Hydrogeological and multi-isotopic approach to define nitrate pollution and denitrification processes in a coastal aquifer (Sardinia,Italy)

Agricultural coastal areas are frequently affected by the superimposition of various processes, with a combination of anthropogenic and natural sources, which degrade groundwater quality. In the coastal multi-aquifer system of Arborea (Italy)—a reclaimed morass area identified as a nitrate vulnerable zone, according to Nitrate Directive 91/676/EEC—intensive agricultural and livestock activities contribute to substantial nitrate contamination. For this reason, the area can be considered a bench test for tuning an appropriate methodology aiming to trace the nitrate contamination in different conditions. An approach combining environmental isotopes, water quality and hydrogeological indicators was therefore used to understand the origins and attenuation mechanisms of nitrate pollution and to define the relationship between contaminant and groundwater flow dynamics through the multi-aquifer characterized by sandy (SHU), alluvial (AHU), and volcanic hydrogeological (VHU) units. Various groundwater chemical pathways were consistent with both different nitrogen sources and groundwater dynamics. Isotope composition suggests a mixed source for nitrate (organic and synthetic fertilizer), especially for the AHU and SHU groundwater. Moreover, marked heterotrophic denitrification and sulfate reduction processes were detected; although, for the contamination related to synthetic fertilizer, the attenuation was inefficient at removing NO₃^? to less than the human consumption threshold of 50 mg/L. Various factors contributed to control the distribution of the redox processes, such as the availability of carbon sources (organic fertilizer and the presence of lagoon-deposited aquitards), well depth, and groundwater flow paths. The characterization of these processes supports water-resource management plans, future actions, and regulations, particularly in nitrate vulnerable zones.     

Rare earth elements in groundwater from different Alpine aquifers

Rare earth elements (REE) were determined in 39 groundwater samples collected at 14 sites under low- and high-flow conditions. Water samples derived from aquifers hosted in crystalline, molasse, flysch, carbonate and evaporite rocks located in Western Switzerland. The concentration of REE in groundwater circulating in different rocks showed large variations: lowest concentrations (ΣREE≤10 ng/L) occurred in groundwater from evaporite aquifers; highest concentrations (ΣREE up to 516 ng/L) were observed in carbonate aquifers, although REE in these waters do vary under different hydrological conditions; groundwater from other aquifers had ΣREE from 10 to 100 ng/L. Distinct REE signatures were observed in waters draining specific rocks. The REE patterns in groundwater from crystalline, molasse and flysch aquifers showed heavy-REE enrichment at different degrees. Groundwaters circulating in crystalline rocks were distinguished by negative anomalies in Ce and Eu, whereas those from carbonate aquifers were nearly flat with ΣREE and the magnitude of negative anomaly in Ce is likely to be controlled by iron concentrations. The REE-Post-Archean Australian Shales (PAAS) normalized patterns appear useful to recognize the aquifer type and suggest the possibility to use the REE as geochemical tracers.     

Release of toxic elements from rocks and mine wastes at the Furtei gold mine (Sardinia, Italy)

The Furtei gold mine in Sardinia (Italy) exploits a volcanic-hosted high-sulphidation epithermal deposit. Large amounts of materials derived from exploitation are present in open pits, waste rock dumps and cyanidation tailings impoundment. Mineralized rocks in outcrops and waste dumps contain significant amounts of sulphides (mainly pyrite and enargite). These materials have a high potential for acid drainage generation and release of toxic elements (notably Cu and As, but also Al, Ni, Co and Cd) as pointed out by laboratory leaching tests and in agreement with chemical composition of waters draining the mining area, that show pH as low as 2, up to 180 mg/L Cu, up to 5 mg/L As, and up to 788 mg/L Al. On the other hand, leaching solutions and waters interacting with mineral assemblages of the propylitic alteration zone (mainly composed of chlorite, quartz, and calcite, with relic magmatic plagioclase) show higher pH, and lower metal loads. Leachates from cyanidation tailings show variable pH (between 6.2 and 9.7, depending on sulphide content in tailings); cyanide concentration varies between 110 µg/L and about 3 mg/L, whereas contents of toxic elements in leachates are, with the exception of Hg, within the limits of Italian regulations for non-dangerous industrial wastes. Reclamation plans provide for confinement of tailings within specific repositories. This measure should effectively reduce the environmental impact of these materials. Reclamation plans should also include an adequate management of other high-sulphide wastes.     

