Elena Collina

Degradation of Octachlorodibenzofuran and Octachlorodibenzo-p-dioxin Spiked on Fly Ash: Kinetics and Mechanism.

Octachlorodibenzofuran (OCDF) degradation kinetics in a moist nitrogen stream and those of octachlorodibenzo-p-dioxin (OCDD) in a dry or moist airstream on pretreated fly ash were studied in a laboratory pilot plant with temperature ranging from 200 to 350 °C and reaction times varying from 15 to 240 min. The mathematical treatment of experimental data indicated that two reaction pathways, decomposition and dechlorination, operated independently because of a partition of the reagents in the fly ash according to a physical and a chemical adsorption. The decomposition reaction was of the first order with respect to the reactant adsorbed physically. The dechlorination reaction involved first-order series reactions. Here, the kinetic scheme for the first two dechlorination steps is discussed. Kinetic constants and partition constants at different temperatures as well as Arrhenius and Eyring parameters and the isosteric enthalpy of adsorption are calculated.

Genome and Phenotype Microarray Analyses of Rhodococcus sp. BCP1 and Rhodococcus opacus R7: Genetic Determinants and Metabolic Abilities with Environmental Relevance

In this paper comparative genome and phenotype microarray analyses of Rhodococcus sp. BCP1 and Rhodococcus opacus R7 were performed. Rhodococcus sp. BCP1 was selected for its ability to grow on short-chain n-alkanes and R. opacus R7 was isolated for its ability to grow on naphthalene and on o-xylene. Results of genome comparison, including BCP1, R7, along with other Rhodococcus reference strains, showed that at least 30% of the genome of each strain presented unique sequences and only 50% of the predicted proteome was shared. To associate genomic features with metabolic capabilities of BCP1 and R7 strains, hundreds of different growth conditions were tested through Phenotype Microarray, by using Biolog plates and plates manually prepared with additional xenobiotic compounds. Around one-third of the surveyed carbon sources was utilized by both strains although R7 generally showed higher metabolic activity values compared to BCP1. Moreover, R7 showed broader range of nitrogen and sulphur sources. Phenotype Microarray data were combined with genomic analysis to genetically support the metabolic features of the two strains. The genome analysis allowed to identify some gene clusters involved in the metabolism of the main tested xenobiotic compounds. Results show that R7 contains multiple genes for the degradation of a large set of aromatic and PAHs compounds, while a lower variability in terms of genes predicted to be involved in aromatic degradation was found in BCP1. This genetic feature can be related to the strong genetic pressure exerted by the two different environment from which the two strains were isolated. According to this, in the BCP1 genome the smo gene cluster involved in the short-chain n-alkanes degradation, is included in one of the unique regions and it is not conserved in the Rhodococcus strains compared in this work. Data obtained underline the great potential of these two Rhodococcus spp. strains for biodegradation and environmental decontamination processes.

Biodegradation of variable-chain-length n -alkanes in Rhodococcus opacus R7 and the involvement of an alkane hydroxylase system in the metabolism

Rhodococcus opacus R7 is a Gram-positive bacterium isolated from a polycyclic aromatic hydrocarbon contaminated soil for its versatile metabolism; indeed the strain is able to grow on naphthalene, o-xylene, and several long- and medium-chain n-alkanes. In this work we determined the degradation of n-alkanes in Rhodococcus opacus R7 in presence of n- dodecane (C12), n- hexadecane (C16), n- eicosane (C20), n- tetracosane (C24) and the metabolic pathway in presence of C12. The consumption rate of C12 was 88%, of C16 was 69%, of C20 was 51% and of C24 it was 78%. The decrement of the degradation rate seems to be correlated to the length of the aliphatic chain of these hydrocarbons. On the basis of the metabolic intermediates determined by the R7 growth on C12, our data indicated that R. opacus R7 metabolizes medium-chain n-alkanes by the primary alcohol formation. This represents a difference in comparison with other Rhodococcus strains, in which a mixture of the two alcohols was observed. By GC-MSD analysis we also identified the monocarboxylic acid, confirming the terminal oxidation.Moreover, the alkB gene cluster from R. opacus R7 was isolated and its involvement in the n-alkane degradation system was investigated by the cloning of this genomic region into a shuttle-vector E. coli-Rhodococcus to evaluate the alkane hydroxylase activity. Our results showed an increased biodegradation of C12 in the recombinant strain R. erythropolis AP (pTipQT1-alk R7) in comparison with the wild type strain R. erythropolis AP. These data supported the involvement of the alkB gene cluster in the n-alkane degradation in the R7 strain.

Viability study of automobile shredder residue as fuel.

Car Fluff samples collected from a shredding plant in Italy were classified based on particle size, and three different size fractions were obtained in this way. A comparison between these size fractions and the original light fluff was made from two different points of view: (i) the properties of each size fraction as a fuel were evaluated and (ii) the pollutants evolved when each size fraction was subjected to combustion were studied. The aim was to establish which size fraction would be the most suitable for the purposes of energy recovery. The light fluff analyzed contained up to 50 wt.% fines (particle size<20 mm). However, its low calorific value and high emissions of polychlorinated dioxins and furans (PCDD/Fs), generated during combustion, make the fines fraction inappropriate for energy recovery, and therefore, landfilling would be the best option. The 50-100 mm fraction exhibited a high calorific value and low PCDD/F emissions were generated when the sample was combusted, making it the most suitable fraction for use as refuse-derived fuel (RDF). Results obtained suggest that removing fines from the original ASR sample would lead to a material product that is more suitable for use as RDF.

