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- Feasibility of co-treating olive mill wastewater and acid mine drainagePublication . Carlier, Jorge; Luís, Ana; Alexandre, Luís Miguel; Costa, Maria ClaraPrevious tests using a growth medium and olive mill wastewater (OMWW) have shown that it supplies carbon and electron donors suitable for sulphate reducing bacteria (SRB). We assessed the co-treatment of acid mine drainage (AMD) and OMWW using SRB-enriched bioreactors and identified the most abundant bacterial populations present under optimized conditions. The process requires a neutralizing agent to create optimal pH conditions for successful removal of the AMD's main contaminants. Concentrations of SO42-, Al, Fe, Cu, Zn, and Mn decreased to below Portugal's maximum admissible values for irrigation waters, and all but Mn were reduced to less than Portugal's emission limit values (ELVs) for wastewater discharges. Phenol concentrations-the main pollutants in OMWW-dropped to values between 1/10 and 1/5 their initial concentrations in batch tests using mixtures of AMD and OMWW, and to 1/2 their initial concentrations in flow-through tests. The final total phenol concentrations were still above the ELV for wastewater discharges, but phenols are not regulated in irrigation waters, and OMWW is used by some producers to irrigate soils. Six main SRB groups were identified as likely having a fundamental role in the bioremediation process: the generaDesulfovibrio,Sulfurospirillum, andAcetobacterand the familiesSphingomonadaceae,Prevotellaceae, andDeferribacteraceae
- Biodegradation of 17α-Ethinylestradiol by strains of Aeromonas Genus isolated from acid mine drainagePublication . Da Luz Palma, Tânia Cristina; Costa, Maria Clara17α-ethinylestradiol (EE2), a synthetically derived analogue of endogenous estrogen, is widely employed as a hormonal contraceptive and is recognized as a highly hazardous emerging pollutant, causing acute and chronic toxic effects on both aquatic and terrestrial organisms. It has been included in the initial Water Watch List. The aim of this study was to isolate bacteria from consortia recovered from mine sediments and acid mine drainage samples, both considered extreme environments, with the ability to degrade EE2. From the most promising consortia, isolates affiliated with the Aeromonas, Rhizobium, and Paraburkholderia genera were obtained, demonstrating the capability of growing at 50 mg/L EE2. Subsequently, these isolates were tested with 9 mg/L of EE2 as the sole carbon source. Among the isolated strains, Aeromonas salmonicida MLN-TP7 exhibited the best performance, efficiently degrading EE2 (95 ± 8%) and reaching concentrations of this compound below the limits of detection within 7 and 9 days. The final metabolites obtained are in accordance with those of the TCA cycle; this may indicate EE2 mineralization. As far as is known, Aeromonas salmonicida was isolated for the first time and identified in acid mine drainage, demonstrating its capacity to degrade EE2, making it a promising candidate for bioaugmentation and suggesting its possible applicability in low pH environments.
- Biological synthesis of nanosized sulfide semiconductors: current status and future prospectsPublication . Costa, João Pinto da; Girão, Ana Violeta; Trindade, Tito; Costa, Maria Clara; Duarte, Armando; Rocha-Santos, TeresaThere have been extensive and comprehensive reviews in the field of metal sulfide precipitation in the context of environmental remediation. However, these works have focused mainly on the removal of metals from aqueous solutions-usually, metal-contaminated effluents-with less emphasis on the precipitation process and on the end-products, frequently centering on metal removal efficiencies. Recently, there has been an increasing interest not only in the possible beneficial effects of these bioremediation strategies for metal-rich effluents but also on the formed precipitates. These metal sulfide materials are of special relevance in industry, due to their optical, electronic, and mechanical properties. Hence, identifying new routes for synthesizing these materials, as well as developing methodologies allowing for the control of the shape and size of particulates, is of environmental, economic, and practical importance. Multiple studies have shown proof-of-concept for the biological synthesis of inorganic metallic sulfide nanoparticles (NPs), resorting to varied organisms or cell components, though this information has scarcely been structured and compiled in a systematic manner. In this review, we overview the biological synthesis methodologies of nanosized metal sulfides and the advantages of these strategies when compared to more conventional chemical routes. Furthermore, we highlight the possibility of the use of numerous organisms for the synthesis of different metal sulfide NPs, with emphasis on sulfate-reducing bacteria (SRB). Finally, we put in perspective the potential of these methodologies in the emerging research areas of biohydrometallurgy and nanobiotechnology for the uptake of metals in the form of metal sulfide nanoparticles. A more complete understanding of the principles underlying the (bio)chemistry of formation of solids in these conditions may lead to the large-scale production of such metal sulfides, while simultaneously allowing an enhanced control over the size and shape of these biogenic nanomaterials.
