Plant-minerals-water interactions: An investigation on Juncus acutus exposed to different Zn sources.

Juncus acutus has been proposed as a suitable species for the design of phytoremediation plans. This research aimed to investigate the role played by rhizosphere minerals and water composition on Zn transformations and dynamics in the rhizosphere-plant system of J. acutus exposed to different Zn sources. Rhizobox experiments were conducted using three different growing substrates (Zn from 137 to 20,400 mg/kg), and two irrigation lines (Zn 0.05 and 180 mg/l). The plant growth was affected by the substrate type, whereas the Zn content in the water did not significantly influence the plant height for a specific substrate. J. acutus accumulated Zn mainly in roots (up to 10,000 mg/kg dw); the metal supply by the water led to variable increases in the total Zn concentration in the vegetal organs, and different Zn distributions both controlled by the rhizosphere mineral composition. Different Zn complexation mechanisms were observed, mainly driven by cysteine and citrate compounds, whose amount increased linearly with Zn content in water, but differently for each of the investigated systems. Our study contributes to gain a more complete picture of the Zn pathway in the rhizosphere-plant system of J. acutus. We demonstrated that this vegetal species is not only capable of developing site-specific tolerance mechanisms, but it is also capable to differently modulate Zn transformation when Zn is additionally supplied by watering. These findings are necessary for predicting the fate of Zn during phytoremediation of sites characterized by specific mineralogical properties and subject to water chemical variations.

Microbial Diversity of Bacteria Involved in Biomineralization Processes in Mine-Impacted Freshwaters.

In order to increase the knowledge about geo-bio interactions in extreme metal-polluted mine waters, we combined microbiological, mineralogical, and geochemical analyses to study the indigenous sulfate-reducing bacteria (SRB) involved in the heavy metal (HM) biomineralization processes occurring in Iglesiente and Arburese districts (SW Sardinia, Italy). Anaerobic cultures from sediments of two different mining-affected streams of this regional framework were enriched and analyzed by 16S rRNA next-generation sequencing (NGS) technique, showing sequences closely related to SRB classified in taxa typical of environments with high concentrations of metals (Desulfovibrionaceae, Desulfosporosinus). Nevertheless, the most abundant genera found in our samples did not belong to the traditional SRB groups (i.e., Rahnella, Acinetobacter). The bio-precipitation process mediated by these selected cultures was assessed by anaerobic batch tests performed with polluted river water showing a dramatic (more than 97%) Zn decrease. Scanning electron microscopy (SEM) analysis revealed the occurrence of Zn sulfide with tubular morphology, suggesting a bacteria-mediated bio-precipitation. The inocula represent two distinct communities of microorganisms, each adapted to peculiar environmental conditions. However, both the communities were able to use pollutants in their metabolism and tolerating HMs by detoxification mechanisms. The Zn precipitation mediated by the different enriched cultures suggests that SRB inocula selected in this study have great potentialities for the development of biotechnological techniques to reduce contaminant dispersion and for metal recovery.

Trace-element XAFS sensitivity: a stress test for a new XRF multi-detector.

X-ray absorption fine-structure (XAFS) spectroscopy can assess the chemical speciation of the elements providing their coordination and oxidation state, information generally hidden to other techniques. In the case of trace elements, achieving a good quality XAFS signal poses several challenges, as it requires high photon flux, counting statistics and detector linearity. Here, a new multi-element X-ray fluorescence detector is presented, specifically designed to probe the chemical speciation of trace 3d elements down to the p.p.m. range. The potentialities of the detector are presented through a case study: the speciation of ultra-diluted elements (Fe, Mn and Cr) in geological rocks from a calcareous formation related to the dispersal processes from Ontong (Java) volcanism (mid-Cretaceous). Trace-elements speciation is crucial in evaluating the impact of geogenic and anthropogenic harmful metals on the environment, and to evaluate the risks to human health and ecosystems. These results show that the new detector is suitable for collecting spectra of 3d elements in trace amounts in a calcareous matrix. The data quality is high enough that quantitative data analysis could be performed to determine their chemical speciation.

