Laura Rocchetti

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.

Evolution of microbial "streamer" growths in an acidic, metal-contaminated stream draining an abandoned underground copper mine.

A nine year study was carried out on the evolution of macroscopic “acid streamer” growths in acidic, metal-rich mine water from the point of construction of a new channel to drain an abandoned underground copper mine. The new channel became rapidly colonized by acidophilic bacteria: two species of autotrophic iron-oxidizers (Acidithiobacillus ferrivorans and “Ferrovum myxofaciens”) and a heterotrophic iron-oxidizer (a novel genus/species with the proposed name “Acidithrix ferrooxidans”). The same bacteria dominated the acid streamer communities for the entire nine year period, with the autotrophic species accounting for ~80% of the micro-organisms in the streamer growths (as determined by terminal restriction enzyme fragment length polymorphism (T-RFLP) analysis). Biodiversity of the acid streamers became somewhat greater in time, and included species of heterotrophic acidophiles that reduce ferric iron (Acidiphilium, Acidobacterium, Acidocella and gammaproteobacterium WJ2) and other autotrophic iron-oxidizers (Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans). The diversity of archaea in the acid streamers was far more limited; relatively few clones were obtained, all of which were very distantly related to known species of euryarchaeotes. Some differences were apparent between the acid streamer community and planktonic-phase bacteria. This study has provided unique insights into the evolution of an extremophilic microbial community, and identified several novel species of acidophilic prokaryotes.

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.

Effects of prokaryotic diversity changes on hydrocarbon degradation rates and metal partitioning during bioremediation of contaminated anoxic marine sediments.

We investigated changes of prokaryotic diversity during bioremediation experiments carried out on anoxic marine sediments characterized by high hydrocarbon and metal content. Microcosms containing contaminated sediments were amended with lactose and acetate and incubated in anaerobic conditions up to 60 d at 20 or 35 °C. Microcosms displaying higher degradation efficiency of hydrocarbons were characterized by the dominance of Alphaproteobacteria and Methanosarcinales and the lack of gene sequences belonging to known hydrocarbonoclastic bacteria. Multivariate analyses support the hypothesis that Alphaproteobacteria are important for hydrocarbon degradation and highlight a potential synergistic effect of archaea and bacteria in changes of metal partitioning. Overall, these results point out that the identification of changes in the prokaryotic diversity during bioremediation of contaminated marine sediments is not only important for the improvement of bio-treatment performance towards hydrocarbons, but also for a better comprehension of changes occurring in metal partitioning which affect their mobility and toxicity.

Improvement of Bioremediation Performance for the Degradation of Petroleum Hydrocarbons in Contaminated Sediments

nutrients or composts were added to the microcosms, while, in thefirst anaerobic phase of the two-step experiment, acetate and/or allochthonous sulfate-reducing bacteria were used. After the treatment under anaerobic conditions, samples were exposed to aerobic conditions in the presence of compost. In the aerobic treatments, 81% hydrocarbon biodegradation was observed after 43 days in the presence of inorganic nutrients. In aerobic conditions in the presence of mature compost, hydrocarbon biodegradation was 51% after 43 days of treatment, whereas it was 47% after 21 days with fresh compost. The two-step experiment allowed us to obtain a hydrocarbon degradation of 91%, after a first anaerobic step with an inoculum of sulfate-reducing prokaryotes.

Chemical and biological strategies for the mobilisation of metals/semi-metals in contaminated dredged sediments: experimental analysis and environmental impact assessment

This study deals with laboratory-scale investigations to evaluate the efficiency of different chemical leaching agents (i.e. sulfuric, oxalic and citric acids) and bioleaching processes (based on different acidophilic bacterial strains) on the mobilisation of metals/semi-metals in contaminated harbour sediments. A simplified life-cycle assessment was also performed in order to compare the investigated strategies in terms of their main environmental impacts. The different chemical leaching agents provided different extraction efficiencies of toxic metals. Among the investigated chemical leaching agents, citric acid 0.5 M and sulfuric acid pH 2 were the most effective, with average mobilisation efficiencies of ∼30% for Zn and Cr, ∼40% for Ni, and 35 and 58% for As, under citric and sulfuric acid, respectively. Similar higher extraction efficiencies of metals were also observed in bioleaching experiments with the presence of ferrous iron. The life-cycle assessment revealed that treatments based on diluted sulfuric acid are a better option considering both resource requirements and emissions, leading to lower environmental impacts compared with the other treatment strategies. Overall results from this study provide new insights for the definition of the most efficient and environmentally friendly strategies to be used for dredged sediments contaminated with metals.

