Alternative end-of-life options for disposable bioplastic products: Degradation and ecotoxicity assessment in compost and soil.

Four different end-of-life options for disposable bioplastic cups were investigated and compared based on their environmental implications. Two products with distinct polymeric composition were tested simulating the following scenarios at laboratory scale: i) industrial composting (180 days at 58 °C); ii) anaerobic digestion followed by industrial composting (45 days at 55 °C and 180 days at 58 °C); iii) anaerobic digestion followed by direct digestate use on soil for agricultural purposes (45 days at 55 °C and 180 days at 25 °C); iv) uncontrolled release into a soil environment (180 days at 25 °C). Ecotoxicity tests were run at the end of each experiment to investigate the effects of the materials on three main groups of terrestrial model organisms: plants, earthworms and nitrifying bacteria. Complete biodegradation of the cups was observed in 180 days in the scenarios involving composting environment. A low degree of biodegradation (22.9 ± 4.5%) of the digestates in soil was observed, warning for a potential micro-bioplastics discharge into the environment. No degradation was observed for the cups in soil during the same testing period. Ecotoxicity tests revealed a negative effect on plants biomass growth across all samples, which was 17-30% lower compared to the blank sample. The experimental campaign highlighted the need for a systematic assessment of controlled treatment of bioplastics, as well as the need for a harmonized legislative framework.

Factor-based assessment of continuous bio-H2 production from cheese whey.

Despite having been widely investigated, dark fermentative H2 production from organic residues is still limited by process-related issues which may hamper the perspectives of full-scale process implementation. Such constraints are mainly due to the process complexity, which is largely affected by multiple and often mutually interacting factors. In the present work, the results of continuous fermentative H2 production experiments using synthetic cheese whey as the input substrate were used to gain detailed knowledge of the process features and identify suitable and critical operating conditions. Specifically, innovative process interpretation involved a combination of analytical characterization of the fermentation broth, mass balance calculations and statistical methods (correlation and principal component analyses) to derive systematic considerations for process characterization and scale-up. The metabolic products mainly included acetate and butyrate, which however were likely to derive (in different proportions depending on the operating conditions) from both hydrogenogenic and competing pathways. For some tests, lactate and succinate were also found to have been formed. It was observed that the main features of the process (H2 yield and rate, stability condition) were correlated with the operational and analytical parameters. The first three principal components identified by the statistical analysis were able to account for: 1) the effect of retention time and total metabolites produced; 2) biogas (H2 and CO2) generation, butyrate production and stability condition; and 3) organic loading rate and propionate production. The results suggested that the main features of hydrogenogenic fermentation can be described by a reduced set of factors that may be usefully adopted for both process monitoring and prediction purposes.

Control of fermentation duration and pH to orient biochemicals and biofuels production from cheese whey.

Batch dark fermentation tests were performed on sheep cheese whey without inoculum addition at different operating pHs, relating the type and production yields of the observed gaseous and liquid by-products to the evolution of fermentation. Cheese whey fermentation evolved over time in two steps, involving an initial conversion of carbohydrates to lactic acid, followed by the degradation of this to soluble and gaseous products including short-chain fatty acids (mainly acetic, butyric and propionic acids) and hydrogen. The operating pH affected the production kinetics and yields, as well as the fermentation pathways. By varying the duration of the fermentation process, different cheese whey exploitation strategies may be applied and oriented to the main production of lactic acid, hydrogen or other organic acids.

Fermentative H2 production from food waste: Parametric analysis of factor effects.

Factorial fermentation experiments on food waste (FW) inoculated with activated sludge (AS) were conducted to investigate the effects of pH and the inoculum-to-substrate ratio (ISR [g VSAS/g TOCFW]) on biohydrogen production. The two parameters affected the H2 yield, the fermentation rate and the biochemical pathways. The minimum and maximum yields were 41 L H2/kg TOCFW (pH = 7.5, ISR = 1.74) and 156-160 L H2/kg TOCFW (pH = 5.5, ISR = 0.58 and 1.74). The range of carbohydrates conversion into H2 was 0.37-1.45 mol H2/mol hexose, corresponding to 9.4-36.2% of the theoretical threshold. A second-order predictive model for H2 production identified an optimum region at low pHs and high ISRs, with a theoretical maximum of 168 L H2/kg TOCFW at pH = 5.5 and ISR = 1.74. The Spearman's correlation method revealed several relationships between the variables, suggesting the potentially governing metabolic pathways, which turned out to involve both hydrogenogenic pathways and competing reactions.

