Elisa Sacchi

Multivariate statistical and GIS-based approach to identify heavy metal sources in soils

The knowledge of the regional variability, the background values and the anthropic vs. natural origin for potentially harmful elements in soils is of critical importance to assess human impact and to fix guide values and quality standards. The present study was undertaken as a preliminary survey on soil contamination on a regional scale in Piemonte (NW Italy). The aims of the study were: (1) to determine average regional concentrations of some heavy metals (Cr, Co, Ni, Cu, Zn, Pb); (2) to find out their large-scale variability; (3) to define their natural or artificial origin; and (4) to identify possible non-point sources of contamination. Multivariate statistic approaches (Principal Component Analysis and Cluster Analysis) were adopted for data treatment, allowing the identification of three main factors controlling the heavy metal variability in cultivated soils. Geostatistics were used to construct regional distribution maps, to be compared with the geographical, geologic and land use regional database using GIS software. This approach, evidencing spatial relationships, proved very useful to the confirmation and refinement of geochemical interpretations of the statistical output. Cr, Co and Ni were associated with and controlled by parent rocks, whereas Cu together with Zn, and Pb alone were controlled by anthropic activities. The study indicates that background values and realistic mandatory guidelines are impossible to fix without an extensive data collection and without a correct geochemical interpretation of the data.

Geochemistry of the formation waters in the Po plain (Northern Italy): an overview.

Abstract The Po Valley brines represent the base level of the Quaternary aquifer located in a thick clay-sands sedimentary sequence. Geochemistry indicates that these are marine waters, evaporated to the stage of gypsum precipitation and trapped at the bottom of the basin in the late Messinian. Most of the groundwater samples collected from different springs and wells in the plain result from a mixture of these Na–Cl brines and shallow groundwaters laterally recharged by the Alpine and Apennine chains. Natural outflows of brackish waters are associated with major tectonic features. Mud volcanoes, located in the eastern sector of the Po plain, are constantly monitored as sudden chemical changes are significant precursors of seismic activity. In the western sector, calcite-filled veins isotopically record different degrees of water-rock interaction. These are outcropping fossil conduits, where mixing between shallow groundwaters and deep seated brines has occurred. The temporal continuity of the hydrological circuits allows the reconstruction of past and present groundwater circulation patterns. This paper summarises and integrates the geochemical data produced over many years in order to obtain a regional picture of brine origins and the natural mechanisms of groundwater flow.

Hydrogeology as a climate recorder: Sahara–Sahel (North Africa) and the Po Plain (Northern Italy)

Abstract Information on palaeoclimate is encoded in groundwater in a variety of measurable “tracers”. A great variety of geochemical and isotopic methods has been developed and tested with the aim of defining the different moments and aspects of the water cycle, providing a fundamental information on the recharge and groundwater flow conditions. Furthermore, environmental tracers allow us to reconstruct past environmental changes. Particular emphasis is put on Western Africa and on the Po valley. In fact, two features are common to these regions: the movement of air masses crossing them and the geological characteristics. From the global perspective, Sahel, North Africa, Mediterranean Basin and Central Europe reveal a relative simple pattern of spatial and temporal composition of precipitation. The displacement of the Intertropical Convergence Zone (ITCZ) and the Azores anticyclone control the climatological regime and, consequently, the isotopic composition of rainfall. Moreover, both regions are characterised by big aquifers in the form of multilayer systems several hundred metres thick in large sedimentary basins. The aquifers are generally formed by sandstones (Sahara) or sands (Po valley) and are interbedded with argillaceous layers and outcrop only in fairly limited areas, constituting the recharge zones. The groundwater movement in confined aquifers is always lower than 1 m year −1 , respecting the conditions of steady-state flow regime and hydraulic continuity, necessary for the “hydro-archives”. The comparison between the Sahara–Sahel and southern Alps allows to define the principal periods of aquifer replenishment associated with the displacement of the Intertropical Convergence Zone (ITCZ) and the Azores anticyclone. Continental isotope archives provide a means of extending the knowledge on the magnitude and the causes of environmental and climate changes. Nevertheless, for a quantitative interpretation of the isotope records preserved in continental archives, it is necessary to know the response of the isotopic composition of precipitation to long-term fluctuations in key climatic parameters over a given area. Further, the transfer functions relating the climate-induced changes of the isotopic composition of precipitation to the isotope record preserved in the given archive should be established. It appears, thus, that stable isotopes can, presently only be used as an indirect proxy dating method for palaeowaters.