Impact of past mining activity on the quality of groundwater in SW Sardinia (Italy)

Hydrogeochemical surveys were carried out in SW Sardinia (Italy) to investigate the impact of past mining activities on the quality of groundwater. The chemistry of waters from flooded galleries, adits and dumps has been compared with that of springs and wells in the same area at sites relatively far from any mine legacy. A feature, common to all waters, is the circumneutral pH, since the carbonate formations in the area neutralise the acidity produced by the oxidation of Fe-bearing sulphide minerals in the mine impacted water. However, groundwater interacting with mine workings is degraded in quality; it shows high dissolved SO₄, Zn, Cd and Pb contents. In some cases groundwater exceeds the limit established by the guidelines of the World Health Organization for Pb content in drinking water, so that groundwater is mixed before entering the local aqueducts. Results from this study suggest that more attention needs to be paid to the impact on the streams from contaminated water flowing out from some mine areas because during the dry season these streams are only fed by mine groundwater. We recommend focusing efforts to reduce the chemical contamination prior to discharge.     

The abandoned Pb-Zn mine of Ingurtosu, Sardinia (Italy)

The Ingurtosu Pb-Zn mine, situated in the southwestern part of Sardinia, has been in production from the beginning of the last century up to 1968. The orebody consists of galena/sphalerite/barite/siderite veins in Ordovician arenaceous and phyllitic sediments, near the contact with a Hercynian batholith.

Abundant tailings were collected in a pond from which they were discharged during the winter months into the sea via the Rio Naracauli stream. Today this area of outstanding scenic beauty, is degraded by tailings and waste rock scattered all along the stream.

Material derived from mining activities was studied for grain size, mineralogical and geochemical composition. The Rio Naracauli was sampled over a length of ten kilometers at regular intervals.

The results can be summarized as follows: (a) tailings contain a varying, but often quite high, percentage of Pb; lower percentages were found for Zn and Cd; (b) a sharp increase in dissolved Zn, Cd and Pb was observed in the Rio Naracauli where it leached the tailings; and (c) tailings and waste rocks should be recycled or revegetated.     

Geochemistry of trace elements in surface waters of the Arno River Basin,northern Tuscany,Italy

Trace element geochemistry of the Arno River and its main tributaries was investigated on the basis of two sampling campaigns carried out in November 1996 and June 1997. By analyzing filtered and unfiltered water samples, Fe and Al are found in solution mainly as colloidal particles of size lower than 0.45 μm. In June (lower flow rate), Fe and Al are enriched in the filtered waters from the main river, and this feature was interpreted in terms of higher water temperature promoting the formation of smaller particles, thus reducing their aggregation properties. Iron and Al show perfectly synchronous downstream profiles along the Arno River, correlate quite well each to other, and display abrupt concentration increases near to Florence, where the lithology of the catchment changes from siliciclastic dominated to clay-sand (lacustrine-marine)-dominated. The same behaviour is shown by most of the other trace elements in the river, thus supporting a general lithological control. Trace elements in the final part of the Arno River are influenced by flocculation processes in addition to mixing. Adsorption phenomena on oxy-hydroxides are denoted by good elemental correlations with Fe (and Al). Sporadic anomalous concentration values, possibly related to anthropogenic contributions, may prevent such correlations. Referring to the quality of waters for potable use and fish life, toxic elements are below the acceptable limits of current European regulations, with few exceptions for Hg exceeding guideline values. Multivariate analysis groups trace elements according to geochemical affinities and natural or anthropogenic sources, thus distinguishing contaminated from uncontaminated samples. The results achieved in this work will help regional and national Authorities for compliance with the EU water policy, especially in assessing the water quality at the river basin scale and its vulnerability to human activities.