Francesca Beolchini

Equilibrium biosorption studies in single and multi-metal systems

Different models were used in order to describe equilibrium data obtained by heavy metal biosorption tests. Arthrobacter sp. biomass was suspended in aqueous solution and tested as biosorbent material for copper and cadmium ions. The effects of pH on biosorption in single metal systems (copper and cadmium) and on the selectivity of biomass in two metal systems (copper–cadmium) was studied. Biosorption trials performed for each single metal (in the range 0–2 mmol/l) at different equilibrium pHs (3–6 units) showed a general positive effect of pH increase on metal specific uptake. Experimental data obtained for each metal were fitted using adsorption models including Langmuir, Freundlich and Redlich–Peterson isotherms. Biosorption tests were also carried out using binary solutions of copper and cadmium at different equilibrium pH to evaluate biomass selectivity. Modified Langmuir and Freundlich models were used to fit these equilibrium data. The biomass tested was more selective for copper ions and this selectivity changes with equilibrium pH. In both single and two metal systems, a simple procedure of model discrimination was performed to establish which of the tested models better represents the experimental behaviour.

Damage and degradation rates of extracellular DNA in marine sediments: implications for the preservation of gene sequences.

The extracellular DNA pool in marine sediments is the largest reservoir of DNA of the world oceans and it potentially represents an archive of genetic information and gene sequences involved in natural transformation processes. However, no information is at present available for the gene sequences contained in the extracellular DNA and for the factors that influence their preservation. In the present study, we investigated the depurination and degradation rates of extracellular DNA in a variety of marine sediment samples characterized by different ages (up to 10 000 years) and environmental conditions according to the presence, abundance and diversity of prokaryotic gene sequences. We provide evidence that depurination of extracellular DNA in these sediments depends upon the different environmental factors that act synergistically and proceeds at much slower rates than those theoretically predicted or estimated for terrestrial ecosystems. These findings suggest that depurination in marine sediments is not the main process that limits extracellular DNA survival. Conversely, DNase activities were high suggesting a more relevant role of biologically driven processes. Amplifiable prokaryotic 16S rDNA sequences were present in most benthic systems analysed, independent of depurination and degradation rates and of the ages of the sediment samples. Additional molecular analyses revealed that the extracellular DNA pool is characterized by relatively low‐copy numbers of prokaryotic 16S rDNA sequences that are highly diversified. Overall, our results suggest that the extracellular DNA pool in marine sediments represents a repository of genetic information, which can be used for improving our understanding of the biodiversity, functioning and evolution of ecosystems over different timescales.

Biosorption of copper by Sphaerotilus natans immobilised in polysulfone matrix: Equilibrium and kinetic analysis

Abstract Copper biosorption by Sphaerotilus natans immobilised in polysulfone matrices has been studied. Firstly, a rough characterisation of biosorbent beads has been performed, and operating conditions for beads preparation aimed at biosorption have been optimised. Then, the equilibrium of the process was studied in order to determine the effect of pH and biomass concentration inside beads; experimental data were successfully fitted by the Langmuir equation, and the highest value for loading was 5.4 mg/g estimated at pH 5.5 and 0.18 g of lyophilised biomass per gram of beads. Biosorption kinetics has also been studied, and an original kinetic model was developed which is able to correlate experimental data. This model was developed from the Shrinking Core Model, considering a variable copper diffusion coefficient dependent on the process conversion. The estimated values for copper diffusion coefficient were obviously lower than copper diffusivity in water, and they depend on biomass concentration inside beads. Beads regeneration was studied using EDTA, HCl and CaCl 2 . Satisfactory biosorption performances were observed also after 10 sorption/desorption cycles, with CaCl 2 as regeneration solution. All the results confirmed the technical feasibility of the biosorption process by a polysulfone-entrapped biomass even though biosorption efficiency should be improved.

Metal recovery from spent refinery catalysts by means of biotechnological strategies.

