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The Pietra del Pertusillo freshwater reservoir is a major artificial lake of environmental, biological, and ecological importance located in the Basilicata region, southern Italy. The reservoir arch-gravity dam was completed in 1963 for producing hydroelectric energy and providing water for human use, and nearby there are potential sources of anthropogenic pollution such as urban and industrial activities. For the first time, the minero-chemistry of the lake and fluvio-lacustrine sediments of the reservoir have been evaluated to assess the environmental quality. Moreover, the composition of fluvial sediments derived from the peri-lacual zone of the reservoir and of local outcropping bedrock were also studied to understand the factors affecting the behavior of elements in the freshwater reservoir, with particular attention paid to heavy metals. In Italy, specific regulatory values concerning the element threshold concentration for lake and river sediments do not exist, and for this reason, soil threshold values are considered the standard for sediments of internal waters. The evaluation of the environmental quality of reservoir sediments has been performed using enrichment factors obtained with respect to the average composition of a reconstructed local upper continental crust. We suggest this method as an innovative standard in similar conditions worldwide. In the studied reservoir sediments, the trace elements that may be of some environmental concern are Cr, Cu, Zn, As, and Pb although, at this stage, the distribution of these elements appears to be mostly driven by geogenic processes. However, within the frame of the assessment and the preservation of the quality of aquatic environments, particular attention has to be paid to As (which shows median value of 10 ppm, reaching a maximum value of 26 ppm in Quaternary sediments), constantly enriched in the lacustrine samples and especially in the fine-grained fraction (median = 8.5 ppm).

The High Agri Valley (southern Italy) is one of the largest intermontane basin of the southern Apennines affected by intensive agricultural and industrial activities. The study of groundwater chemical features provides much important information useful in water resource management. In this study, hydrogeochemical investigations coupled with multivariate statistics, saturation indices, and stable isotope composition (δD and δ18O) were conducted in the High Agri Valley to determine the chemical composition of groundwater and to define the geogenic and anthropogenic influences on groundwater quality. Twenty-four sampling point ( including well and spring waters) have been examined. The isotopic data revealed that groundwater has a meteoric origin. Well waters, located on recent alluvial-lacustrine deposits in shallow porous aquifers at the valley floor, are influenced by seasonal rainfall events and show shallow circuits; conversely, spring waters from fissured and/or karstified aquifers are probably associated to deeper and longer hydrogeological circuits. The R -mode factor analysis shows that three factors explain 94% of the total variance, and F1 represents the combined effect of dolomite and silicate dissolution to explain most water chemistry. In addition, very low contents of trace elements were detected, and their distribution was principally related to natural input. Only two well waters, used for irrigation use, show critical issue for NO3- concentrations, whose values are linked to agricultural activities. Groundwater quality strongly affects the management of water resources, as well as their suitability for domestic, agricultural, and industrial uses. Overall, our results were considered fulfilling the requirements for the inorganic component of the Water Framework Directive and Italian legislation for drinking purposes. The water quality for irrigation is from “good to permissible” to “excellent to good” although salinity and relatively high content of Mg2+ can occasionally be critical.

In this study Cr(tot), Cr(VI), major and trace elements were determined in groundwater of northern sector of the Pollino Massif (southern Italy). The investigated area is characterized by ophiolitic rocks consisting of metabasites, shales and calcschists and fractured serpentinites. Two main hydro-facies were observed, reflecting low temperature water–rock interaction. The Mg-HCO3 hydrofacies is due to the weathering of serpentinites, Ca-HCO3 groundwaters are linked to the interaction with calcschist and metabasites. High Cr(VI) concentrations were detected, exceeding the maximum admissible concentrations by Italian regulation, due to the release of Cr(III) from ophiolitic rocks into water and its oxidation to the hexavalent state. Remediation tests were carried out using two synthetized nanomaterials, Fe(0) and magnetite, characterized by a mean size lower than 50 nm. The experiments were conducted at fixed nanoparticles/Cr(VI) molar ratio and according to previous studies. In addition, the kinetic data were interpreted with a suitable mathematical model.

