Behaviour of boron and strontium isotopes in groundwater–aquifer interactions in the Cornia Plain (Tuscany,Italy)

The Cornia Plain alluvial aquifer, in Tuscany, is exploited intensely to meet the demand for domestic, irrigation and industrial water supplies. The B concentration of groundwater, however, is often above the European limit of 1 mg L⁻¹, with the result that exploitation of these water resources requires careful management. Boron and Sr isotopes have been used as part of a study on the origin and distribution of B dissolved in groundwater, and indirectly as a contribution to the development of appropriate water management strategies.The geochemistry of the Cornia Plain groundwater changes from a HCO₃ facies in the inland areas to a Cl facies along the coastal belt, where seawater intrusion takes place. The B concentration of groundwater increases towards the coastal areas, while the ¹¹B/¹⁰B ratio decreases. This indicates that there is an increasing interaction between dissolved B and the sediments forming the aquifer matrix, whose B content is in the order of 100 mg kg⁻¹. Adsorption–desorption exchanges take place between water and the sediment fine fraction rich in clay minerals, with a net release of B from the matrix into the groundwater, and a consequent δ¹¹B shift from positive to negative values. The aquifer matrix sediments therefore seem to be the major source of B dissolved in the groundwater.The groundwater–matrix interactions triggered by the ionic strength increase caused by seawater intrusion can also be detected in the Ca–Na ion exchanges. Dissolved Sr follows a trend similar to that of Ca, while the ⁸⁷Sr/⁸⁶Sr ratio is equal to that of the exchangeable Sr of the aquifer matrix and therefore does not change significantly.These results have helped to define a new strategy for groundwater exploitation, with the final objective of reducing B concentration in the water extracted from the aquifer.     

Olocenic alluvial aquifer of the River Cornia coastal plain (southern Tuscany, Italy): database design for groundwater management

 Hydrogeological research is in progress, utilizing GIS methods, with the principal aim of modelling the Olocenic alluvial aquifer of the River Cornia coastal plain (southern Tuscany, Italy), which has been exploited for drinking water, irrigation, and industrial uses. A consequence of exploitation has been the appearance of wide seawater intrusion. The alluvial aquifer has recently been subjected to new well fields for the supply of drinking water, with an increase of total average discharge of about 4×10⁶ m³/year. This paper presents results obtained from updating and integrating basic knowledge and structuring the database. The hydrogeological study allowed the recognition of the extension of areas that are characterized by a hydraulic head under the sea level, the progressive salinization of the aquifer, and the increase of water deficit in the aquifer which is produced by a progressive extraction of water superior to the natural recharge. In addition, benefits and disadvantages resulting from the location of new well fields in a hydrogeologically favourable zone, and the boundary conditions for much of the area studied have been defined. The GIS was used as support for making and updating the tabular and spatial database with the aim of integrating the local and regional hydrogeological knowledge. This study will permit the realization of a numerical simulation of the groundwater flow of the aquifer aimed at correcting the management of water resources, by means of the GIS-modelling integration. Received: 23 June 1998 · Accepted: 16 November 1998     

Natural Cr(VI) contamination of groundwater in the Cecina coastal area and its inner sectors (Tuscany,Italy)

A detailed hydrogeochemical study of groundwater in the Cecina coastal plain (Livorno province, Italy) and its inner sectors was undertaken in 2008, as chemical analyses carried out on groundwater since 2006 have revealed Cr(VI) concentrations of up to 49 μg/L (well above the permissible limit of 5 μg/L). Ophiolite outcrops are present throughout the study area, and their fragments likely represent a significant portion of the existing multilayered aquifer skeleton. Waters delivered by the serpentinite outcrops have a typically Mg–HCO₃ composition, whereas those of the coastal plain are prevailingly of the Ca/Mg–HCO₃ type with significant Mg contents. Significant NO₃ contamination characterises the studied coastal plain, and an interesting negative correlation exists between Cr(VI) and both NO₃ and SO₄ deriving from the widespread use of (NH₄)₂SO₄ as a farm fertilizer. Chromium speciation calculations carried out using the EQ3NR code reveal that the prevailing Cr(VI) species in solution is CrO₄ ^2?; however, CaCrO₄° and MgCrO₄° neutral complexes represent significant percentages (up to 42 %). These findings suggest that the mobility and consequently the bioavailability of Cr(VI) can be significantly enhanced by these neutral complexes, which are not considered to be affected by adsorption/desorption processes. The Cr(VI) source, investigated by means of the Mg/SiO₂ molar ratio, seems to be represented mainly by Mg-bearing minerals of the chlorite group. Petrographic observations confirm the occurrence of this mineral group. The interaction between rainwater and the local serpentinite rock was simulated at different $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ conditions by reaction path modelling using the EQ3/6 software package. $P_{{{\text{O}}_{ 2} }}$ was varied in accordance with the assumption that redox conditions are determined in part by NO₃. Results are in good agreement with experimental data on spring waters and subordinately with data on some coastal plain groundwater, which plot in a rather wide $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ field. Although the dissolved Cr content is mostly of natural origin, fertilization may affect its fate.     