Environmental impact assessment of different end-of-life LCD management strategies

The strong growth of the electrical and electronic equipment production combined with its short lifespan are causing the production of a significant amount of waste to treat. In particular, the present paper focuses on end-of-life liquid crystal displays (LCDs) for their significant content of valuable materials, like plastic, glass and metals that could be recovered after dismantling. In the recent literature, traditional LCD recycling processes are combined with innovative treatments, which allow to recover critical raw materials, such as indium. In this context, we have evaluated the environmental impact of four different strategies of end-of-life LCD management: the disposal in landfilling sites, the incineration, the traditional recycling treatment and an innovative process also addressed to the recovery of indium. The traditional recycling treatment resulted to be the best scenario for the environment. Indeed, a life cycle assessment study gave following environmental burdens (if negative they are credits): 18, 81, -68, -60kg CO2-equiv. and 0.08, 0.01, -0.25, -0.18mol H+-equiv., for the four scenarios in the categories of global warming and acidification, respectively. The limit of the variability of LCD composition was overcome including additional literature data in the study. In order to improve the innovative process sustainability, a system of water recirculation was optimized with a consequent impact decrease of 35% in the global warming category. Nevertheless, this action should be combined with an increase of indium concentration in the panel because the low metal content represents the bottleneck of the overall approach. In this regard, a sensitivity analysis showed that an increase of at least five times in indium concentration in the waste is needed to observe an advantage of the innovative vs the traditional recycling process, when the impact category of climate change is considered. As a whole, the life cycle assessment was confirmed as a key tool for the choice of the best option of WEEE management.

An environmentally friendly process for the recovery of valuable metals from spent refinery catalysts

The present study dealt with the whole valorization process of exhaust refinery catalysts, including metal extraction by ferric iron leaching and metal recovery by precipitation with sodium hydroxide. In the leaching operation the effects on metal recovery of the concentration and kind of acid, the concentration of catalyst and iron (III) were determined. The best operating conditions were 0.05 mol L−1 sulfuric acid, 40 g L−1 iron (III), 10% catalyst concentration; almost complete extraction of nickel and vanadium, and 50%extraction efficiency of aluminium and less than 20% for molybdenum. Sequential precipitation on the leach liquor showed that it was not possible to separate metals through such an approach and a recovery operation by means of a single-stage precipitation at pH 6.5 would simplify the procedures and give a product with an average content of iron (68%), aluminium (13%), vanadium (11%), nickel (6%) and molybdenum (1%) which would be potentially of interest in the iron alloy market. The environmental sustainability of the process was also assessed by means of life cycle assessment and yielded an estimate that the highest impact was in the category of global warming potential with 0.42 kg carbon dioxide per kg recovered metal.

Recovery of critical metals from LCDs and Li-ion batteries

In 2014, the European Union defined a list of 20 raw materials critical for economic importance and high supply risk. The aim of this work is to present the main results achieved within the EU-FP7 Project HydroWEEE-Demo dealing with the recovery of indium and cobalt, metals included in such European list, from LCD scraps and end of life Li-ion batteries, respectively. A complete indium recovery was achieved carrying out an acidic leaching, followed by a zinc cementation. Cobalt was extracted from the electrodic powder according to the following main operations: leaching (by acid reducing conditions), primary purification (by precipitation of metal impurities), solvent extraction with D2EPHA (for the removal of metal impurities), solvent extraction with Cyanex 272 (for the separation of cobalt from nickel), cobalt recovery (by precipitation as cobalt hydroxide). Co products with 95% purity were obtained by implementation of the solvent extraction with D2EHPA and Cyanex 272.