Kinetic modeling of the formation and destruction of polychlorinated dibenzo-p-dioxin and dibenzofuran from fly ash native carbon at 300 °C.

The kinetics for the oxidative breakdown of native carbon in raw fly ash samples (RFA) and for the formation and destruction of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF), abbreviated PCDD/F, were investigated using a flow-over solid system in which the RFA samples were thermally treated at 300 °C under synthetic air. This study investigated the correlation between the disappearance of the reagent and the formation of the products to gain insight into the underlying mechanisms that govern these reactions at congener groups level. The detailed analyses of the experimental concentration-time data revealed significant differences in the behavior between the 2,3,7,8-substituted PCDD and the 2,3,7,8-substituted PCDF, non-2,3,7,8-substituted PCDD and PCDF. The chlorine balance for the former was always negative, that is, chlorine was released regardless of reaction time and primarily resulted from the dechlorination of the hepta- and octa-homologues. However, for the others, the balance was substantially positive up to approximately 240 min and became negative at longer intervals when the dechlorination reactions took over. The processes involving PCDD and PCDF in which the thermal destruction was only partial were found to increase the total equivalent toxicity (TEQ) levels rather than reduce them.

Characterization of fly ash from municipal solid waste incinerators using differential scanning calorimetry

Abstract Endothermic (in the 30–300°C range) and exothermic (in the 300–500°C range) processes were identified through differential scanning calorimetry experiments on fly ash in an air atmosphere. The endothermic processes are thermodynamically controlled and include the desorption of organic compounds along with a phase transition. Instead, exothermic processes are kinetically controlled and include two distinct combustion reactions. Their nature was confirmed by the flatness in DSC scans performed in nitrogen. The apparent activation energies of the two reactions are in very good agreement with those previously obtained from kinetic studies. Based on these laboratory experiments, the energy balance of the thermal process on the fly ash was performed.

14th congress of combustion by-products and their health effects—origin, fate, and health effects of combustion-related air pollutants in the coming era of bio-based energy sources

The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the “Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources”. The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.

Lab-scale pyrolysis of the Automotive Shredder Residue light fraction and characterization of tar and solid products

The general aim of this study is the recovery of Automotive Shredder Residue (ASR). The ASR light fraction, or car fluff, that was collected at an Italian shredding plant was pyrolysed at various temperatures (500-800°C) in a lab-scale reactor. The condensable gases (tar) and solid residue yields increased with decreasing temperature, and these products were characterized to suggest a potential use to reclaim them. The higher heating value (HHV) of tar was 34-37MJ/kg, which is comparable with those of fossil fuels. Furthermore, the ash content was low (0.06-4.98%). Thus, tar can be used as an alternative fuel. With this prospect, the concentrations of polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in tar were determined. The toxicity of tar changes with temperature (1-5ng I-TEQ/g), and the PCDFs significantly contribute to tar toxicity, which was 75-100% with a maximum of 99.6% at 700°C. Regarding the characterization of the solid residue, the low HHV (2.4-3.3MJ/kg) does not make it suitable for energy recovery. Regarding material recovery, we considered its use as a filler in construction materials or a secondary source for metals. It shows a high metal concentration (280,000-395,000mg/kg), which is similar at different pyrolysis temperatures. At 500°C, polycyclic aromatic hydrocarbons (PAHs) were not detected in the solid residue, whereas the maximum total PAH concentration (19.41ng/g, 700°C) was lower than that in fly ash from MSWI. In conclusion, 500°C is a suitable pyrolysis temperature to obtain valuable tar and solid residue.

Biological devulcanization of ground natural rubber by Gordonia desulfuricans DSM 44462T strain

Due to the rapid increase of waste vulcanized rubber products, the development of low-cost, efficient, and selective devulcanization processes is needed. In this paper, the devulcanization ability of Gordonia desulfuricans DSM 44462T was evaluated by a design of experiments. The aim of the experimental design was to investigate the importance of parameters influencing the bacterial growth, such as the glucose concentration (C), dibenzothiophene concentration (DBT), and initial biomass (optical density, OD) in biodevulcanization process. The complex viscosity (η*) was chosen as experimental response for the experimental design. A multiple linear regression was used to model the relationship between the response and the process variables. In addition, the crosslink density and gel fraction were measured. Furthermore, the automated ribosomal intergenic spacer analysis (ARISA) as a microbiological method was performed to assess the persistence of the inoculated strain during the experiments. Reduced regression models were obtained considering only the significant variables and interactions. The glucose concentration C and OD variables and C–DBT and DBT–OD interactions resulted to the relevant parameters for the process. The fingerprinting showed the persistence of G. desulfuricans DSM 44462T, despite the presence of other bacterial population after the VGNR sterilization. These results highlight the importance to support the physics analysis with microbiological analyses to evaluate the bacterial persistence during the treatment.

Nitrogen activation of carbon-encapsulated zero-valent iron nanoparticles and influence of the activation temperature on heavy metals removal

This work was financially supported by University of Milano-Bicocca fund (2016-ATESP-0597) and University of Alicante (UAFPU2013-5791).