ZnAl-SO4 Layered Double Hydroxide and Allophane for Cr(VI), Cu(II) and Fe(III) Adsorption in Wastewater: Structure Comparison and Synergistic Effects.

Owing to their structure, layered double hydroxides (LDHs) and allophane are nowadays considered as promising materials for application in different fields. The goal of this work is to compare the efficacy of allophane and ZnAl-SO4 LDH to remove, by adsorption, some cationic and anionic pollutants from industrial wastewater. Both compounds were synthesized via the co-precipitation route (direct method) followed by hydrothermal treatment, obtaining nanoscopic crystallites with a partially disordered turbostratic (ZnAl-SO4 LDH) or amorphous (allophane) structure. The characterization of the obtained compounds was performed by means of powder x-ray diffraction (PXRD), thermal gravimetry analysis (TGA), field emission scanning electron microscopy analysis (FESEM), and Fourier-transform infrared spectroscopy (FT-IR). The sorbents were tested using wastewater produced by a real metalworking plant and containing ionic species such as Cu(II), Fe(III) and Cr(VI), whose concentration was measured by means of inductively coupled plasma-optical emission spectrometry (ICP-OES). This investigation represents an alternative procedure with respect to standard protocols based on customarily made and artificially lab-produced wastewaters. Both sorbents and their combination proved to be efficient in Cr(VI) removal, irrespective of the presence of cations like Cu(II) and Fe(III). A synergistic effect was detected for Cu(II) adsorption in a mixed allophane/LDH sorbent, leading to a Cu(II) removal rate of 89.5%.

Machine learning-based prediction of toxic metals concentration in an acid mine drainage environment, northern Tunisia.

In northern Tunisia, Sidi Driss sulfide ore valorization had produced a large waste amount. The long tailings exposure period and in situ minerals interactions produced an acid mine drainage (AMD) which contributed to a strong increase in the mobility and migration of huge heavy metal (HM) quantities to the surrounding soils. In this work, the soil mineral proportions, grain sizes, physicochemical properties, SO42- and S contents, and Machine Learning (ML) algorithms such as the Random Forest (RF), Support Vector Machine (SVM), and Artificial Neural Network (ANN) models were used to predict the soil HM quantities transferred from Sidi-Driss mine drainage to surrounding soils. The results showed that the HM concentrations had significantly increased with the increase of decomposition and oxidation of galena, marcasite, pyrite, and sphalerite-marcasite and Fe-oxide-hydroxides quantities and the sulfate dissolution (marked with SO42- ions increase) that produced the decreased soil pH. Compared to SVM, and ANN models outputs, the RF model that revealed higher R2val, RPD, RPIQ, and lower error indices had satisfactorily predicted the soil HM accumulation coming from the AMD environment.

Environmental implications of one-century COPRs evolution in a single industrial site: From leaching impact to sustainable remediation of CrVI polluted groundwater.

The Stoppani factory manufactured chromium for more than one century, dumping millions of tons of Chromite Ore Processing Residues (COPRs) over decades. The massive presence of COPRs resulted in an intense CrVI leaching and consequent contamination of percolating groundwater. The site offers a unique opportunity to follow COPRs evolution from the primary roasting process to the aged Cr-bearing mineral phases. Herein, new insights on COPRs mineralogy evolution and their role in CrVI release are provided by a dry sample preparation protocol, coupled with in-depth multi-technique characterization. Besides typical COPRs mineral assemblages, highly soluble Na2CrO4 and the first evidence of crocoite (PbCrO4) in a COPR contaminated site are revealed. Selective extraction experiments confirmed a strong reactivity for Cr-bearing minerals as confirmed by concentrations as high as 375 mg L-1 of leached CrVI. The mineralogical approach was combined with a nanotechnological solution for CrVI wastewater remediation. The application of naked colloidal maghemite (γ-Fe2O3) nanoparticles (SAMNs) on the complex industrial wastewater, led to > 90% CrVI removal, either under acidic or in-situ conditions. The present case study of a highly polluted site, ranging from mineral characterization to wastewater remediation, highlights the use of multidisciplinary approaches to cope with complex environmental issues.

Sediment distribution on the continental shelf in relation to stream inputs and contamination: hydrodynamic, chemical, mineralogical, and sedimentological characteristics (Ligurian Sea, Italy).

River estuaries, continental shelf, and sediment contamination are closely linked from the point of view of sediment transport and diffusion that is governed by different factors such as sea waves and currents, river flows and floods, and sediment characteristics. Taking these factors into consideration, we have examined marine environmental and marine bottom sediments off the mouth of a stream to highlight the main ways of sediment and contaminant transport and diffusion on the continental shelf. For this purpose, we followed a multidisciplinary approach, studying circulation of water masses, hydrological characteristics of water column, distribution and main characteristics of sediment grain size, sediment mineralogical composition, and metal concentrations of bottom sediments. Our results allowed identifying the presence of preferential ways of sediment deposition and areas of sediment spread for the Entella Stream, as well as the origin of some metals.