In the Tethyan realm the carbonate-dominated Meso-Cenozoic South Tethyan Phosphogenic Province is of considerable economic importance since it represents the greatest accumulation of sedimentary phosphorites. In southern Italy, in the Salentine peninsula (the southern part of the Apulian Carbonate Platform, ACP), is well documented the occurrence of Cenozoic P-rich levels consisting of nodules and pebbles and showing a large P2O5 fluctuation (4.07–22.07 wt%), due to variable calcite abundance. The mainly observed P-bearing minerals are hydroxyapatite and carbonate fluorapatite and U, together with Sr and Pb, preferentially acts as Ca substitutes in both lattices. Minor authigenic monazite (LREE-bearing phosphate) and xenotime (HREE+Y-bearing phosphate), likely formed during sediment burial compaction and diagenesis. The total REEs' abundances and the shape of the shale-normalized REE-patterns in the P-rich nodules are in the range of those typically observed in Paleocene-Eocene through Pleistocene-Recent P-rich sediments, supporting the idea of a broadly consistent ocean chemistry in this span of geological time. The (La/Yb)N proxy is within the modern seawater range, signifying early diagenetic adsorption played only a minor role in affecting the REEs' distribution. The Ce and Pr anomalies suggest some P-rich nodules experienced very localized hypoxic to anoxic conditions promoting Ce/Ce* spurious results in a generally oxic to hypoxic environment causing real negative Ce anomaly. This scenario is reinforced by the lack of the coupled uranium-vanadium enrichment typically observed in an anoxic environment. Since the Pliocene the eastern Mediterranean was variously affected by oxygenation and productivity and it is likely the ACP phosphate-rich sediments formed under low sedimentation rates and authigenesis in a bottom current-dominated regime, as also indicated by the glauconite occurrence. Transgressions and sea levels rising following major glaciations may have favored the deposition of phosphate sediments by creating new restricted basin configurations and increased nutrient input promoted by upwelling processes.

The Sardinia microplate in the western Mediterranean represents an ideal example for examining the relationship between fluid geochemistry, tectonic and heat sources in hydrothermal circuits. It consists of a portion of Variscan basement partly covered by sedimentary (mainly carbonate) and volcanic successions that record significant Permian to Pliocene geodynamic events within the southern European margin. The regional structure of the northern Sardinia is dominated by Tertiary ENE–WSW trending strike-slip and NNW–SSE trending normal faults, both capable of controlling deep and shallow fluid circulation. In this paper, results of a detailed geochemical investigation of waters and gases coming from a W-E trending section of central-north Sardinia are presented in order to explain the contrasting thermal and geochemical features of two - already known groups - of fluids. The Volcanic Logudoro Waters (VLW) is a group of cold to hypothermal Na–HCO3 waters characterised by high CO2 contents and mantle-derived He, that are localized in the volcanic-dominated Tertiary grabens. The He mantle signature within the VLW waters is associated with Plio-Pleistocene Quaternary volcanism where the outgassing of mantle-derived fluids is reasonably due recently active magma sources at depth. The currently active emission of mantle-derived gas linked to cold and hypothermal waters, provides evidence that the heat diffusion associated with the Plio-Pleistocene volcanism has already ended. In contrast, the Granite Variscan Basement Waters (GBW) group is characterised by hot-NaCl-rich waters, containing high concentrations of both dissolved N2 and radiogenic 4He. The high contribution of 4He produced by radiogenic decay of U and Th in the crust indicates a supply of radiogenic heat to the hydrothermal system localized within the granitic basement or in the tectonic contact between granite and Tertiary covers.

A comprehensive study of the serpentinite and associated veins belonging to the Frido Unit in the Pollino Massif (southern Italy) is presented here with the aim to provide new constraints about the hydrothermal system hosted by the accretionary wedge of the southern Apennines. The studied serpentinites are from two different sites: Fosso Arcangelo and Pietrapica. In both sites, the rocks show mylonitic-cataclastic structures and pseudomorphic and patch textures and are traversing by pervasive carbonate and quartz-carbonate veins. The mineralogical assemblage of serpentinites consists of serpentine group minerals (with a predominance of lizardite), amphiboles, pyroxene, chlorite, titanite, magnetite, and talc. In some samples, hydro-garnet was also detected and documented here for the first time. As for cutting veins, different mineralogical compositions were observed in the two sites: calcite characterizes the veins from Fosso Arcangelo, whereas quartz and dolomite are the principal minerals of the Pietrapica veins infill, suggesting a different composition of mineralizing fluids. Stable isotopes of C and O also indicate such a different chemistry. In detail, samples from the Pietrapica site are characterized by &delta, 13C fluctuations coupled with a &delta, 18O shift documenting calcite formation in an open-system where mixing between deep and shallow fluids occurred. Conversely, &delta, 13C and &delta, 18O of the Fosso Arcangelo veins show a decarbonation trend, suggesting their developing in a closed-system at deeper crustal conditions. Precipitation temperature calculated for both sites indicates a similar range (80 &deg, C to 120 &deg, C), thus suggesting carbonate precipitation within the same thermal system.

