Assessing the efficiency and eco-sustainability of bioremediation strategies for the reclamation of highly contaminated marine sediments.

Coastal sediments subjected to high anthropogenic impacts can accumulate large amounts of polycyclic aromatic hydrocarbons (PAHs) and metals, demanding effective and eco-sustainable remediation solutions. In this study, we carried out bioremediation experiments on marine sediments highly contaminated with PAHs and metals. In particular, we investigated the effects of biostimulation (by the addition of inorganic nutrients), bioaugmentation (by the addition of fungi belonging to Aspergillus sp.) and microbial fuel cell-based strategies on PAH degradation and on changes in metal partitioning. Results reported here indicate that all biotreatments determined a significant decrease of PAH concentrations (at least 60%) in a relatively short time interval (few weeks) and that biostimulation was the most effective approach (>90%). Biostimulation determined a faster degradation rate of high than low molecular weight PAHs, indicating a preferential biodegradation of specific PAH congeners. At the same time, the biotreatments changed the partitioning of metals, including their solubilization, suggesting the need of parallel environmental risk assessment. Our findings also suggest that ex situ biotreatments can have a lower carbon footprint than current management options of contaminated sediments (i.e., landfill disposal and/or disposal in confined aquatic facilities), but integration with other strategies for metal removal (e.g. through bioleaching) from sediments is needed for their safe re-use. Overall, results presented here provide new insights into the development of effective and eco-sustainable bioremediation strategies for the reclamation of highly contaminated marine sediments.

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.

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.

Treatment of concentrated arsenic(V) solutions by micellar enhanced ultrafiltration with high molecular weight cut-off membrane.

In this work arsenic removal by micellar enhanced ultrafiltration (MEUF) was investigated using cetylpyridinium chloride (CPC) and a cross-flow polyethersulphone (PES) membrane apparatus. The effects of some operating factors on permeate flux, arsenic and CPC rejections were investigated and, in particular, transmembrane pressure, pH, CPC concentration, As concentration and ionic strength. The novel aim of this work is evaluating the possible advantages of using large molecular weight cut-off membrane (100 kDa) and reduced surfactant concentrations (1-3 mM) for treating high fluxes of concentrated arsenic-bearing solutions (6-10 ppm). The experimental results reported in this paper show that PES membrane apparatus with high molecular weight cut-off allowed to treat large fluxes of concentrated arsenic-bearing solutions (6-10 ppm) even by using low surfactant concentration (1-3mM). In particular arsenic removal ranged from 93-98% to 70-74% depending on initial As concentration (6 and 10 ppm, respectively). In addition surfactant leakage in the permeate was always below CMC due to presieving of concentration polarisation layer. The favourable combination of high MWCO membranes and low surfactant concentration can benefit to overall process economics for the lower membrane area requirement (due to greater flux) and the reduced surfactant consumption.

Micellar enhanced ultrafiltration for arsenic(V) removal: effect of main operating conditions and dynamic modelling.

In this work arsenic removal by micellar enhanced ultrafiltration (MEUF) was investigated using cetylpyridinium chloride (CPC) in ceramic membrane apparatus. Permeability tests and discontinuous diafiltration tests were performed in different operating conditions to evaluate the effect of membrane pore size (20 and 50 nm), transmembrane pressure, pH, surfactant concentration (1-3 mM), and arsenic concentration (10-40 mg/L) on permeate flux decline, arsenic, and CPC rejections. These preliminary experimental results showed that a ceramic membrane with large pore size allows treament of high fluxes of concentrated arsenic-bearing solutions even by using low surfactant concentrations. Arsenic concentration in the permeate was at the 1 ppm level, with feed As concentrations (10 ppm) that are larger than those generally used in MEUF studies and with CPC amounts that are lower than the usual ones. In addition, operating conditions adopted in these tests obtained CPC concentrations in the permeate always lower than its critical micellar concentration (0.9 mM). Dynamic simulations of discontinuous two-step diafiltration tests allowed a simple and adequate representation of the performance of the process especially for 1 mM CPC, while discrepancies for 2.5 mM CPC level denoted complex interactions between CPC and As.

Ionic strength effect on copper biosorption by Sphaerotilus natans: equilibrium study and dynamic modelling in membrane reactor.