Baseline of distribution and origin of Rare Earth Elements in marine sediment of the coastal area of the Eastern Gulf of Tigullio (Ligurian Sea, North-West Italy).

A study on the Rare Earth Element (REE) distribution in the bottom sediments of the Gulf of Tigullio (north-west Italy) was conducted. The results constitute a baseline for this zone of the Ligurian Sea and enabled the obtaining of valuable information on the origin and transport of sediments in the gulf. The distribution of REEs is controlled by phosphates, mainly monazite, and is generally homogeneous in the study area, reflecting the homogeneous distribution of the minerals. Some differences in REE and Sc distribution allow us to identify two sub-basins (Entella and Gromolo torrent sub-basins) characterised by slightly different geological frameworks. The "hat-shaped" observed patterns seem to indicate an overprinting of the original REE patterns due to exchanges between phosphates and seawater. REEs seem to be related with the rocks outcropping in the area, although an indirect effect of anthropic activity could be seen near a fish farm.

Geomicrobiology of a seawater-influenced active sulfuric acid cave.

Fetida Cave is an active sulfuric acid cave influenced by seawater, showing abundant microbial communities that organize themselves under three main different morphologies: water filaments, vermiculations and moonmilk deposits. These biofilms/deposits have different cave distribution, pH, macro- and microelement and mineralogical composition, carbon and nitrogen content. In particular, water filaments and vermiculations had circumneutral and slightly acidic pH, respectively, both had abundant organic carbon and high microbial diversity. They were rich in macro- and microelements, deriving from mineral dissolution, and, in the case of water filaments, from seawater composition. Vermiculations had different color, partly associated with their mineralogy, and unusual minerals probably due to trapping capacities. Moonmilk was composed of gypsum, poor in organic matter, had an extremely low pH (0-1) and low microbial diversity. Based on 16S rRNA gene analysis, the microbial composition of the biofilms/deposits included autotrophic taxa associated with sulfur and nitrogen cycles and biomineralization processes. In particular, water filaments communities were characterized by bacterial taxa involved in sulfur oxidation and reduction in aquatic, aphotic, microaerophilic/anoxic environments (Campylobacterales, Thiotrichales, Arenicellales, Desulfobacterales, Desulforomonadales) and in chemolithotrophy in marine habitats (Oceanospirillales, Chromatiales). Their biodiversity was linked to the morphology of the water filaments and their collection site. Microbial communities within vermiculations were partly related to their color and showed high abundance of unclassified Betaproteobacteria and sulfur-oxidizing Hydrogenophilales (including Sulfuriferula), and Acidiferrobacterales (including Sulfurifustis), sulfur-reducing Desulfurellales, and ammonia-oxidizing Planctomycetes and Nitrospirae. The microbial community associated with gypsum moonmilk showed the strong dominance (>60%) of the archaeal genus Thermoplasma and lower abundance of chemolithotrophic Acidithiobacillus, metal-oxidizing Metallibacterium, Sulfobacillus, and Acidibacillus. This study describes the geomicrobiology of water filaments, vermiculations and gypsum moonmilk from Fetida Cave, providing insights into the microbial taxa that characterize each morphology and contribute to biogeochemical cycles and speleogenesis of this peculiar seawater-influenced sulfuric acid cave.

Baseline evaluation of metal contamination in teleost fishes of the Gulf of Tigullio (north-western Italy): Histopathology and chemical analysis.

Metals, whether essential (Cu, Zn, Cr, Fe, Mn) or non-essential (Al, As, Cd, Ni, Pb, Hg) for organism metabolism, occur naturally in the marine environment and their abundance can increase due to the presence of human activities. In this study, fish were used as bio-indicators, to determine a correlation between the bio-accumulation of metals in muscle and gill tissues and the health status of fish. The study area was the Gulf of Tigullio (north-western Italy), which is impacted by various sources of metal contamination. Histopathology served as a significant tool to investigate possible alterations in gills, one of the main organs involved in fish physiology. Results highlighted some correlations between certain metals (e.g. Pb, Ni) and gill alterations (e.g. epithelial hyperplasia, epithelial lifting), providing baseline data from a pool of different fish species, which can be used for comparison purposes in further studies.

Environmental implications of metal mobility in marine sediments receiving input from a torrent affected by mine discharge.