Ex situ phytoremediation trial of Sardinian mine waste using a pioneer plant species.

The mitigation of metals contamination is currently a crucial issue for the reclamation of mine sites. Indeed, mine wastes are often disposed in open dumps and consequently pollutants are subjected to dispersion in the surrounding areas. In this study, the potential use of Helichrysum microphyllum subsp. tyrrhenicum for phytostabilization was evaluated in ex situ conditions. Ninety specimens were randomly selected and were planted in three substrates (reference substrate, mine waste materials, and mine wastes with compost). Mineralogical compositions of substrates, rhizosphere, and roots were assessed through X-ray diffraction (XRD). Zn, Pb, and Cd concentrations of substrates, rhizosphere, soil pore waters, and plant tissues were determined. The phytostabilization potential was determined through the application of biological accumulation coefficient (BAC), biological concentration factor (BCF), and translocation factor (TF). Moreover, survival and biometric parameters were assessed on plant specimens. The polluted substrates and related rhizosphere materials were mainly composed of dolomite, quartz, pyrite, and phyllosilicate. Zn was the most abundant metal in substrates, rhizosphere, and soil pore waters. XRD analysis on roots showed the presence of amorphous cellulose and quartz and Zn was the most abundant metal in plant tissues. H. microphyllum subsp. tyrrhenicum restricts the accumulation of the metals into roots limiting their translocation in aereal parts, indicating its potential use as phytostabilizer (BCF, BAC, TF < 1). Survival and growth data showed a great adaptability to different substrates, with an evident positive effect of the implementation of compost which increased the plant survival and decreased the metals uptake into roots.

Plastics, (bio)polymers and their apparent biogeochemical cycle: An infrared spectroscopy study on foraminifera.

To understand the fate of plastic in oceans and the interaction with marine organisms, we investigated the incorporation of (bio)polymers and microplastics in selected benthic foraminiferal species by applying FTIR (Fourier Transform Infrared) microscopy. This experimental methodology has been applied to cultured benthic foraminifera Rosalina globularis, and to in situ foraminifera collected in a plastic remain found buried into superficial sediment in the Mediterranean seafloor, Rosalina bradyi, Textularia bocki and Cibicidoides lobatulus. In vitro foraminifera were treated with bis-(2-ethylhexyl) phthalate (DEHP) molecule to explore its internalization in the cytoplasm. Benthic foraminifera are marine microbial eukaryotes, sediment-dwelling, commonly short-lived and with reproductive cycles which play a central role in global biogeochemical cycles of inorganic and organic compounds. Despite the recent advances and investigations into the occurrence, distribution, and abundance of plastics, including microplastics, in marine environments, there remain relevant knowledge gaps, particularly on their effects on the benthic protists. No study, to our knowledge, has documented the molecular scale effect of plastics on foraminifera. Our analyses revealed three possible ways through which plastic-related molecules and plastic debris can enter a biogeochemical cycle and may affect the ecosystems: 1) foraminifera in situ can grow on plastic remains, namely C. lobatulus, R. bradyi and T. bocki, showing signals of oxidative stress and protein aggregation in comparison with R. globularis cultured in negative control; 2) DEHP can be incorporated in the cytoplasm of calcareous foraminifera, as observed in R. globularis; 3) microplastic debris, identified as epoxy resin, can be found in the cytoplasm and the agglutinated shell of T. bocki. We hypothesize that plastic waste and their associated additives may produce modifications related to the biomineralization process in foraminifera. This effect would be added to those induced by ocean acidification with negative consequences on the foraminiferal biogenic carbon (C) storage capacity.

Cigarette butts, a threat for marine environments: Lessons from benthic foraminifera (Protista).