- N,N '-dimethyl-N,N '-dicyclohexylsuccinamide: A novel molecule for the separation and recovery of Pd(II) by liquid-liquid extractionPublication . Costa, Maria Clara; Assunção, Ana; Almeida, Rúben; Rosa da Costa, Ana; Nogueira, Carlos; Paiva, Ana PaulaN,N'-dimethyl-N,N'-dicyclohexylsuccinamide (DMDCHSA) is investigated as a potential molecule for the liquid-liquid extraction of Pd(II) from chloride solutions for the first time. The effect of several parameters on Pd(II) extraction, such as the contact period between both phases, hydrochloric acid, extractant and hydrogen ion concentrations, is evaluated. Pd(II) extraction equilibrium is very fast (30 s) and the extraction percentage (%E) increases with the HCI concentration in the aqueous phases, being higher than 60% for [HCl] > 5 M. The loading capacity of DMDCHSA for Pd(II) is reasonable (molar ratio extractant/metal higher than 16). Several stripping agents (e.g. distilled water, 1 M HCl, seawater and 20 g/L chloride solution as NaCl) were successfully used to transfer Pd(II) to a new aqueous phase, and data obtained from five successive extraction-stripping cycles suggest a good DMDCHSA stability pattern. Attempts to replace 1,2-dichloroethane (1,2-DCE) by commercial and more environmentally friendly diluents showed much worse %E for Pd(II). Selectivity tests with binary, ternary and more complex metal ion solutions were carried out to evaluate the performance of DMDCHSA towards Pd(II) recovery from 6 M HCl, when in presence of Pt(IV), Fe(III), Zn(II), Al(III) and Ce(III), metal ions usually present in solutions that may result from the hydrometallurgical treatment of spent automobile catalytic converters. It was generally observed that the additional metal ions do not affect the recovery of Pd(II) by DMDCHSA, although Fe(III) and Pt(IV) were co-extracted in a great extent. A solvent extraction (SX) scheme is proposed, based on a previous separation of Fe(III) with tributylphosphate (TBP) and on the selective and sequential stripping of Pt(IV) and Pd(II) from the loaded DMDCHSA with 0.01 M thiourea in 0.5 M HCI and seawater, respectively. The dependence of the Pd(II) distribution ratios on DMDCHSA and acidity, complemented with UV-Visible spectroscopy data, points out to DMDCHSA:Pd(II) extracted species with a 2:1 molar ratio and suggests the occurrence of an outer-sphere ion pair reaction, in which both [PdCl4](2-) and HCI are extracted.
- Prokaryotic diversity in stream sediments affected by acid mine drainagePublication . Carlier, Jorge; Ettamimi, Sara; Cox, Cymon J.; Hammani, Khalil; Ghazal, Hassan; Costa, Maria ClaraThe microbial communities in mining impacted areas rely on a variety of mechanisms to survive in such extreme environments. In this work, a meta-taxonomic approach using 16S rRNA gene sequences was used to investigate the prokaryotic diversity of sediment samples from water bodies affected by acid mine drainage at the Sao Domingos mining area in the south of Portugal. Samples were collected in summer and winter from the most contaminated sites from where the water flows downstream to the freshwater of Chanca's river reservoir. The prokaryotic diversity on water bodies' sediments allowed us to distinguish the highly contaminated sites (pH approximate to 2) from sites with intermediate levels of contamination (pH approximate to 3-6.5), and from sites without contamination (pH approximate to 7.5). The abundances of acidophiles of generaAcidiphilium, Acidibacter, Acidobacterium and Acidocellain the sediments were correlated with the level of acid mine drainage contamination. The two first genera were among the 30 most abundant prokaryotes in all contaminated samples, including one (SS2w), where the contamination was very diluted, thereby emphasizing the impact that such type of pollution can have in the microbial communities of sediments. In addition, the high abundances of archaeal taxa from classThermoplasmataand of bacteria from family RCP1-48 in the sediments from the most contaminated site corroborate their importance in such ecosystems and a putative role in the generation of acid mine drainage.
