effect of pretreatment on anaerobic digestion was studied through biochemical methane potential assays. The results demonstrated the effectiveness of the NaOH pretreatment in improving olive pomace solubilization as well as its biodegradability. Maximum specific methane yields were achieved at different NaOH dosages depending on the pretreatment temperature. Consequently, it was concluded that the two operating parameters of the pretreatment stage (NaOH dosage and temperature) may exert a joint effect on substrate biodegradability and methane yields. The highest methane yield (242NmLCH4/gVS) was obtained for the material pretreated at 90°C, at a dosage of 1mmol/gVS (4% of VS).

CO2 sequestration through aqueous accelerated carbonation of BOF slag: A factorial study of parameters effects.

A factorial study was conducted on basic oxygen furnace slag from a steelmaking industry with the aim of systematically identifying the individual and joint effects of the operating parameters (total pressure, CO2 concentration in the gas phase and temperature) on the CO2 sequestration yield of a direct aqueous carbonation process. Each operating parameter was varied over a range of three levels according to a 3(3) factorial design, resulting in 27 carbonation experiments. The carbonation performance and the changes in particle size and mineralogical characteristics of the slag were investigated in detail. The analysis of the experimental results indicated large effects of the operating factors on CO2 uptake, which was observed to span the range 6.7-53.6 g CO2/100 g slag. The best carbonation performance achieved was particularly significant compared to previous studies, even more considering the relative mild operating conditions adopted (P = 5 bar, C = 40% vol. CO2, T = 50 °C, t = 4 h). The analysis of the solid and liquid phases at the end of the carbonation treatment evidenced significant changes in the physical, chemical and mineralogical composition of the material. In particular, evidence was gained of other elements (Mg, Fe, Mn, Zn) in addition to Ca being intensively involved in the carbonation reactions, with a variety of carbonate phases being produced in addition to calcium carbonate forms.

Land suitability for waste disposal in metropolitan areas.

Site selection for waste disposal is a complex task that should meet the requirements of communities and stakeholders. In this article, three decision support methods (Boolean logic, index overlay and fuzzy gamma) are used to perform land suitability analysis for landfill siting. The study was carried out in one of the biggest metropolitan regions of Italy, with the objective of locating suitable areas for waste disposal. Physical and socio-economic information criteria for site selection were decided by a multidisciplinary group of experts, according to state-of-the-art guidelines, national legislation and local normative on waste management. The geographic information systems (GIS) based models used in this study are easy to apply but require adequate selection of criteria and weights and a careful evaluation of the results. The methodology is arranged in three steps, reflecting the criteria defined by national legislation on waste management: definition of factors that exclude location of landfills or waste treatment plants; classification of the remaining areas in terms of suitability for landfilling; and evaluation of suitable sites in relation to preferential siting factors (such as the presence of quarries or dismissed plants). The results showed that more than 80% of the provincial territory falls within constraint areas and the remaining territory is suitable for waste disposal for 0.72% or 1.93%, according to the model. The larger and most suitable sites are located in peripheral areas of the metropolitan system. The proposed approach represents a low-cost and expeditious alternative to support the spatial decision-making process.

Mechanical properties and leaching modeling of activated incinerator bottom ash in Portland cement blends.

In the present study the evolution of mechanical strength and the leaching behavior of major and trace elements from activated incinerator bottom ash/Portland cement mixtures were investigated. Chemical and mechanical activation were applied with the purpose of improving the reactivity of bottom ash in cement blends. Chemical activation made use of NaOH, KOH, CaCl(2) or CaSO(4), which were selected for the experimental campaign on the basis of the results from previous studies. The results indicated that CaCl(2) exhibited by far the best effects on the evolution of the hydration process in the mixtures; a positive effect on mechanical strength was also observed when CaSO(4) was used as the activator, while the gain in strength produced by KOH and NaOH was irrelevant. Geochemical modeling of the leaching solutions provided information on the mineral phases responsible for the release of major elements from the hardened materials and also indicated the important role played by surface sorption onto amorphous Fe and Al minerals in dictating the leaching of Pb. The leaching of the other trace metal cations investigated (Cu, Ni and Zn) could not be explained by any pure mineral included in the thermodynamic database used, suggesting they were present in the materials in the form of complex minerals or phase assemblages for which no consistent thermodynamic data are presently available in the literature.