Cigarette butts are the most common form of litter in the world and their environmental impact is related to both persistence and potential toxic effects for chemical composition. The objective of this study was to assess the acute toxicity (LC50-48 h) of human-smoked cigarette butts leachate on 3 cultured genera of benthic foraminifera: the calcareous perforate Rosalina globularis, the calcareous imperforate Quinqueloculina spp., and the agglutinated Textularia agglutinans. The specimens were exposed to 16, 8, 4, 2, and 1 cigarette butts/L concentrations that prove to be acutely toxic to all taxa. Starting from 4 cigarette butts/L, both calcareous genera showed shell decalcification, and death of almost all the individuals, except for the more resistant agglutinated species. These results suggest the potential harmfulness of cigarette butts leachate related to pH reduction and release of toxic substances, in particular nicotine, which leads to physiology alteration and in many cases cellular death.

A two-step pH control method to remove divalent metals from near-neutral mining and metallurgical waste drainages by inducing the formation of layered double hydroxide.

A neutral M2+-rich and M3+-poor (M = metal) metallurgical waste drainage was used to test a metal removal method based on the precipitation of layered double hydroxide (LDH). The LDH precipitation was induced by adding a salt of Al3+ (trivalent metal missing in the drainage) and maintaining or restoring the pH to a circum-neutral value. The precipitates were characterized by chemical analysis, XRD, ESEM, HRTEM and XAS. The main parameter controlling the removal of metals and the type of precipitate appeared to be the pH. As a function of pH variation during the experiments, analyses of precipitates and solutions showed either the formation of poor crystalline LDH combined with very high removal of Zn, Ni and Pb (92-100%), more variable removal of Mn (46-98%) and less Cd (33-40%), or the formation of more crystalline LDH combined with lower removal of Zn (62%), Mn (43%), Ni (88%), Pb (64%) and especially Cd (1%). The different metal removal efficiency in the two cases is only indirectly due to the different LDH crystallinity, and it is clearly affected by the following factors: 1) the two pH steps of the method; 2) the direction of pH variation within each step. In particular, the highest removal of metals is obtained when the first pH step goes towards acidic conditions, as a consequence of Al salt addition, and precipitation of a quasi-amorphous hydrated hydroxysulfate of Al (probably a precursor of felsÓ§bányaite Al4(SO4)(OH)10 · 4H2O) occurs. This first acidic pH step removes little or no metals (just 0-3%) but it is essential so that the second pH step towards slightly alkaline conditions, as a consequence of NaOH addition, can be highly efficient in removing divalent metals as the quasi-amorphous hydrated hydroxysulfate of Al gradually turns into an LDH incorporating Zn, Mg and other metals. On the contrary, when both pH steps remain in the neutral-alkaline range, only LDH precipitation occurs and a lower metal removal is observed. These results encourage further investigations on the removal of metals by inducing LDH precipitation as a simple and effective method for the treatment of circum-neutral polluted drainages.

Monitoring of Airborne Mercury: Comparison of Different Techniques in the Monte Amiata District, Southern Tuscany, Italy.

In the present study, mercury (Hg) concentrations were investigated in lichens (Flavoparmelia caperata (L.) Hale, Parmelia saxatilis (L.) Ach., and Xanthoria parietina (L.) Th.Fr.) collected in the surrounding of the dismissed Abbadia San Salvatore Hg mine (Monte Amiata district, Italy). Results were integrated with Hg concentrations in tree barks and literature data of gaseous Hg levels determined by passive air samplers (PASs) in the same area. The ultimate goal was to compare results obtained by the three monitoring techniques to evaluate potential mismatches. Lichens displayed 180-3600 ng/g Hg, and Hg concentrations decreased exponentially with distance from the mine. Mercury concentration was lower than in Pinus nigra barks at the same site. There was a moderate correlation between Hg in lichen and Hg in bark, suggesting similar mechanisms of Hg uptake and residence times. However, correlation with published gaseous Hg concentrations (PASs) was moderate at best (Kendall Tau = 0.4-0.5, p > 0.05). The differences occurred because a) PASs collected gaseous Hg, whereas lichens and barks also picked up particulate Hg, and b) lichens and bark had a dynamic exchange with the atmosphere. Lichen, bark, and PAS outline different and complementary aspects of airborne Hg content and efficient monitoring programs in contaminated areas would benefit from the integration of data from different techniques.

Chemical data on environmental matrices from an abandoned mining site.