- Mechanism of uranium (VI) removal by two anaerobic bacterial communitiesPublication . Martins, Mónica; Faleiro, Leonor; Rosa da Costa, Ana; Chaves, Sandra; Tenreiro, Rogério; Matos, António Pedro; Costa, Maria ClaraThe mechanism of uranium (VI) removal by two anaerobic bacterial consortia, recovered from an uncontaminated site (consortium A) and other from an uranium mine (consortium U), was investigated. The highest efficiency of U (VI) removal by both consortia (97%) occurred at room temperature and at pH 7.2. Furthermore, it was found that U (VI) removal by consortium A occurred by enzymatic reduction and bioaccumulation, while the enzymatic process was the only mechanism involved in metal removal by consortium U. FTIR analysis suggested that after U (VI) reduction, U (IV) could be bound to carboxyl, phosphate and amide groups of bacterial cells. Phylogenetic analysis of 16S rRNA showed that community A was mainly composed by bacteria closely related to Sporotalea genus and Rhodocyclaceae family, while community U was mainly composed by bacteria related to Clostridium genus and Rhodocyclaceae family.
- Design of remediation pilot plants for the treatment of industrial metal-bearing effluents (BIOMETAL DEMO project): Lab testsPublication . Ballester, Antonio; Castro, Laura; Clara Costa, Maria; Carlier, Jorge; Garcia-Roig, Manuel; Perez-Galende, Patricia; Alvarez, Angela; Bertagnolli, Caroline; Guibal, EricCurrent research is the first part of the BIOMETAL DEMO project, funded by the European Union, focusing on the development of complementary and modular biotreatment processes for the removal of metal ions from industrial effluents (issued from mining industry, surface treatment and ceramics). Metal bio-precipitation (in form of metal sulfides and metal phosphates) using sulfate-reducing bacteria (SRB), phytase and phosphatase enzymes, biosorption using sugar-beet pulp, algal biomass and alginate- or chitosan-based composites (immobilizing polyethyleneimine derivatives by encapsulation) have been extensively studied using synthetic and industrial effluents. These preliminary results allow designing a treatment flow-sheet including pre-treatment of the effluent using biologically-assisted precipitation followed by biosorption (for mining effluents that contain sulfate anions). For surface treatment and ceramics effluents, bio-precipitation combined with biosorption processes and physicochemical pretreatment followed by biosorption process represent, respectively, a promising solution. The carbon-source for the SRB process, the optimization of process parameters and the biosorbents have been selected taking into account both the technical performance and the economic viability. (C) 2016 Elsevier B.V. All rights reserved.
- Oxidative leaching process with cupric ion in hydrochloric acid media for recovery of Pd and Rh from spent catalytic convertersPublication . Nogueira, C. A.; Paiva, A. P.; Oliveira, P. C.; Costa, Maria Clara; Costa, Ana M. Rosa daThe recycling of platinum-group metals from wastes such as autocatalytic converters is getting growing attention due to the scarcity of these precious metals and the market pressure originated by increase of demand in current and emerging applications. Hydrometallurgical treatment of such wastes is an alternative way to the most usual pyrometallurgical processes based on smelter operations. This paper focuses on the development of a leaching process using cupric chloride as oxidising agent, in HCl media, for recovery of palladium and rhodium from a spent catalyst. The chloride media allows the adequate conditions for oxidising and solubilising the metals, as demonstrated by equilibrium calculations based on thermodynamic data. The experimental study of the leaching process revealed that Pd solubilisation is clearly easier than that of Rh. The factors temperature, time, and HCl and Cu(2+) concentrations were significant regarding Pd and Rh leaching, the latter requiring higher factor values to achieve the same results. Leaching yields of 95% Pd and 86% Rh were achieved under optimised conditions (T = 80 °C, t = 4h, [HCl] = 6M, [Cu(2+)] = 0.3M).