Identifying the effects of human pressure on groundwater quality to support water management strategies in coastal regions: A multi-tracer and statistical approach (Bou-Areg region, Morocco)

Groundwater pollution from anthropogenic sources is a serious concern affecting several coastal aquifers worldwide. Increasing groundwater exploitation, coupled with point and non-point pollution sources, are the main anthropogenic impacts on coastal environments and are responsible for severe health and food security issues. Adequate management strategies to protect groundwater from contamination and overexploitation are of paramount importance, especially in arid prone regions, where coastal aquifers often represent the main freshwater resource to sustain human needs. The Bou-Areg Aquifer (Morocco) is a perfect example of a coastal aquifer constantly exposed to all the negative externalities associated with groundwater use for agricultural purposes, which lead to a general increase in aquifer salinization. In this study data on 61 water samples, collected in June and November 2010, were used to: (i) track groundwater composition changes related to the use of irrigation water from different sources, (ii) highlight seasonal variations to assess aquifer vulnerability, and (iii) present a reproducible example of multi-tracer approach for groundwater management in rural coastal areas. Hydrogeochemical results show that Bou-Areg groundwater is characterized by - high salinity, associated with a remarkable increase in bicarbonate content in the crop growing season, due to more intense biological activity in irrigated soils. The coupled multi-tracer and statistical analysis confirms the strong dependency on irrigation activities as well as a clear identification of the processes governing the aquifers hydrochemistry in the different seasons. Water Rock Interaction (WRI) dominates the composition of most of groundwater samples in the Low Irrigation season (L-IR) and Agricultural Return Flow (ARF) mainly affects groundwater salinization in the High Irrigation season (H-IR) in the same areas naturally affected by WRI. In the central part of the plain River Recharge (RR) from the Selouane River is responsible for the high groundwater salinity whilst Mixing Processes (MIX) occur in absence of irrigation activities.

Geochemical changes at the Bagni di Triponzo thermal spring during the Umbria-Marche 1997–1998 seismic sequence

After the earthquakes of September 26, 1997, that hit the Umbria-Marcheboundary (Apennine, Central Italy), with a maximum 6.0 Mw, aprogram of geochemical surveying together with a collection ofhydrogeological changes episodes was extended throughout theepicentre-area, taking the yearly period of the seismic sequence as a whole.After a first areal screening, the Bagni di Triponzo thermal spring wasselected for a discrete temporal monitoring (weekly and monthly basis),being the unique thermal spring throughout the epicentre area. This sitedeserves peculiar interest in deepening the knowledge about deep fluidscirculation changing during seismicity.Laboratory and on-field analyses included major, minor and trace elementsas well as dissolved gases (He, Ar, CH4, CO2, H2S,222Rn, NH4, As, Li, Fe, B, etc...) and selected isotopic ratios(C, H, O, He, Sr, Cl), meaningful from tectonic point of view.The chemistry and isotopic chemistry of the spring were fully outlined anddiscussed, pointing out the main process involving the thermal aquifer: thewater-rock interaction inside the Evaporite Triassic Basement (ETB),possibly involving also the Paleozoic Crystalline Basement. On theother hand, sudden and apparent geochemical and hydrogeologicalvariations during the seismic sequence ruled out an evolution in thewater-rock interaction processes. They occurred both at depth, i.e.,induced by fluid remobilization within the crust explained by the Coseismic Strain Model and by the Fault Valve Activity Model, and in the shallow part of the reservoir (i.e., meteoric watercontamination). A statistical multivariable analysis (Factor Analysis) wasaccomplished to better constrain the correlation between the paroxysmalphases of the seismic sequence and the observed trends and spike-likeanomalies. The groundwater variations was inferred to occur mainly insidethe ETB, from depth (1–2 km) up to surface, particularly in associationof the Sellano earthquake (14/10/1997) and of the seismic re-activationof the sequence at the end of March 1998 (Gualdo Tadino-Rigali andVerchiano areas). The lack of deeper input from below the ETB (slightsignature of PCB), as the lack of He mantle signature, during the seismicperiod as a whole, accounted for seismogenic fault segments rooted onlyin the crust. The results also provide useful information about theearthquake-related response mechanisms occurring at this site, thatrepresent the basic task for planning and managing the impendinghydro-geochemical network aimed at defining the relationships betweenseismic cycle, fluids and reliable earthquake forerunners.