This article contains analytical data on chemical composition of waters and solid samples (mining wastes and biominerals) collected in an abandoned mining area, and they are related with the research article "Geochemistry of rare earth elements in water and solid materials at abandoned mines in SW Sardinia (Italy)" (Medas et al., 2013). Specifically, we present physicochemical data (temperature, electrical conductivity, pH, and redox potential), major components and the main contaminants (Zn, Mn, Cd, Ni, Cu, Pb) detected in stream waters and drainages from mine wastes. Waters were monitored from 2009 to 2011 during different seasonal conditions to give an insight into metal dispersion under different hydrological conditions.

XRD-Thermal Combined Analyses: An Approach to Evaluate the Potential of Phytoremediation, Phytomining, and Biochar Production.

A method for evaluating the potential of reuse of biomasses for economic purposes is here presented starting from a case study. Juncus acutus plants and rhizospheres were harvested from abandoned Zn-Pb mine areas of southwest Sardinia (Italy). Thermogravimetry and Differential Thermal analyses were performed to evaluate the temperatures at which significant reactions occur. X-ray Diffraction (XRD) analysis was carried out on raw samples and on samples heated ex-situ (by a conventional diffractometer) or in-situ (by synchrotron-based diffraction). Raw samples mainly consist of quartz, phyllosilicates, and feldspars with minor amounts of sulfides, sulfates, and Fe, Pb, and Zn carbonates, concentrated in the rhizosphere. After heating, Zn and Fe oxides and willemite are observed in internal roots and stems, revealing the presence of these metals in the plant tissues. In-situ heating was less effective than ex-situ in revealing minor phases in organic samples, probably because the scarcity of oxygen within the sample holder did not allow the degradation of organic compounds and the oxidation of sulfides, resulting in a low quality XRD signal even if obtained with the high resolution ensured by a synchrotron light source. This method can be applied to plants from polluted sites for metal exploitation, and/or to biomasses from unpolluted sites for biochar production, since both applications take advantage of the knowledge of the minerals formed after heating.

Geochemical and mineralogical datasets on waters and stream precipitates from an abandoned mining site: Montevecchio-Ingurtosu district, Rio Irvi (SW Sardinia).

Geochemical modelling data and Powder X-Ray Diffraction data on samples collected along Rio Irvi (Montevecchio-Ingurtosu mining district, SW Sardinia, Italy) are reported in this paper. The data show the results of data processing to calculate water chemical speciation of ions and saturation indices of relevant mineral phases. These data are related with the research article: De Giudici G. et al (2018), Application of hydrologic-tracer techniques to the Casargiu adit and Rio Irvi (SW-Sardinia, Italy): Using enhanced natural attenuation to reduce extreme metal loads, Applied Geochemistry, vol.96, 42-54. The comparison of the calculated saturation indices of relevant Fe-bearing phases with the PXRD data of samples collected along the stream confirm the quality of the SI dataset and the good correlation between the calculations and the observed data. The comparison of this dataset with others can help to deeper understand and quantify the impact of past and current mining activity on water bodies, contributing to implement the scientific background for the application of remediation actions.

Data on rare earth elements in mining environments under non-acidic conditions.

This article contains analytical data on Rare Earth Elements (REE) concentration in waters and solid samples (mining wastes and biominerals) collected in an abandoned mining site characterized by near-neutral conditions, and they are related with the research article "Geochemistry of rare earth elements in water and solid materials at abandoned mines in SW Sardinia (Italy)" (Medas et al., 2013). REE can show specific signatures due to fractionation processes, giving an insight to the understanding of the natural processes ruling the water-rock interactions and the geo-bio-interactions. Most researches on REE behavior were performed in acidic environments, while only few data on REE are available for neutral waters. Elaboration of this dataset can be useful to evaluate the reactions controlling the geochemical behavior of REE under near-neutral to slightly alkaline conditions, driving the scientific community toward an efficient management of monitoring actions and remediation technologies.

Impact of Zn excess on biomineralization processes in Juncus acutus grown in mine polluted sites.