Effect of ultrasonication on anaerobic degradability of solid waste digestate.

This paper evaluates the effect of ultrasonication on anaerobic biodegradability of lignocellulosic residues. While ultrasonication has been commonly applied as a pre-treatment of the feed substrate, in the present study a non-conventional process configuration based on recirculation of sonicated digestate to the biological reactor was evaluated at the lab-scale. Sonication tests were carried out at different applied energies ranging between 500 and 50,000kJ/kg TS. Batch anaerobic digestion tests were performed on samples prepared by mixing sonicated and untreated substrate at two different ratios (25:75 and 75:25 w/w). The results showed that when applied as a post-treatment of digestate, ultrasonication can positively affect the yield of anaerobic digestion, mainly due to the dissolution effect of complex organic molecules that have not been hydrolyzed by biological degradation. A good correlation was found between the CH4 production yield and the amount of soluble organic matter at the start of digestion tests. The maximum gain in biogas production was 30% compared to that attained with the unsonicated substrate, which was tentatively related to the type and concentration of the metabolic products.

Leaching modelling of slurry-phase carbonated steel slag.

In the present work the influence of accelerated mineral carbonation on the leaching behaviour of basic oxygen furnace steel slag was investigated. The environmental behaviour of the material as evaluated through the release of major elements and toxic metals under varying pH conditions was the main focus of the study. Geochemical modelling of the eluates was used to derive a theoretical description of the underlying leaching phenomena for the carbonated material as compared to the original slag. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases, and lower-Ca/Si-ratio minerals were found to control leaching in carbonated slag eluates as compared to the corresponding untreated slag sample as a result of Ca depletion from the residual slag particles. Clear evidence was also gained of solubility control for Ca, Mg and Mn by a number of carbonate minerals, indicating a significant involvement of the original slag constituents in the carbonation process. The release of toxic metals (Zn, V, Cr, Mo) was found to be variously affected by carbonation, owing to different mechanisms including pH changes, dissolution/precipitation of carbonates as well as sorption onto reactive mineral surfaces. The leaching test results were used to derive further considerations on the expected metal release levels on the basis of specific assumptions on the relevant pH domains for the untreated and carbonated slag.

Effects of thin-film accelerated carbonation on steel slag leaching.

This paper discusses the effects of accelerated carbonation on the leaching behaviour of two types of stainless steel slags (electric arc furnace and argon oxygen decarburisation slag). The release of major elements and toxic metals both at the natural pH and at varying pH conditions was addressed. Geochemical modelling of the eluates was used to theoretically describe leaching and derive information about mineralogical changes induced by carbonation. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases; geochemical modelling indicated that the Ca/Si ratio of Ca-controlling minerals shifted from ∼ 1 for the untreated slag to 0.5-0.67 for the carbonated samples, thus showing that the carbonation process left some residual Ca-depleted silicate phases while the extracted Ca precipitated in the form of carbonate minerals. For toxic metals the changes in leaching induced by carbonation appeared to be mainly related to the resulting pH changes, which were as high as ∼ 2 orders of magnitude upon carbonation. Depending on the specific shape of the respective solubility curves, the extent of leaching of toxic metals from the slag was differently affected by carbonation.

Thin-film versus slurry-phase carbonation of steel slag: CO2 uptake and effects on mineralogy.