Vertical vulnerability evaluation of middle-low Esino River valley alluvial aquifer (Marche, Italy)

 The methodology applied in this research work allows the evaluation of the vertical vulnerability of the Esino River alluvial aquifer (Marche). Main factors determining the ease with which possible pollutant may come from the soil surface to reach the groundwater beneath, through a prevalently vertical path, have been evaluated. Following a "raster" logic, the study area has been discretized into a set of elemental areas. For each of these areas, dimensionless indices able to characterize the actual possibility for the groundwater to be reached by polluting substances have been estimated. Received: 25 February 1997 · Accepted: 13 November 1997     

Fault array evolution in extensional basins: insights from statistical analysis of gravel deposits in the Cecina River (Tuscany,Italy)

Two statistical analyses of gravel clasts from the Lower Pleistocene deposits in the Lower Cecina Valley (Tuscany, Italy) have been combined to unravel changes in the palaeo‐drainage system. Data from 16 outcrops were collected and 6400 clasts described. Facies analysis, micro‐palaeontology and macro‐palaeontology and petrographic characteristics of the gravel deposits have highlighted the presence of three allostratigraphic units. Clast lithology is the main discriminator among these units. Cluster and principal component analyses of the 6400 clasts have improved understanding of the stratigraphy of the Lower Pleistocene deposits and constrain the re‐routing of the lower palaeo‐Cecina River from a supposedly south‐east to north‐west direction to the present east to west direction. Short rivers feeding small fan deltas represented by the oldest allostratigraphic units were abandoned in the Lower Pleistocene, when the re‐routing of the Cecina River caused the capture of these streams. This evolution suggests a change in the tectonic regime of the area. The fan deltas developed on the hanging wall of normal faults sub‐parallel to the coast; a change to a transtensile tectonic regime caused the deviation of the main river channel toward the present coast and the formation of a pull‐apart basin, which is now exploited by the Cecina River. This study illustrates the value of lithological analyses of gravel deposits for understanding the tectonic evolution of an area.     

Groundwater resource degradation in coastal plains: The example of the Cecina area (Tuscany – Central Italy)

The paper describes the degradation of the groundwater resources in the Cecina area, where seawater intrusion, B contamination and NO₃ pollution are all affecting the heavily exploited Pleistocene aquifer. Over-pumping has brought water levels to about 0 m.a.s.l. as far as about 7 km from the shore line, thereby promoting the seawater intrusion. The intrusion, which is characterized by cation exchange phenomena and Ca–Cl type waters, enters the plain mostly through the shallower horizons. The saline front, which advanced from 0.5 to 1 km in 4 a, has by now reached the foot of the hills to the east of the town, where it is also affecting wells of the local aqueduct. Boron contamination, linked to past discharge of industrial waste transported downstream by the river, reached concentrations as high as 3.5 mg/L in the mid-1980s. Although a decreasing trend is now under way, B content is still close to 1 mg/L. The presence of high NO₃, which, together with the seawater intrusion, represents a major issue for groundwater management in the area, is linked to the widespread utilization of fertilizers. Nitrate concentration, which reaches a maximum of about 300 mg/L in the shallow aquifer horizons and then decreases rather regularly with depth, is strongly influenced by precipitation. However, irrigation also contributes significantly to transporting the NO₃ contamination to depth, as clearly shown by δ¹⁸O data. The severe decline in the quality of the groundwater resource in the Cecina area is further compounded by an overall decrease in water availability in the region of Tuscany, as evidenced by long-term monitoring of precipitation and fluvial discharge.     