Juncus acutus, an halophite plant pioneer in extremely polluted mine areas, was harvested in three different locations of Sardinia (Italy), having Zn soil concentration up to 80g/kg, and Zn water concentration ranging between 10-3g/L and 10-1g/L. Rhizosphere and plant samples were investigated combining X-ray microscopy (XM)/spectroscopy (XAFS) and infrared microspectroscopy (FTIR) to elucidate the chemical composition, (bio)mineralogy and Zn coordinative environment. The multi-technique approach allowed recognizing different biomineralization processes, and Zn complexes in the plant tissues. The Zn chemical environment in root biominerals is multi-phase and, depending on the sampling site, can comprise amorphous Zn silicate, Zn apatite, hydrozincite, and Zn sulphate. Zn cysteine and Zn histidine, complexes quoted as part of a detoxification strategy, were found mainly in plants from the site where the Zn water concentration has the highest values. This different site-specific mode of Zn biomineralization has relevant implications for phytoremediation techniques and for further biotechnology development, which can be better designed and developed after knowledge of site-specific-molecular processes ruling mineral evolution and biomineralization. Carboxylic groups and organic compounds (lignin, cellulose, hemicellulose, pectin and esters) were identified by FTIR analysis, thought the Zn speciation is not apparently linked to these carboxylic group rich biopolymers.

Zinc incorporation in marine bivalve shells grown in mine-polluted seabed sediments: a case study in the Malfidano mining area (SW Sardinia, Italy).

Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0-80 mg/kg of Zn, 5.4-60 mg/kg of Fe and 0.5-4.5 mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.

Binding of bis-(2-ethylhexyl) phthalate at the surface of hydrozincite nanocrystals: An example of organic molecules absorption onto nanocrystalline minerals.

As a contribution to understand the interactions between mineral surfaces and organic molecules, this study reports an accurate characterization of the bis-(2-ethylhexyl) phthalate (DEHP)-Hydrozincite (DEHP-HY), that has been conduced combining the following techniques: FTIR, NMR, XAS spectroscopies and XRD. XRD patterns indicate that the HY is made of nanocrystals whose size is not influenced by the presence of DEHP. The (1)H NMR analysis of DEHP-HY samples points out the presence of interactions of DEHP with HY. CPMAS NMR analysis suggests that the interaction is operated by ester carbonyl groups while the aliphatic chain, as expected, is not involved. MAS and CPMAS NMR measurements, performed on (13)C ester carbonyl enriched DEHP, allow to demonstrate that there are two ester carbonyl linkage sites interacting at the HY surface: an acid site with a strong link and a second one with weak chemical interactions. Zn K-edge XAS spectroscopy demonstrates that the local atomic structure around Zn in DEHP-HY sample remains essentially unchanged with respect to that of HY. Such a weak structural effect suggests that HY interaction with DEHP is limited to the nanoparticle surface.

Microscopic processes ruling the bioavailability of Zn to roots of Euphorbia pithyusa L. pioneer plant.

Euphorbia pithyusa L. was used in a plant growth-promoting assisted field trial experiment. To unravel the microscopic processes at the interface, thin slices of E. pithyusa roots were investigated by micro-X-ray fluorescence mapping. Roots and rhizosphere materials were examined by X-ray absorption spectroscopy at the Zn K-edge, X-ray diffraction, and scanning electron microscopy. Results indicate some features common to all the investigated samples. (i) In the rhizosphere of E. pithyusa, Zn was found to exist in different phases. (ii) Si and Al are mainly concentrated in a rim at the epidermis of the roots. (iii) Zn is mostly stored in root epidermis and does not appear to be coordinated to organic molecules but mainly occurs in mineral phases such as Zn silicates. We interpreted that roots of E. pithyusa significantly promote mineral evolution in the rhizosphere. Concomitantly, the plant uses Si and Al extracted by soil minerals to build a biomineralization rim, which can capture Zn. This Zn silicate biomineralization has relevant implications for phytoremediation techniques and for further biotechnology development, which can be better designed and developed after specific knowledge of molecular processes ruling mineral evolution and biomineralization processes has been gained.