This paper deals with petrography and mineralogy of serpentinitic rocks occurring in the Southern Apennines (Italy) with the aim to review the already available literature data and furnish new details on asbestos minerals present in the studied area. Two sites of Southern Italy were taken into account: the Pollino Massif, at the Calabrian-Lucanian border, and the surroundings of the Gimigliano and Mt. Reventino areas where serpentinites of Frido Unit are mainly exposed. Textural and mineralogical features of the studied rocks point to a similar composition for both sites including asbestos minerals such as chrysotile and tremolite-actinolite series mineral phases. Only in the Pollino Massif serpentinites edenite crystals have been detected as well; they are documented here for the first time. This amphibole forms as fibrous and/or prismatic crystals in aggregates associated with serpentine, pyroxene, and calcite. Metamorphism and/or metasomatic alteration of serpentinites are the most probable processes promoting the edenite formation in the Southern Apennine ophiolitic rocks.

This work focuses on two fault-controlled deposits, the Atella and Rapolla travertines, which are associated with high-angle extensional faults of the Bradano Trough, southern Apennines (Italy). The Atella travertine is along a NW-SE striking, deep-seated extensional fault, already described in literature, which crosscuts both Apulian carbonates and the overlying foredeep basin infill. The Rapolla travertine is on top of a NE-SW striking, shallow-seated fault, here described for the first time, which is interpreted as a tear fault associated with a shallow thrust displacing only the foredeep basin infill. The results of structural, sedimentological, mineralogical, and C and O isotope analyses are here reported and discussed to assess the provenance of mineralizing fluids, and to evaluate the control exerted by the aforementioned extensional faults on deep, mantle-derived and shallow, meteoric fluids. Sedimentological analysis is consistent with five lithofacies in the studied travertines, which likely formed in a typical lacustrine depositional environment. Mineralogical analysis show that travertines mainly consist of calcite, and minor quartz, feldspar and clay minerals, indicative of a terrigenous supply during travertine precipitation. The isotope signature of the two studied travertines shows different provenance for the mineralizing fluids. At the Atella site, the δ13CPDB values range between + 5.2 and + 5.7‰ and the δ18OPDB values between − 9.0 and − 7.3‰, which are consistent with a mantle-derived CO2 component in the fluid. In contrast, at the Rapolla site the δ13CPDB values vary from − 2.7 to + 1.5‰ and the δ18OPDB values from − 6.8 to − 5.4‰, suggesting a mixed CO2 source with both biogenic-derived and mantle-derived fluids. The results of structural analyses conducted along the footwall damage zone of the fault exposed at the Rapolla site, show that the whole damage zone, in which fractures and joints likely channeled the mixed fluids, acted as a distributed conduit for both fault-parallel and cross-fault fluid migration.

In this paper we provide a systematic geochemical study of the Monticchio maar lakes, on the Mt. Vulture volcano, southern Italy, to understand the processes affecting the distribution of chemical elements. A high-resolution conductivity–temperature–depth profile was obtained, and water samples were collected at various depths for analyses of major and trace elements. Although the two lakes are separated by less than 200 m, they exhibit different behaviour. The Ca–Na–HCO 3 composition of “Lago Grande” water suggests that low-temperature fluids are leached from the host volcanic rocks. Na–Ca–HCO 3 in near-surface “Lago Piccolo” water is derived from the dissolution of local volcanic rocks, while the deepest water samples are bicarbonate alkaline-earth in composition and generally show an enrichment in solutes with respect to the epilimnion layer (except for SO 4 2 − content). The hypolimnion water is principally governed by both the input of saline groundwater from the lake bottom and authigenic processes within bottom sediments. In addition, the occurrence of anoxic conditions and microbial activity is responsible for the transformation of sulphates to hydrogen sulphide, and for the precipitation of Fe sulphide phases. Both processes cause a change in the chemical composition of saline groundwater as it moves upwards. Overall, the water chemistry of the Monticchio lakes is principally affected by: i) the input of CO 2 -rich volcanic gas; ii) evaporative processes that deplete near-surface water in some elements; and iii) the occurrence of chemical, physical and biological conditions causing the transformation of molecular complexes and consequently promoting mineral precipitation.