Using hydrochemistry and environmental isotopes in the assessment of groundwater quality in the Euphrates alluvial aquifer,Syria

Hydrochemical and environmental isotope methods were used to characterize the groundwater quality in ten wells belonging to the Euphrates alluvial aquifer in Syria, with the aim to assess the origin and dynamic of groundwater salinization in this system. The Euphrates River (ER) water along its entire course in Syria is rather fresh (TDS < 0.5 g/L), and thus, it is suitable for drinking and irrigation purposes. Groundwater salinity progressively increases from north to south, changing from almost freshwater (TDS < 0.6 g/L), with a Ca–Mg and HCO₃ type near the Syrian–Turkish border to brackish water (1 < TDS < 3 g/L), with a Ca–Mg or Na–Ca–Mg and SO₄–HCO₃ type in the vicinity of Al-Raqqa, and hence it can safely be used for irrigation. Downstream Deir-Ezzor the groundwater quality becomes fairly saline to very saline (3 < TDS < 29 g/L), with a Na–Cl type, and therefore it has an absolute hazard (SAR > 5) for irrigation uses. This pattern of chemical evolution, which is also clearly reflected in the variations of groundwater ionic ratios, completely agrees with the thermodynamic simulation results obtained by an experimental evaporation essay of a water sample taken from the ER near Deir-Ezzor. Stable isotopes permit the distinction between three main evaporation processes: under high, intermediate and low humidity conditions. Radioisotopes (³H and ¹⁴C) indicate the recent age and renewability of groundwater in this aquifer and confirm that its origin is entirely belonged to the ER water, either by direct bilateral interconnection or by vertical infiltration of the irrigation water totally taken from the ER. Relationships between major ions and δ¹⁸O values of the groundwater allow to differentiate between two main enrichment processes: either evaporation only or evaporation plus dissolution, that can explain altogether the development of groundwater salinity in such a dry area.     

Integrated hydrochemical assessment of the Quaternary alluvial aquifer of the Guadalquivir River, southern Spain

The alluvial aquifer of the Guadalquivir River comprises shallow Quaternary deposits located in the central-eastern part of the Province of Jaén in southern Spain, where groundwater resources are used mainly for crop irrigation in an important agricultural area. In order to establish the baseline hydrochemical conditions and processes determining the groundwater quality, groundwater and river water samples were collected as part of an integrated investigation that coupled multivariate statistical analysis with hydrochemical methods to identify and interpret the groundwater chemistry of the aquifer system. Three main hydrochemical types (Mg–Ca–HCO₃, Ca–Mg–SO₄–HCO₃–Cl and Na–Ca–Mg–Cl–SO₄) were identified. Further interpretation, using R-mode principal components analysis (PCA) conducted with 13 hydrochemical variables, identified two principal components which explain ⅔ of the variance in the original data. In combination with the hydrochemical interpretation, mineralogical analyses of the aquifer sediment together with inverse geochemical modelling using NETPATH showed that dedolomitization (calcite precipitation and dolomite dissolution driven by gypsum dissolution) is the principal hydrochemical process controlling the regional groundwater chemistry. Other processes such as silicate weathering, ion exchange, mixing between river water and groundwater, and agricultural practices also affect the groundwater chemistry.     

Hydrogeological study of the intensely exploited aquifer of the Santa Croce leather-producing district, Tuscany (central Italy)

A hydrogeological study was undertaken to define the groundwater circulation in the Santa Croce area (Tuscany, central Italy) where the existing multilayered aquifer has long been intensively exploited. Investigations carried out on about 150 wells revealed the existence of a deep piezometric depression (to 20?m below sea level) which drains groundwater from the entire surrounding area. Samples from about 70 water points, collected twice in 2007, were analysed for major elements and stable isotope composition. Three major groups of waters, which mix in the study area, have been distinguished: (1) waters of the Ca?CMg?CHCO₃ type mainly flowing along the Arno River Plain; (2) waters of the Na?CK?CCl/Ca?CMg?CHCO₃?CSO_4, type with SO₄ content up to 275?mg/L, inflowing from the Pisane Hills; (3) relatively high-salinity waters mainly of the Na?CHCO₃ type which, with Cl concentrations up to 750?mg/L, likely arise from a normal fault located at the foot of the northern hills. The characteristics of the different components are greatly affected by significant modifying processes such as cation exchange and sulfate reduction. The achieved conceptual model suggests the southern hills as the main recharging area of the aquifer system from which water circulation, characterized by pathways of different length and depth, develops.     