The results of direct aqueous accelerated carbonation of three types of steel manufacturing residues, including an electric arc furnace (EAF) slag and two basic oxygen furnace (BOF) slags, are reported. Batch accelerated carbonation tests were conducted at different temperatures and CO2 pressures applying the thin-film route (liquid to solid, L/S, ratio=0.3L/kg) or the slurry-phase route (L/S ratio=5L/kg). The CO2 uptake strongly depended on both the slag characteristics and the process route; maximum yields of 280 (EAF), 325 (BOF1) and 403 (BOF2) gCO2/kg slag were achieved in slurry phase at T=100°C and pCO2=10 bar. Differently from previous studies, additional carbonates (other than Ca-based phases) were retrieved in the carbonated BOF slags, indicating that also Mg-, Fe- and Mn-containing phases partially reacted with CO2 under the tested conditions. The results hence show that the effects of accelerated carbonation in terms of CO2 uptake capacity, yield of mineral conversion into carbonates and mineralogy of the treated product, strongly rely on several factors. These include, above all, the mineralogy of the original material and the operating conditions adopted, which thus need specific case-by-case optimization to maximize the CO2 sequestration yield.

An experimental study on fermentative H2 production from food waste as affected by pH.

Batch dark fermentation experiments were performed on food waste and mixtures of food waste and wastewater activated sludge to evaluate the influence of pH on biological H2 production and compare the process performance with and without inoculum addition. The effect of a preliminary thermal shock treatment of the inoculum was also investigated as a means to harvest the hydrogenogenic biomass. The best performance in terms of both H2 generation potential and process kinetics was observed at pH=6.5 under all experimental conditions (no inoculum, and untreated or thermally treated inoculum added). H2 production from food waste was found to be feasible even without inoculum addition, although thermal pre-treatment of the inoculum notably increased the maximum production and reduced the lag phase duration. The analysis of the fermentation products indicated that the biological hydrogen production could be mainly ascribed to a mixed acetate/butyrate-type fermentation. However, the presence of additional metabolites in the digestate, including propionate and ethanol, also indicated that other metabolic pathways were active during the process, reducing substrate conversion into hydrogen. The plateau in H2 generation was found to mirror the condition at which soluble carbohydrates were depleted. Beyond this condition, homoacetogenesis probably started to play a role in the degradation process.

A review of dark fermentative hydrogen production from biodegradable municipal waste fractions.

Hydrogen is believed to play a potentially key role in the implementation of sustainable energy production, particularly when it is produced from renewable sources and low energy-demanding processes. In the present paper an attempt was made at critically reviewing more than 80 recent publications, in order to harmonize and compare the available results from different studies on hydrogen production from FW and OFMSW through dark fermentation, and derive reliable information about process yield and stability in view of building related predictive models. The review was focused on the effect of factors, recognized as potentially affecting process evolution (including type of substrate and co-substrate and relative ratio, type of inoculum, food/microorganisms [F/M] ratio, applied pre-treatment, reactor configuration, temperature and pH), on the fermentation yield and kinetics. Statistical analysis of literature data from batch experiments was also conducted, showing that the variables affecting the H2 production yield were ranked in the order: type of co-substrate, type of pre-treatment, operating pH, control of initial pH and fermentation temperature. However, due to the dispersion of data observed in some instances, the ambiguity about the presence of additional hidden variables cannot be resolved. The results from the analysis thus suggest that, for reliable predictive models of fermentative hydrogen production to be derived, a high level of consistency between data is strictly required, claiming for more systematic and comprehensive studies on the subject.

Accelerated carbonation of different size fractions of bottom ash from RDF incineration.

This paper investigates the effects of accelerated carbonation on the characteristics of bottom ash from refuse derived fuel (RDF) incineration, in terms of CO(2) uptake, heavy metal leaching and mineralogy of different particle size fractions. Accelerated aqueous carbonation batch experiments were performed to assess the influence of operating parameters (temperature, CO(2) pressure and L/S ratio) on reaction kinetics. Pressure was found to be the most relevant parameter affecting the carbonation yield. This was also found to be largely dependent on the specific BA fraction treated, with CO(2) uptakes ranging from approximately 4% for the coarse fractions to approximately 14% for the finest one. Carbonation affected both the mineralogical characteristics of bottom ash, with the appearance of neo-formation minerals, and the leaching behaviour of the material, which was found to be mainly related to the change upon carbonation in the natural pH of the ash.

Chemical activation in view of MSWI bottom ash recycling in cement-based systems.

