With this study, we investigate the mineralogical variations associated with the low-temperature (<100°C) alteration of normal tholeiitic pillow basalts varying in age from 0.8 to 3.5 Ma. Their alteration intensity varies systematically and is related to several factors, including (1) the aging of the igneous crust, (2) the increase of temperatures from the younger to the older sites, measured at the sediment/basement interface, (3) the local and regional variations in lithology and primary porosity, and (4) the degree of pillow fracturing. Fractures represent the most important pathways that allow significant penetration of fluids into the rock and are virtually the only factor controlling the alteration of the glassy rim and the early stages of pillow alteration. Three different alteration stages have been recognized: alteration of glassy margin, oxidizing alteration through fluid circulation in fracture systems, and reducing alteration through diffusion. All the observed mineralogical and chemical variations occurring during the early stages of alteration are interpreted as the result of the rock interaction with "normal," alkaline, and oxidizing seawater, along preferential pathways represented by the concentric and radial crack systems. The chemical composition of the fluid progressively evolves while moving into the basalt, leading to a reducing alteration stage, which is initially responsible for the precipitation of Fe-rich saponite and minor sulfides and subsequently for the widespread formation of carbonates. At the same time, the system evolved from being "water dominated" to being "rock dominated." No alteration effects in pillow basalts were observed that must have occurred at temperatures higher than those measured during Leg 168 at the basement/sediment interface (e.g., between 15° and 64°C).

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Active acid mine drainage (AMD) processes at the Libiola Fe-Cu sulphides mine are mainly triggered by water-rock interaction occurring within open-air tailing and waste-rock dumps. These processes are mainly controlled by exposure to weathering agents, the grain size of the dumped materials, and by the quantity of sulphides, the sulphide types, and their mode of occurrence. Due to these factors, several paragenetic stages of evolution have been recognised at different depths at different sites and within the same site. The dump samples were investigated with mineralogical (reflected-and transmitted-light optical microscopy, XRPD, and SEM-EDS) and geochemical (ICP-AES, Leco) techniques. The AMD evaluation of the tailing and waste-rock samples was performed by calculating the Maximum Potential Acidity, the Acid Neutralising Capacity, (and the Net Acid Producing Potential. The results allowed us to demonstrate that the open-air tailings had already superseded their AMD apex and are now practically inert material composed mainly of stable goethite ± lepidocrocite ± hematite assemblages. On the contrary, the sulphide-rich waste rocks still have a strong potential to produce long term AMD, causing the acidification of circulating waters and the release of several hazardous elements.

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In this work, we investigated a 3 ha sulphidebearing waste-rock dump (Libiola Mine, Italy) using mineralogical, geochemical, and geostatistical analyses. The dumped materials were highly heterogeneous in grain size and lithology and varied both laterally and vertically. Other than the host rock of the ore, basalts and serpentinites, the dumped materials contained high amounts of low-grade chalcopyriteand pyrite-rich mineralisations. Due to these characteristics and to the absence of minerals able to neutralise acidity, this waste-rock dump can be classified as an acid mine drainage (AMD) producer. The study confirms that AMD is still active and, in the best scenario, can persist for up to 6.17 9 10 3 years. The consequences of this process are of serious environmental concern as it involves strong acidification of the circulating waters, the release of potentially toxic metals into the soil, streams and rivers and the precipitation of huge quantities of secondary Fe-oxides and Fe-oxyhydroxides.