The Mt. Vulture volcanic aquifer is an important reservoir of effervescent mineral water in southern Italy. This area is included in the Vulture Regional Park and is located on a popular tourist route for its high scenic and ecological value. Unfortunately, signs of anthropogenic impact have recently increased. Among minor elements, boron and its isotopes are considered useful environmental tracers since different anthropogenic and natural sources can be distinguished. In this study, B content and (δ11B) isotope composition were determined in the Mt. Vulture groundwaters. The groundwater chemistry is strongly influenced by input of CO2-rich volcanic gases, and two different hydrofacies are observed. The first water type (BAW) has bicarbonate alkaline and alkaline-earth composition and relatively low salinity, whereas the second one (HSW) has bicarbonate-sulphate alkaline composition and higher salinity. The HSW are enriched in boron and have low δ11B values (from –9.6‰ to –4.3‰) similar to those measured in the local magmas suggesting that B contents in these waters are influenced by prolonged interaction between local meteoric water and volcanic rocks. As to BAW, a wide variability in B concentrations (from 14 μg/l to 769 μg/l) and B isotope composition (from -16.1‰ to +23‰) has been observed. A possible anthropogenic input is thought to be responsible for such variability. The water samples with high B concentrations and negative δ11B values (−12.2‰ to −16.1‰) are probably influenced by agricultural activities; for water samples characterized by positive δ11B values (from +5.8‰ to +7.9‰) and low B contents, a slight contamination by sewage effluents cannot be excluded. These conclusions are also supported by B/Cl molar ratios (7.8E−3 to 1.6E−2) different from those of the HSW group (1.1E−2 to 7.0E−2). This study highlights that also in the Mt. Vulture volcanic area B isotopes coupled to the B/Cl ratio can be a useful tool for the assessment of natural and anthropogenic contaminant sources.

The Mount Vulture basin, which mainly consists of pyroclastic and subordinate lava flow layers, is one of the most important aquifers for drinking water and irrigation supply in southern Italy. In this study, we investigated the geochemical behaviour of the rare earth elements (REEs) in the groundwater of this aquatic system, assessing fractionation patterns and performing speciation calculations to elucidate the geochemical processes affecting the REEs' distribution. The groundwater collected was separated into two subsets corresponding to recharge and discharge water. Overall, the groundwater exhibited REE concentrations well below 1000 ng/l, and the average content measured in the discharge water is approximately three times higher than that of the recharge water. In the recharge water, the shale normalised patterns are characterised by a more negative average Ce anomaly, a more positive average Eu anomaly, and a larger average (La/Yb)PAAS. The observed relationship between Ce anomalies and dissolved oxygen (DO) supports the idea that Ce oxidative scavenging has a role in determining the size and shape of the Ce anomaly. Further, the less negative average size of the Ce anomaly in the discharge zone also suggests Ce desorption due to changes in redox conditions. As for the Eu anomalies, the largest Eu* are associated with the recharge zone, characterised by higher average Eh and DO values. The volcanics in the Mt. Vulture lithologies have post-Archean average shale (PAAS) normalised patterns showing positive Eu anomalies due to feldspars occurrence. This indicates that the Eu* of groundwater in the recharge zone is mostly produced by the dissolution of feldspars. In the discharge zone, most samples are in equilibrium with smectite and Eu2+ adsorption onto the clay phase surface or its inclusion in the mineral structure as exchangeable cations likely lead to the smaller average size of Eu*. The possible occurrence of secondary minerals preferentially scavenging light REEs may also explain the difference in the (La/Yb)PAAS index observed between the recharge and discharge zones. Speciation calculations indicate that dissolved REEs consist mainly of carbonato complexes (LnCO3+) whereas the percentage of dicarbonato complexes (Ln(CO3)2−) increases in samples with circa-neutral pH. At acidic pH, the Ln3+ species are numerous and, in samples with large amounts of dissolved sulphate, derived by feldspathoids dissolution, from the discharge zone, the percentage of LnSO4+ species is not negligible.