In the present study, the feasibility of recycling incinerator bottom ash in cementitious systems by means of chemical activation was investigated. Different Na-, K- and Ca-based hydroxides and salts were selected for the experiments on the basis of their recognized effects on activation of typical pozzolanic materials. The evolution of mechanical properties of bottom ash/Portland cement mixtures and the leaching of trace metals from the materials were a matter of major concern. The experiments were arranged according to a full factorial design, which also allowed to derive a predictive model for unconfined compressive strength as affected by bottom ash content as well as activator type and dosage. Among the activators tested, calcium chloride was found to affect mechanical strength far more positively than the other species used, at the same time ensuring low metal release from the material. On the other hand, the use of potassium sulfate was observed to cause a significant increase in metal leaching at pH<12, which was probably associated to the release of contaminants initially immobilized within the structure of ettringite as soon as it converted into monosulfate over time.

The effect of operating variables on chelant-assisted remediation of contaminated dredged sediment.

The paper shows the results from a number of lab-scale washing treatments using the four chelating agents EDTA, NTA, citric acid and [S,S]-EDDS aiming at the remediation of a real heavy metal-contaminated sediment. Investigation of the influence of chelant type and concentration as well as solution pH was the major focus of the work. The analysis of speciation of metals and chelating agents in solution was carried out through geochemical speciation modelling in order to identify the optimal conditions for the washing process as well as to evaluate the competition phenomena of metal-chelant complexes in solution. The major competing cations were found to be Ca above all and Mg under specific conditions. Among the investigated chelating agents, EDDS appeared to be less affected by competition by major cations while ensuring adequate heavy metal extraction efficiencies. For a 1:1 chelant/metal ratio, the following ranking was observed: EDDS>Cit>NTA>EDTA for As, EDDS>NTA congruent withEDTA>>Cit for Cu, EDDS congruent withEDTA congruent withNTA>Cit for Zn, EDTA>NTA>EDDS>Cit for Pb at pH 5 and EDTA congruent withEDDS congruent withNTA>>Cit for Pb at pH 8. For a 10:1 chelant/metal ratio geochemical modelling indicated that at the equilibrium the extracting solutions were dominated by the free form of the chelating agents, indicating the inability of such species to complex trace metals due the strong interactions existing between heavy metal ions and sediment constituents.

A kinetic study of chelant-assisted remediation of contaminated dredged sediment.

A study on the remediation of a real heavy metal-contaminated sediment was conducted using the four chelating agents ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), citric acid and the S,S-isomer of the ethylenediaminedisuccinic acid ([S,S]-EDDS). Different chelant washing experiments were carried out at a chelant/total metal content of 1 and 10 mol/mol for treatment durations from 0.5 to 48 h to study the extraction kinetics of trace metals and major cations. The objective was to evaluate the removal efficiency of conventional chelating agents as compared to innovative, biodegradable species. Among the target contaminants, Cd, Cu, Pb and Zn were found to be adequately removed by both EDTA and EDDS, while NTA and citric acid yielded unsatisfactory results in some cases. It was also found that As was a critical contaminant which would require an additional specific treatment step, since the residual concentrations after the washing treatment were still far above the regulatory limit values.

Engineering and environmental properties of thermally treated mixtures containing MSWI fly ash and low-cost additives.

An experimental work was carried out to investigate the feasibility of application of a sintering process to mixtures composed of Municipal Solid Waste Incinerator (MSWI) fly ash and low-cost additives (waste from feldspar production and cullet). The proportions of the three constituents were varied to adjust the mixture compositions to within the optimal range for sintering. The material was compacted in cylindrical specimens and treated at 1100 and 1150 degrees C for 30 and 60 min. Engineering and environmental characteristics including weight loss, dimensional changes, density, open porosity, mechanical strength, chemical stability and leaching behavior were determined for the treated material, allowing the relationship between the degree of sintering and both mixture composition and treatment conditions to be singled out. Mineralogical analyses detected the presence of neo-formation minerals from the pyroxene group. Estimation of the extent of metal loss from the samples indicated that the potential for volatilization of species of Pb, Cd and Zn is still a matter of major concern when dealing with thermal treatment of incinerator ash.