Acid Mine Drainage (AMD) is one of the most important sources of pollution in fluvial systems and can enrich rivers in dissolved and suspended metals of environmental concern. Colloidal particles may favour the transport of metals to the sea, where metals can be accumulated in bottom sediments. The aim of this paper was to evaluate the mobility of metals in the "Baia delle Favole" bottom sediments (Sestri Levante, Italy), which receive the input of the AMD impacted Gromolo Torrent, using chemical speciation (BCR sequential extraction). Basing on the Risk Assessment Code (RAC), our results showed a systematic and widespread high risk classification for Mn, whereas a medium risk is associated to Co, Cu, and Zn in the sediments collected near the mouth of the Gromolo Torrent. Moreover, in these sediments the occurrence of Fe oxyhydroxides has been observed, reflecting an increase of metals in the reducible fraction obtained with BCR.

Benthic diatom community response to metal contamination from an abandoned Cu mine: Case study of the Gromolo Torrent (Italy).

Environmental contamination has become a global problem of increasing intensity due to the exponential growth of industrialization. One main debated issue is the metal contamination of rivers receiving Acid Mine Drainage (AMD) from active/abandoned mines. In order to assess the quality of lotic systems, diatoms are commonly used, as their assemblage modifies on the basis of changes in environmental parameters. Benthic diatom changes were analyzed along the metal-impacted Gromolo Torrent (Liguria, NW Italy) with the aim of understanding the effects of input from the abandoned Libiola Cu mine. The results support the hypothesis that metals from AMD lead to massive changes in diatoms, resulting in low biological diversity and in a shift of dominance, passing from the genera Cymbella and Cocconeis to more tolerant and opportunistic species, such as Achnanthidium minutissimum and Fragilaria rumpens. The high concentrations of labile metals, measured through Diffusion Gradients in Thin-films (DGT) immediately downstream of the two AMD inputs in the torrent, corresponded to a sudden decrease in the presence of diatoms, indicating the possible reaching of acute toxic levels. In particular, A. minutissimum dominated the mining area and was positively correlated with Cu and Zn; whereas F. rumpens bloomed downstream of this area, where the metal content was diluted, and was positively correlated with As and Pb. Finally, an important abundance of Nitzschia palea and teratological forms of A. minutissimum and F. rumpens were observed downstream from the mine, indicating that metals may have an important impact on diatoms up to the torrent mouth.

Microbial diversity and biosignatures of amorphous silica deposits in orthoquartzite caves.

Chemical mobility of crystalline and amorphous SiO2 plays a fundamental role in several geochemical and biological processes, with silicate minerals being the most abundant components of the Earth's crust. Although the oldest evidences of life on Earth are fossilized in microcrystalline silica deposits, little is known about the functional role that bacteria can exert on silica mobility at non-thermal and neutral pH conditions. Here, a microbial influence on silica mobilization event occurring in the Earth's largest orthoquartzite cave is described. Transition from the pristine orthoquartzite to amorphous silica opaline precipitates in the form of stromatolite-like structures is documented through mineralogical, microscopic and geochemical analyses showing an increase of metals and other bioessential elements accompanied by permineralized bacterial cells and ultrastructures. Illumina sequencing of the 16S rRNA gene describes the bacterial diversity characterizing the consecutive amorphization steps to provide clues on the biogeochemical factors playing a role in the silica solubilization and precipitation processes. These results show that both quartz weathering and silica mobility are affected by chemotrophic bacterial communities, providing insights for the understanding of the silica cycle in the subsurface.

Diclofenac affects early embryo development in the marine bivalve Mytilus galloprovincialis.

Diclofenac-DCF, one of the most widely prescribed non-steroidal anti-inflammatory drug, is globally detected in environmental compartments. Due to its occurrence in freshwater and potential impact on aquatic organisms, it has been added to the watch list of chemicals in the EU Water Directive; consequently, research on the impact of DCF in model aquatic organisms has great regulatory implications towards ecosystem health. DCF is also detected in coastal waters at concentrations from ng/L to 1 µg/L, as well as in marine organisms, such as the mussel Mytilus. Increasing evidence indicates that environmental concentrations of DCF have multiple impacts in adult mussels. Moreover, in M. galloprovincialis, DCF has been shown to affect early embryo development. The developmental effects of DCF in mussels were further investigated. DFC (1 and 10 µg/L) was added at different times post-fertilization (30 min and 24 hpf) and the effects were compared in the 48 hpf embryotoxicity assay. Shell mineralization and morphology were investigated by polarized light microscopy, X-Ray Spectrometry-XRD and Scanning Electron Microscopy-SEM. Transcriptional profiles of 12 selected genes physiologically regulated across early embryo development were assessed at 24 and 48 hpf. DCF induced shell malformations, irrespectively of concentration and time of exposure. DCF phenotypes were characterized by convex hinges, undulated edges, fractured shells. However, no changes in biomineralization were observed. DCF affected gene transcription at both times pf, in particular at 1 µg/L. The most affected genes were those involved in early shell formation (CS, CA, EP) and biotransformation (ABCB, GST). The results confirm that Mytilus early development represents a significant target for environmental concentrations of DCF. These data underline how the standard embryotoxicity assay, in combination with a structural and transcriptomic approach, represents a powerful tool for evaluating the early impact of pharmaceuticals on mussel embryos, and identification of the possible underlying mechanisms of action.