Nitrogen inputs to a river course in a heavily impacted watershed: A combined hydrochemical and isotopic evaluation (Oglio River Basin, N Italy)

This study aims at evaluating sources and processes affecting NO₃(-) concentrations in the Oglio River. Five sampling campaigns considered the main watercourse, tributaries, point pollution sources, springs, and groundwater. Physico-chemical parameters, N forms, B, Sr(2+), stable isotopes (δ(2)HH₂O, δ(18)OH₂O, δ(15)NNO₃, δ(18)ONO₃, δ(11)B) and discharge were measured. Hydrological modelling was performed using mass balance and End Member Mixing Analysis equations. During the irrigation period, in the upstream reach, up to 90% of the natural river flow is diverted for irrigation and industrial purposes; excess water drained from agricultural fields is returned to river in the downstream reach. Results evidenced, in the middle reach, a large input of NO₃(-)-rich groundwater which could be quantified using hydrological modelling. Groundwater inputs are responsible for the sharp, tenfold increase in NO₃(-) in the river water, from 2.2-4.4 up to 33.5 mgL(-1), and are more evident in summer, when discharge is lower. Nevertheless, river water preserves its natural B isotopic composition, indicating that the two tracers do not have a common origin and are not co-migrant. In the lower plain, surface-groundwater interconnections and human disturbances in the water cycle favour the recycling of the compounds in the environment, and lead to a similarity in composition of the different water bodies (Oglio River, tributaries and groundwater). The long lasting agronomical practices have profoundly modified the surface-groundwater equilibrium and chemical characteristics, resulting in a highly buffered system. Infiltrating irrigation water leaches down NO₃(-) which is subsequently denitrified; when returned to the Oglio River, groundwater modifies the river water composition by dilution, in the case of NO₃(-), or by addition, for other constituents (e.g. Cl(-), B). The results of this study indicate that, in order to reduce the NO3(-) transport towards the Adriatic Sea, groundwater contamination should be addressed first, with expected long recovery times.

Origin of Arsenic in Groundwater from the Multilayer Aquifer in Cremona (Northern Italy)

An analysis of 70 wells that tap groundwater from depths of up to 260 m in and around the town of Cremona, N. Italy, shows that 50 of them contain more than 10 μg/L of arsenic. Concentrations of As >10 ppb are accompanied by concentrations of Fe ranging from <0.1 to 6 mg/L and high concentrations of NH4 and Mn (<19 and <1.3 mg/L, respectively). The associations suggest that the mechanism of mobilization of As is the reductive dissolution of Fe oxides driven by the degradation of peat, which is commonly found in the aquifer system. Groundwater in the aquifer has a component of downward flow via leakage through aquitards and flow through lateral discontinuities in them. Along these flow paths, As is released by reductive dissolution of Fe oxides in shallow and intermediate aquifers (0-85 m below surface), reaching up to 183 μg/L, and is attenuated (<95 μg/L) at greater depths (100-150 m). Coprecipitation in iron sulfides could play an important role in As attenuation at these depths. The lower As concentration (<37 μg/L) in the deepest aquifer (160-260 m) is less related to the As concentration of the overlying aquifers because the groundwater here has a component of upward flow.

Water quality decline in coastal aquifers under anthropic pressure: the case of a suburban area of Dakar (Senegal).

In recent years, the unregulated increase of the population in coastal areas of developing countries has become source of concern for both water supply and quality control. In the region of Dakar (Senegal), approximately 80% of water resources come from groundwater reservoirs, which are increasingly affected by anthropogenic pressures. The identification of the main sources of pollution, and thus the aquifer vulnerability, is essential to provide a sound basis for the implementation of long-term geochemically based water management plans in this sub-Saharan area. With this aim, a hydrochemical and isotopic survey on 26 wells was performed in the so-called Peninsula of Cap-Vert. Results show that seawater intrusion represents the main process affecting groundwater chemical characteristics. Nitrates often exceed the World Health Organization drinking water limits: stable isotopes of dissolved nitrate (

Integrated socio-hydrogeological approach to tackle nitrate contamination in groundwater resources. The case of Grombalia Basin (Tunisia)

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AMS measurement of 129I, 36Cl and 14C in underground waters from Mururoa and Fangataufa atolls

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