Biosorption of copper by Sphaerotilus natans in different conditions of ionic strength and pH was studied by performing sorption tests in batch and membrane reactors. Equilibrium batch tests evidenced the negative effect of ionic strength and the positive effect of pH on biosorption performances: the highest determined value for copper specific uptake, q, was about 60 mg/g at pH 6 and about 15 mg/g at pH 4. A competitive equilibrium model was successfully fitted to experimental data at different ionic strength levels to account for copper-sodium competition. In membrane reactor tests, experimental profiles of copper concentration in the permeate vs. time did not evidence a significant effect of ionic strength at low pH values (4 and 5). On the other hand a more remarkable effect of ionic strength on copper concentration in the permeate was observed at pH 6. Experimental profiles of continuous biosorption in the membrane reactors were successfully simulated by developing a dynamic model accounting for Cu-Na competition and for binding ability of cells fragments.

Sorption of copper by olive mill residues.

A study on olive mill residues (OMR) as copper adsorbing material is reported in this work. A rough characterization of this waste material has been performed, by microanalysis and SEM pictures. Sorption tests with suspended OMR evidenced copper removal from solution, of about 60% in the investigated experimental conditions. The COD release in solution was also monitored during biosorption. Considering that it was significant, OMR washings with water were performed before biosorption. In this case the COD release in solution was reduced to less than 600 mg/L after two washings, while the OMR metal sorption properties did not change. Regenerated residues by acid solutions gave a copper removal of about 40%, in the same experimental conditions of the first adsorption test: regeneration with EDTA at different concentrations suggested that it presents a damage of adsorption active sites. On the other hand, the use of HCl and CaCl(2) led to completely regenerate the biosorbent material. Tests were also performed with a column filled with 80 g of OMR and the breakpoint was demonstrated to take place after that about 1L solution was treated in the investigated experimental conditions. Regeneration tests permitted to demonstrate that a concentration factor of about 2 can be obtained in no-optimized conditions, highlighting the possibility of using OMR for the treatment of metal bearing effluents. The main advantage of the process would be the "low cost" biosorbing material, considering that it represents a waste in the olive oil production.

Modeling of copper biosorption by Arthrobacter sp. in a UF/MF membrane reactor.

Copper biosorption by Arthrobacter sp. has been studied in this work. The process has been realized inside of a ultrafiltration/microfiltration (UF/MF) reactor in order to confine cells. A mathematical model has been developed that is able to predict experimental data under different operating conditions. The model takes into account different phenomena, which might occur during the process, such as a dependence of equilibrium parameters on pH, a partial cell disruption, and a change in the membrane retention properties at high biomass concentrations. Experimental tests have been performed under different operating conditions: a full factorial design has been implemented with pH (levels: 4, 5, and 6 units) and biomass concentration (levels: 1 and 5 g/L) as factors. A simple mathematical model based on metal mass balance taking into account the effect of pH on the Langmuir equilibrium adsorption parameters well fitted experimental data at low pH values and biomass concentrations. A more complex mathematical model, which considers a partial cell disruption during the biosorption trial, was proposed to understand and analyze the anomalous system behavior at pH = 6 and biomass concentration equal to 5 g/L. The effect of mechanical stress on biomass performances was also examined by using a discontinuous system (test tube trials) simulating the membrane reactor apparatus. In this alternative system biosorption trials were carried out in test tubes in such a way to avoid or at least minimize the disruption due to mechanical stress. Experimental results obtained by using this system can be modeled up to pH = 5 without considering cell disruption phenomenon, while at pH = 6 possible chemical reactions of biomass constituents could happen.

Female gonad of moles, genus Talpa (Insectivora, mammalia): ovary or ovotestis?

The female gonads of moles (genus Talpa) are composed of a cortex, functioning as an ovary, and a medulla, which is structurally similar to that of the testis. In the female reproductive apparatus there are masculine glandular annexes, such as a bilobate prostate, two Cowper glands, and a penis-like clitoris. All these features have recently led to the hypothesis of the presence of hermaphroditism due to sex-reversal in Talpa. The purpose of this study is to understand the functional significance of the structural organization of the female gonads in order to verify this hypothesis. Histological, histochemical and ultrastructural analyses have been carried out on several gonads of both sexes of two species: T. europaea and T. romana, including three fetuses. In both species, the cortical region of the female gonad shows a regular oogenetic activity. While the medulla is composed of interstitial cells that are partly organized in cord-like structures, no spermatogenetic activity has been ever observed inside of them. A histochemical analysis shows that in both sexes the interstitial cells secrete steroids, presumably estrogens as well as androgens. The presence of androgens in the female gonads would therefore explain the persistence of male glandular annexes in the female reproductive apparatus and both the sexual and behavioral monomorphism typical of the genus Talpa. Nonetheless, the female gonad of moles is a real ovary and a well-defined gonochorism exists. Therefore, there is no reason to assert the presence of hermaphroditism due to sex reversal.