A bioleaching study aimed at recovering metals from hazardous spent hydroprocessing catalysts was carried out. The exhaust catalyst was rich in nickel (4.5 mg/g), vanadium (9.4 mg/g) and molybdenum (4.4 mg/g). Involved microorganisms were iron/sulphur oxidizing bacteria. Investigated factors were elemental sulphur addition, ferrous iron addition and actions contrasting a possible metal toxicity (either adding powdered activated charcoal or simulating a cross current process by means of periodical filtration). Ferrous iron resulted to be essential for metal extraction: nickel and vanadium extraction yields were 83% and 90%, respectively, while about 50% with no iron. The observed values for molybdenum extraction yields were not as high as Ni and V ones (the highest values were around 30-40%). The investigated actions aimed at contrasting a possible metal toxicity resulted not to be effective; in contrast, sequential filtration of the liquor leach had a significant negative effect on metals extraction. Nickel and vanadium dissolution kinetics resulted to be significantly faster than molybdenum dissolution ones. Furthermore, a simple first order kinetic model was successfully fitted to experimental data. All the observed results supported the important role of the indirect mechanism in bioleaching of LC-Finer catalysts.

Environmental Impact Assessment of Hydrometallurgical Processes for Metal Recovery from WEEE Residues Using a Portable Prototype Plant

Life cycle assessment (LCA) was applied to hydrometallurgical treatments carried out using a new portable prototype plant for the recovery of valuable metals from waste electrical and electronic equipment (WEEE). The plant was fed with the WEEE residues from physical processes for the recycling of fluorescent lamps, cathode ray tubes (CRTs), Li-ion accumulators and printed circuit boards (PCBs). Leaching with sulfuric acid was carried out, followed by metal recovery by selective precipitation. A final step of wastewater treatment with lime was performed. The recovered metals included yttrium, zinc, cobalt, lithium, copper, gold, and silver. The category of global warming potential was the most critical one considering the specifications for southern European territories, with 13.3 kg CO(2)/kg recovered metal from the powders/residues from fluorescent lamps, 19.2 kg CO(2)/kg from CRTs, 27.0 kg CO(2)/kg from Li-ion accumulators and 25.9 kg CO(2)/kg from PCBs. Data also show that metal extraction steps have the highest load for the environment. In general, these processes appear beneficial for the environment in terms of CO(2) emissions, especially for metal recovery from WEEE residues from fluorescent lamps and CRTs.

Bioremediation of marine sediments contaminated by hydrocarbons: Experimental analysis and kinetic modeling

This work deals with bioremediation experiments on harbor sediments contaminated by aliphatic and polycyclic aromatic hydrocarbons (PAHs), investigating the effects of a continuous supply of inorganic nutrients and sand amendments on the kinetics of microbial growth and hydrocarbon degradation. Inorganic nutrients stimulated microbial growth and enhanced the biodegradation of low and high molecular weight hydrocarbons, whereas sand amendment increased only the removal of high molecular weight compounds. The simultaneous addition of inorganic nutrients and sand provided the highest biodegradation (>70% for aliphatic hydrocarbons and 40% for PAHs). A semi-empirical kinetic model was successfully fitted to experimental temporal changes of hydrocarbon residual concentrations and microbial abundances. The estimated values for parameters allowed to calculate a doubling time of 2.9 d and a yield coefficient biomass/hydrocarbons 0.39 g C biomass g-1C hydrocarbons, for the treatment with the highest hydrocarbon biodegradation yield. A comparison between the organic carbon demand and temporal profiles of hydrocarbons residual concentration allowed also to calculate the relative contribution of contaminants to carbon supply, in the range 5-32%. This suggests that C availability in the sediments, influencing prokaryotic metabolism, may have cascade effects on biodegradation rates of hydrocarbons. Even if these findings do not represent a general rule and site-specific studies are needed, the approach used here can be a relevant support tool when designing bioremediation strategies on site.