Modelling heavy metal and anion effects on physical and mechanical properties of portland cement by means of factorial experiments.

The aim of the present work was to investigate the influence of a number of heavy metals (Cd, Cr(III), Cu, Pb and Zn), as well as anions (Cl-, SO4(2-)) on the physical and mechanical properties of cementitious pastes, including setting time, bulk density and unconfined compressive strength. The above mentioned species and their concentrations were selected in order to simulate addition of 20% municipal solid waste incinerator ash to Portland cement. Spiking experiments were performed according to a 2IV(7-3) fractional factorial design by addition of pure compounds containing the contaminants of interest to Portland cement. The results from the experimental campaign, which were interpreted using statistical analysis techniques, showed that the investigated contaminants variously affected the hydration process of cement. The ranking for final setting time values was Zn(NO3)2 > K2SO4 > NaCl > mean response > Cr(NO3)3 > NaCl+Cr(NO3)3, Cd(NO3)2+Pb(NO3)2 or CuCl2+Zn(NO3)2 interaction, whereas the ranking for UCS values during hardening was Zn(NO3)2 > CuCl2 > NaCl+K2SO4, CuCl2+Pb(NO3)2 or Cd(NO3)2+Zn(NO3)2 interaction > mean response. Conversely, none of the selected contaminants was found to significantly influence ultimate strength.

Physical and mechanical properties of cement-based products containing incineration bottom ash.

This paper presents the results of a wider experimental programme conducted in the framework of the NNAPICS ("Neural Network Analysis for Prediction of Interactions in Cement/Waste Systems") project funded by the European Commission and a number of industrial partners under Brite-EuRamIII. Based on the fact that bottom ashes from waste incineration are classified as non-hazardous wastes according to the European Waste Catalogue, the aim of the present work was to investigate the feasibility of addressing the potential use of such residues in cement-based mixtures. This issue was suggested by the analysis of the properties of different bottom ashes coming from Italian municipal and hospital solid waste incinerators, which showed a chemical composition potentially suitable for such applications. Different mixes were prepared by blending bottom ash with ordinary Portland cement in different proportions and at different water dosages. The solidified products were tested for setting time and bulk density, unconfined compressive strength and evaporable water content at different curing times. The results of the experimental campaign were analysed through a statistical procedure (analysis of variance), in order to investigate the effect of mixture composition (waste replacement level and water dosage) on the product properties.

Management of municipal solid waste incineration residues.

The management of residues from thermal waste treatment is an integral part of waste management systems. The primary goal of managing incineration residues is to prevent any impact on our health or environment caused by unacceptable particulate, gaseous and/or solute emissions. This paper provides insight into the most important measures for putting this requirement into practice. It also offers an overview of the factors and processes affecting these mitigating measures as well as the short- and long-term behavior of residues from thermal waste treatment under different scenarios. General conditions affecting the emission rate of salts and metals are shown as well as factors relevant to mitigating measures or sources of gaseous emissions.

Fractional factorial design to investigate the influence of heavy metals and anions on acid neutralization behavior of cement-based products.

A major concern of cement-based solidification/stabilization of hazardous wastes is the interaction of waste contaminants on cement properties. Literature contains many examples of studies on the interference of individual contaminants on cement properties. Conversely, little information is available on how the interactions between contaminants affectthe properties of cement/waste systems. This paper provides a discussion on the interference mechanisms exerted by seven contaminants, five heavy metals and two anions, on cement hydration. The seven contaminants were selected on the basis of the typical composition of municipal solid waste incineration (MSWI) fly ash. Spiking experiments using pure compounds were performed according to a 2IV(7-3) fractional factorial design to simulate addition of MSWI fly ash to ordinary Portland cement. The acid neutralization behavior of the laboratory cement-contaminant mixtures was studied to detect the presence of solid phases responsible for the buffering capacity of the solid matrix. The results from the experimental work showed that Zn, Cl-, and SO4(2-) were the major factors influencing, occasionally in combination with other contaminants, strength and acid neutralization capacity of the cementitious products. The release of Cd, Cr, Cu, and Pb in the eluates as a function of pH also suggested possible chemical immobilization mechanisms of such metals within the hardened matrix.