Hydrogeology and geochemistry of the multilayered confined aquifer of the Pisa plain (Tuscany – central Italy)

The Pisa plain contains a multilayered confined aquifer made up of Pleistocene sands and gravels. The groundwater from the wells tapping these horizons are generally of poor quality: they exhibit significant TDS, relatively high Cl content and considerable hardness. During geothermal prospecting of the Pisa plain, about 80 wells ranging in depth from 20 to 250 m were sampled, and both chemical (major ions) and isotope analyses were conducted. The data collected show that TDS is strongly influenced by HCO₃ and Cl, and that a 3-component mixing process affects the groundwater’s chemical composition. The end members of this mixing process have been identified as: (a) diluted HCO₃ meteoric water, which enters the plain mainly from the eastern and northern sides of the study area; (b) Cl-rich water, which largely characterizes the shallow sandy horizons of the multilayered aquifer system and has been attributed to the presence of seawater, as also suggested by δ¹⁸O data; and (c) SO₄-rich groundwater, which is linked to the hot groundwater circulation within Mesozoic carbonate formations and, at first sight, seemed to affect only the gravelly aquifer. A SO₄-rich water also contributes to the sandy aquifer; it probably enters the plain both laterally, from the margins of the Pisan Mountains and from depth, but promptly undergoes substantial SO₄ reduction processes by bacteria. That such processes are at work is suggested both by the low SO₄ and high HCO₃ concentrations found in the well waters and by their C and S isotope compositions. The collected data have allowed zones with higher quality waters to be identified, which may someday be used for the local water supply.     

Geochemistry of regional aquifer systems hosted by carbonate-evaporite formations in Umbria and southern Tuscany (central Italy)

In central Italy Mesozoic carbonates represent the principal reservoir of freshwater of the region. The hydrogeological setting is linked to the geological evolution of the Apennine chain and is generally characterised by a lower aquifer and one or more shallower aquifers separated by thin aquicludes. In these systems, groundwater composition is the result of a complex array of regional and local geochemical processes. The main geochemical processes are the dissolution of calcite, the influx of deeply derived CO₂ related to a regional process of mantle degassing, dedolomitization and mixing with deep saline fluids. The occurrence of saline fluids, characterised by a Na–Cl(HCO₃) composition, is related to the presence of a deep regional aquifer at the base of Mesozoic carbonates. The extremely high pCO₂ values computed for the saline waters suggest that the deep aquifer is also a structural trap for the mantle derived CO₂ during its ascent towards the surface. In central Italy, geological and geophysical data highlight the presence of two different crustal sectors: the eastern sector, where the geometry of the Apennine thrust belt is still preserved, and the western sector, where the compressive structures are dislocated by important extensional deformations. In the western sector, the normal faults disrupting the compressive structures allow the mixing of the deep Na–Cl(HCO₃) fluids with the shallow groundwater causing a salinity increase and the natural deterioration of groundwater quality.     

Thermal modelling of the Larderello geothermal field (Tuscany,Italy)

We present a 3-D thermal model of the Larderello geothermal field (Tuscany) to evaluate (1) the extent and contribution of the heat transfer mechanisms (conduction vs. convection) at the intermediate-upper crust levels, (2) the variability of the heat and mass fluxes entering from below and (3) the crucial role of the formation permeability. The model, composed by three main layers, considers the upper 10 km of the crust to better constrain the simulations with experimental data from borehole, fluid inclusion studies and hypocentral distributions. Several sets of simulations were carried out with different bottom boundary temperatures and different formation permeabilities for the two deeper layers. The results indicate that the present temperature (T) and pressure distributions in the Larderello field require deep reservoir rocks with higher permeability than the overlying capping units and underlying intermediate crust. Permeability values of 1 mDarcy for the reservoir rocks are enough to allow fluid convection, if the temperature at 10 km depth is as high as 500 ± 50°C. The presence of localized zones with formation permeability 50–100 times higher than the surrounding rocks strongly favours the migration of over-pressurized fluids, which episodically break through the overburden, feeding the presently exploited geothermal fields.     