Recovery of yttrium from fluorescent powder of cathode ray tube, CRT: Zn removal by sulphide precipitation

This work is focused on the recovery of yttrium and zinc from fluorescent powder of cathode ray tube (CRT). Metals are extracted by sulphuric acid in the presence of hydrogen peroxide. Leaching tests are carried out according to a 2(2) full factorial plan and the highest extraction yields for yttrium and zinc equal to 100% are observed under the following conditions: 3M of sulphuric acid, 10% v/v of H2O2 concentrated solution at 30% v/v, 10% w/w pulp density, 70°C and 3h of reaction. Two series of precipitation tests for zinc are carried out: a 2(2) full factorial design and a completely randomized factorial design. In these series the factors investigated are pH of solution during the precipitation and the amount of sodium sulphide added to precipitate zinc sulphide. The data of these tests are used to describe two empirical mathematical models for zinc and yttrium precipitation yields by regression analysis. The highest precipitation yields for zinc are obtained under the following conditions: pH equal to 2-2.5% and 10-12%v/v of Na2S concentrated solution at 10%w/v. In these conditions the coprecipitation of yttrium is of 15-20%. Finally further yttrium precipitation experiments by oxalic acid on the residual solutions, after removing of zinc, show that yttrium could be recovered and calcined to obtain the final product as yttrium oxide. The achieved results allow to propose a CRT recycling process based on leaching of fluorescent powder from cathode ray tube and recovery of yttrium oxide after removing of zinc by precipitation. The final recovery of yttrium is 75-80%.

Assessment of biotechnological strategies for the valorization of metal bearing wastes.

The present work deals with the application of biotechnology for the mobilization of metals from different solid wastes: end of life industrial catalysts, heavy metal contaminated marine sediments and fluorescent powders coming from a cathode ray tube glass recycling process. Performed experiments were aimed at assessing the performance of acidophilic chemoautotrophic Fe/S-oxidizing bacteria for such different solid matrices, also focusing on the effect of solid concentration and of different substrata. The achieved results have evidenced that metal solubilization seems to be strongly influenced by the metal speciation and partitioning in the solid matrix. No biological effect was observed for Ni, Zn, As, Cr mobilization from marine sediments (34%, 44%, 15%, 10% yields, respectively) due to metal partitioning. On the other hand, for spent refinery catalysts (Ni, V, Mo extractions of 83%, 90% and 40%, respectively) and fluorescent powders (Zn and Y extraction of 55% and 70%, respectively), the improvement in metal extraction observed in the presence of a microbial activity confirms the key role of Fe/S oxidizing bacteria and ferrous iron. A negative effect of solid concentration was in general observed on bioleaching performances, due to the toxicity of dissolved metals and/or to the solid organic component.

Auto- and heterotrophic acidophilic bacteria enhance the bioremediation efficiency of sediments contaminated by heavy metals

This study deals with bioremediation treatments of dredged sediments contaminated by heavy metals based on the bioaugmentation of different bacterial strains. The efficiency of the following bacterial consortia was compared: (i) acidophilic chemoautotrophic, Fe/S-oxidising bacteria, (ii) acidophilic heterotrophic bacteria able to reduce Fe/Mn fraction, co-respiring oxygen and ferric iron and (iii) the chemoautotrophic and heterotrophic bacteria reported above, pooled together, as it was hypothesised that the two strains could cooperate through a mutual substrate supply. The effect of the bioremediation treatment based on the bioaugmentation of Fe/S-oxidising strains alone was similar to the one based only on Fe-reducing bacteria, and resulted in heavy-metal extraction yields typically ranging from 40% to 50%. The efficiency of the process based only upon autotrophic bacteria was limited by sulphur availability. However, when the treatment was based on the addition of Fe-reducing bacteria and the Fe/S oxidizing bacteria together, their growth rates and efficiency in mobilising heavy metals increased significantly, reaching extraction yields >90% for Cu, Cd, Hg and Zn. The additional advantage of the new bioaugmentation approach proposed here is that it is independent from the availability of sulphur. These results open new perspectives for the bioremediation technology for the removal of heavy metals from highly contaminated sediments.

Kinetic analysis of Kluyveromyces lactis fermentation on whey: batch and fed-batch operations

A kinetic analysis of Kluyveromyces lactis fermentation on whey is reported. Batch and fed-batch operations have been considered in 10, 100 and 1000 l fermentors. A simple kinetic model for cell growth during batch and fed-batch operation was used. As expected, the specific growth rate was well represented by the Monod equation. Parameters have been estimated by fitting the model to experimental results achieved in the batch step. Results obtained in the fed-batch operation showed the ability of the model to predict K. lactis fermentation courses on whey in different scales.