Enhanced electrokinetic treatment of marine sediments contaminated by heavy metals and PAHs.

Dredged sediments contaminated by heavy metals and PAHs were subjected to both unenhanced and enhanced electrokinetic remediation under different operating conditions, obtained by varying the applied voltage and the type of conditioning agent used at the electrode compartments in individual experiments. While metals were not appreciably mobilized as a result of the unenhanced process, metal removal was found to be significantly improved when both the anodic and cathodic reservoirs were conditioned with the chelating agent EDTA, with removal yields ranging from 28% to 84% depending on the contaminant concerned. As for the effect on organic contaminants, under the conditions tested the electrokinetic treatment displayed a poor removal capacity towards PAHs, even when a surfactant (Tween 80) was used to promote contaminant mobilization, indicating the need for further investigation on this issue. Further research on organics removal from this type of materials through electrokinetic remediation is thus required. Furthermore, a number of technical and environmental issues will also require a careful evaluation with a view to full-scale implementation of electrokinetic sediment remediation. These include controlling side effects during the treatment (such as anodic precipitation, oxidation of the conditioning agent, and evolution of toxic gases), as well as evaluating the potential ecotoxicological effects of the chemical agents used.

The effects of accelerated carbonation on CO(2) uptake and metal release from incineration APC residues.

This work presents the results of a study on accelerated carbonation of incinerator air pollution control residues, with a particular focus on the modifications in the leaching behaviour of the ash. Aqueous carbonation experiments were carried out using 100% CO(2) at different temperatures, pressures and liquid-to-solid ratios, in order to assess their influence on process kinetics, CO(2) uptake and the leaching behaviour of major and trace elements. The ash showed a particularly high reactivity towards CO(2), owing to the abundance of calcium hydroxides phases, with a maximum CO(2) uptake of approximately 250g/kg. The main effects of carbonation on trace metal leaching involved a significant decrease in mobility for Pb, Zn and Cu at high pH values, a slight change or mobilization for Cr and Sb, and no major effects on the release of As and soluble salts. Geochemical modelling of leachates indicated solubility control by different minerals after carbonation. In particular, in the stability pH range of carbonates, solubility control by a number of metal carbonates was clearly suggested by modelling results. These findings indicate that accelerated carbonation of incinerator ashes has the potential to convert trace contaminants into sparingly soluble carbonate forms, with an overall positive effect on their leaching behaviour.

Enhanced electrokinetic treatment of different marine sediments contaminated by heavy metals.

In the present work, the application of an assisted electrokinetic process for the removal of heavy metals from real contaminated sediments was investigated. The process made use of both chemical and physical methods, including addition of chelating and acid agents, as well as application of a hydraulic gradient. Lab-scale electrokinetic runs were applied on two different dredged sediments varying the applied voltage gradient and the treatment duration. The use of EDTA significantly improved the overall performance of the electrokinetic treatment for sediment V (more than 60% mobilized for each metal), while only aggressive acid conditioning with nitric acid was able to remove significant amounts of heavy metals (up to 40.5% for Pb) from sediment S due to the strong buffering capacity of this material. This clearly assesses that the specific characteristics of the materials under concern and the reactions occurring at the electrodes must be carefully evaluated when applying an electroremediation process.

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues.

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO(2) partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO(2) emissions. In particular, the modification of ash properties that occur upon carbonation and the CO(2) sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a "finishing step" for both ash treatment and reduction of CO(2) emissions.

The leaching behavior of incinerator bottom ash as affected by accelerated ageing.

Different artificial ageing treatments were applied to fresh incinerator bottom ash with the aim of promoting/accelerating the natural reactions occurring over time on the mineral phases in the material. The weathering treatments included accelerated carbonation, treatment with air and treatment with nitrogen gas. Both fresh and treated bottom ashes were characterized for their mineralogical composition, acid neutralization capacity and leaching behavior of metals. The results were compared to those obtained from similar characterization of bottom ash samples weathered under atmospheric conditions for 4 years. The findings from the experimental campaign indicated that both the release of metals and the type of solubility-controlling solid phases varied as a function of the duration and type of ageing treatment. The most appreciable influence on mineralogy, acid neutralization behavior and metal leaching was observed for the 48 h carbonation treatment. It was also observed that 4-day aeration of bottom ash was capable of producing similar buffering behavior to that displayed by naturally aged bottom ash.