- Comparative study of the antioxidant and enzyme inhibitory activities of two types of Moroccan Euphorbia entire honey and their phenolic extractsPublication . Boutoub, Oumaima; EL-GUENDOUZ, Soukaina; Manhita, Ana; Dias, Cristina Barrocas; Estevinho, Letícia M.; Paula, Vanessa B.; Carlier, Jorge; Costa, Maria Clara; Rodrigues, Brígida; Raposo, Sara; Aazza, Smail; El Ghadraoui, Lahsen; Miguel, Maria GraçaHoney is a natural food product very famous for its health benefits for being an important source of antioxidant and phenolic compounds. Euphorbia honeys obtained from different regions of Morocco were evaluated for their ability to inhibit acetylcholinesterase, lipoxygenase, tyrosinase and xanthine oxidase activities. Their antioxidant properties were evaluated using the: 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging capacity, nitric oxide scavenging activity (NO) and scavenging ability of superoxide anion radical. Then, the phenolic extracts of the same entire honey samples were evaluated by liquid chromatography coupled to diode array detection and mass spectrometry (LC-DAD-MS) and tested for the biological activities previously evaluated on the entire honeys, in order to conduct a comparative study between both (honey and phenolic extracts). The chromatographic profiles for the studied Euphorbia honey extracts were different. Phenolic compounds gallic acid, 4-hydroxybenzoic acid and p-coumaric acid were detected in all samples, whereas kampferol was only present in two samples. Physicochemical parameters and total phenolic content were also determined. Entire honey that recorded the highest rate of phenols was sample M6 (E. resinifera) = 69.25 mg GAE/100 g. On the other hand, the phenolic extracts had better antioxidant and enzyme inhibitory activities than the entire honeys, regardless the monofloral honey type. In conclusion, the studied Euphorbia honeys may have a great potential as antioxidant, anti-inflammatory and anti-tyrosinase sources for pharmaceutical and cosmetic applications.
- N,N′-tetrasubstituted succinamides as new molecules for liquid–liquid extraction of Pt(IV) from chloride mediaPublication . Costa, Maria Clara; Almeida, Ruben; Assunção, Ana; Costa, Ana M. Rosa da; Nogueira, Carlos; Paiva, Ana PaulaDue to the increasing demand of platinum group metals (PGM’s), among which platinum, the search for new alternatives aiming to their extraction and recovery is nowadays of great importance. Thus, two N, N0-tetrasubstituted succinamides, N,N0-dicyclohexyl-N,N0-dimethylsuccinamide (DMDCHSA) and N,N0- dimethyl-N,N0-diphenylsuccinamide (DMDPHSA) were synthesized and investigated, for the first time, as potential molecules for the liquid–liquid extraction of Pt(IV) from chloride solutions. According to the extraction and stripping results obtained in a single contact, these succinamides can be considered promising extractants for the recovery of platinum(IV) from hydrochloric acid media, since DMDCHSA is able to extract more than 95% Pt(IV) from 4 M HCl or higher concentrations, and DMDPHSA extracts 80% and 92% Pt(IV) from 6 M and 8 M HCl solutions, respectively. Furthermore, platinum(IV) can successfully be stripped through a simple contact with seawater: 93% Pt(IV) were recovered from DMDCHSA, while 60% stripping were obtained from DMDPHSA. For each compound, the time necessary to reach equilibrium, and the effects of the type of diluent and different extractant concentrations on the Pt(IV) extraction percentage were investigated. The loading capacity of DMDCHSA and DMDPHSA toward Pt (IV) was also evaluated, and the results show that both extractants present a very high loading capacity. In addition, data obtained from successive extraction-stripping cycles suggest a good stability pattern for both succinamides.