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements.

A synthetic Cu-Al-SO4 layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu1-xAlx(SO4)x/2(OH)2·nH2O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO4 LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO4 LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5-8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis.

Impact of cationic polystyrene nanoparticles (PS-NH2) on early embryo development of Mytilus galloprovincialis: Effects on shell formation.

The potential release of nanoparticles (NPs) into aquatic environments represents a growing concern for their possible impact on aquatic organisms. In this light, exposure studies during early life stages, which can be highly sensitive to environmental perturbations, would greatly help identifying potential adverse effects of NPs. Although in the marine bivalve Mytilus spp. the effects of different types of NPs have been widely investigated, little is known on the effects of NPs on the developing embryo. In M. galloprovincialis, emerging contaminants were shown to affect gene expression profiles during early embryo development (from trocophorae-24 hpf to D-veligers-48 hpf). In this work, the effects of amino-modified polystyrene NPs (PS-NH2) on mussel embryos were investigated. PS-NH2 affected the development of normal D-shaped larvae at 48 hpf (EC50 = 0.142 mg/L). Higher concentrations (5-20 mg/L) resulted in high embryotoxicity/developmental arrest. At concentrations ≅ EC50, PS-NH2 affected shell formation, as shown by optical and polarized light microscopy. In these conditions, transcription of 12 genes involved in different biological processes were evaluated. PS-NH2 induced dysregulation of transcription of genes involved in early shell formation (Chitin synthase, Carbonic anhydrase, Extrapallial Protein) at both 24 and 48 hpf. Decreased mRNA levels for ABC transporter p-glycoprotein-ABCB and Lysozyme were also observed at 48 hpf. SEM observations confirmed developmental toxicity at higher concentrations (5 mg/L). These data underline the sensitivity of Mytilus early embryos to PS-NH2 and support the hypothesis that calcifying larvae of marine species are particularly vulnerable to abiotic stressors, including exposure to selected types of NPs.

Metal transport and remobilisation in a basin affected by acid mine drainage: the role of ochreous amorphous precipitates.

Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.

Penicillium expansum Link strain for a biometallurgical method to recover REEs from WEEE.

Due to the wide range of applications in high-tech solutions, Rare Earth Elements (REEs) have become object of great interest. In the last years several studies regarding technologies for REE extraction from secondary resources have been carried out. In particular biotechnologies, which use tolerant and accumulator microorganisms to recover and recycle precious metals, are replacing traditional methods. This paper describes an original biometallurgical method to recover REEs from waste electrical and electronic equipment (WEEE) by using a strain of Penicillium expansum Link isolated from an ecotoxic metal contaminated site. The resulting product is a high concentrated solution of Lanthanum (up to 390ppm) and Terbium (up to 1520ppm) obtained from WEEE. Under this perspective, the proposed protocol can be considered a method of recycling exploiting biometallurgy. Finally, the process is the subject of the Italian patent application n. 102015000041404 submitted by the University of Genoa.

Molecular level interactions in brushite-aminoacids composites.

The interaction of aminoacids (Glycine, Proline, Lysine) with brushite based bone cements has been investigated by several techniques (FTIR spectroscopy, Thermogravimetry-TG, Scanning Electron Microscopy-SEM, mechanical properties studies), with the aim to elucidate the properties of the resulting composite materials and the interaction occurring at molecular level between the inorganic matrix and the organic moieties. Brushite phase is predominantly obtained also in the presence of aminoacids added during preparation of the bone cement. Focusing on Glycine incorporation, the presence of a fraction of bulk Glycine, weakly interacting with the inorganic matrix, together with Glycine specifically interacting with adsorption sites can be envisaged, as pointed out by FT IR and thermogravimetric data. In detail, FT-IR data evidenced changes in shape and position of bands associated to stretching modes of the carboxylic groups in Glycine structure, which can be explained by the coordination of these functional groups with the Ca ions in the matrix. Heating this composite at controlled temperature results in the detection of a condensation products, either cyclic condensation product, either dipeptide. Diffuse and not specific H-bonding seems to be the main form of interaction of Proline and Lysine with brushite. Due to the coordination with Ca ions here described, Glycine can act as retardant during brushite preparation, allowing good workability of the resulting composite.