Occurrence and hydrogeochemistry of fluoride in alluvial aquifer of Weihe River,China

Fluoride (F^?) has significant impacts on human health. High fluoride groundwater (up to 1.90 mg/L) has been found in upper confined aquifer underlying the first terrace of Weihe River during a hydrogeological investigation for water supply in 2005. To reveal the occurrence and hydrogeochemistry of high F^? groundwater, hydrogeochemical tools such as saturation index, ionic ratios and correlation analysis were used in this study. The study shows that the concentrations of most physiochemical parameters from phreatic water, influenced by intensive evaporation and anthropogenic activities such as unregulated sewage and excreta disposal and agricultural practices in the area, are higher than those of confined water. The F^? concentration in phreatic water is within the acceptable limits set by China and the World Health Organization (WHO), while that of upper confined water shows a decreasing trend northwestward as the Weihe River approaches, with F^? concentration in the first terrace beyond the national and the WHO standards. High F^? groundwater is observed in alkaline environment associated with high Na⁺, pH, HCO₃ ^? and low Ca²⁺ and Mg²⁺. The enrichment of F^? is controlled by geologic and hydrogeological conditions, fluorine-bearing minerals presented in alluvial formations and their dissolution/precipitation under the alkaline environment along groundwater flow. Ion exchange, human activities and the mixing of different recharge waters may influence the enrichment of F^? as well.     

Irrigation related arsenic contamination of a thin,alluvial aquifer,Madison River Valley,Montana, U.S.A.

The arsenic concentration in 13 water samples from wells in the thin, alluvial aquifer of the Madison River Valley, Montana, U.S.A. ranged from 26 to 150 μg/l. The Madison River, which originates in Yellowstone National Park, has a mean arsenic concentration of 51 μg/l (σ=26 μg/l), based upon very limited sampling in the study area during the main irrigation period. Groundwater arsenic concentration increases down the valley can be best correlated with the intensity of ditch irrigation in this semiarid area. No other sources of dissolved arsenic as concentrated as that of the river water have been identified. Evaporative concentration of river-derived irrigation water is believed to have been the overwhelming factor in the contamination of this shallow aquifer.     

Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano,Italy

This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and ⁸⁷Sr/⁸⁶Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and ⁸⁷Sr/⁸⁶Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water–rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average ⁸⁷Sr/⁸⁶Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704–0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher ⁸⁷Sr/⁸⁶Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO₄ and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites).     

Nitrate source and fate at the catchment scale of the Vibrata River and aquifer (central Italy): an analysis by integrating component approaches and nitrogen isotopes

The aim of this study is to apply an integrated approach to determine nitrate sources and fate in the alluvial aquifer of the River Vibrata (Abruzzi, central Italy) by coupling the Isotope and the Component approaches. Collected data include concentration and nitrogen isotope composition of groundwater samples from the alluvial aquifer and nitrogen loads arising from agricultural and non-agricultural sources. The adopted methodology identified synthetic fertilizers as main sources of nitrate in the Vibrata alluvial aquifer. At the catchment scale, two different zones have been identified: the Upper Valley, where infiltration to groundwater is dominant and nitrogen easily migrates into the aquifer; in this area, nitrate content in groundwater is stable and normally higher than EU requirements. Moreover, streamwaters are fed by groundwater with a nitrate content likely lowered by denitrification processes occurring in the hyporheic zone. In the Lower Valley, runoff processes dominate and the nitrate content in surface waters is higher. Nevertheless, groundwater is locally affected by denitrification that breaks down the nitrate content, which often reaches values consistent with law limits.     

Use of chloride-mass balance and environmental isotopes for evaluation of groundwater recharge in the alluvial aquifer, Wadi Tharad, western Saudi Arabia

Groundwater recharge estimation has become a priority issue for humid and arid regions, especially in regions like Saudi Arabia, where the precipitation varies over space and time as a result of topography and seasonality. Wadi Tharad is a typical arid area in western Saudi Arabia. Within its drainage area of 400 km², the groundwater system shows a graded hydrochemical zonation from the hydrocarbonate in the upper reach to the chloride zone in the lower reach. The saturation index (SI) varies depending on the concentrations of carbonate minerals; the mean for calcite and dolomite is about in equilibrium (e.g., zero value). As halite and gypsum indices are negative, it is undersaturated. Isotopic compositions of H and O in the groundwater show that the groundwater recharge resources are mainly from meteoric water. The chloride-mass balance method was refined to estimate the amount of recharge, which is probably 11% of the effective annual rainfall. These results can be used to improve the accuracy of future groundwater management and development schemes.