A comprehensive monitoring approach for a naturally anoxic aquifer beneath a controlled landfill.

The processes leading to high levels of arsenic (As), iron (Fe), and manganese (Mn) in groundwater, in a naturally reducing aquifer at a controlled municipal landfill site, are investigated. The challenge is to distinguish the natural water-rock interaction processes, that allow these substances to dissolve in groundwater, from direct pollution or enhanced dissolution of hydroxides as undesired consequences of the anthropic activities above. Ordinary groundwater monitoring of physical-chemical parameters and inorganic compounds (major and trace elements) was complemented by environmental isotopes of groundwater (tritium, deuterium, oxygen-18 and carbon-13) and dissolved gases (carbon-13 of methane and carbon dioxide and carbon-14 of methane). Pearson/Spearman correlation indices, as well as Principal Component Analysis (PCA), were used to determine the main correlations among variables. The concurrent presence of As, Fe and CH4, as reported in similar anoxic environments, suggests that anaerobic oxidation of methane could drive the reductive dissolution of As-rich Fe(III)(hydro)oxides. Manganese is more sensitive to carbon dioxide, possibly due to a decrease in pH which accelerates the dissolution of Mn-oxides. Finally, we found that tritium and deuterium, which have been used for decades as leachate tracer in groundwater, may be subject to false positives due to the reuse of water recovered from leachate treatment (which has the same isotopic signature of leachate) within the plants, to comply with the requirements of the circular economy. The integration of the environmental isotope analysis into the traditional monitoring approach can effectively support the comprehension of processes. However, this strategy needs to be complemented by a good conceptual hydrogeological model and expert evaluation to avoid misinterpretations.

A double pre-selection method for natural background levels assessment in coastal groundwater bodies.

To evaluate the chemical status of groundwater bodies (GWB) according to the European Groundwater Directive, EU Member States are required to take into account natural background levels (NBLs) where needed. Assessing the NBLs in coastal GWBs is complicated by seawater intrusion which can be amplified by groundwater withdrawals increasing the salinization of such groundwater systems. This paper proposes a new method for the NBLs assessment in coastal areas based on a double pre-selection (PS) with fixed/dynamic limits. A case study in the Apulia region, located in southeastern Italy, is proposed, where we investigated four adjacent GWBs which form the complex karst, fractured Murgia aquifer, hosted in the Jurassic-Cretaceous carbonate platform, bounded by two seas and sustained by saltwater of marine intrusion in the coastal areas. Data related to 139 monitoring stations (MSs) of the regional groundwater monitoring network were used. The first PS, "static", based on a fixed limit of anthropogenic contamination markers (NO3 and NH4), allows for the elimination of MSs impacted by human activities. On these, the second PS, "dynamic", based on the identification of Cl anomalous values, allows for the identification of additional MSs affected by saline contamination. The residual dataset of MSs was used for the definition of NBLs of Cl, SO4, F and B. A statistical comparison with historical Cl observations finally allowed us to verify if the salinity of current groundwater is representative of pristine conditions. The calculated NBLs of salinity parameters are higher for the two coastal GWBs, with chloride values between 0.8 and 2 mg/L. Conversely, fluorides always show very low NBLs. The double PS approach seems more effective for NBLs calculation in coastal aquifers affected by saline contamination, where the use of a fixed Cl limit fails. It may respond to the international needs for a standardized procedure for NBL assessment.

MWCNT/rGO/natural rubber latex dispersions for innovative, piezo-resistive and cement-based composite sensors.

The present study is focused on the development and characterization of innovative cementitious-based composite sensors. In particular, multifunctional cement mortars with enhanced piezoresistive properties are realized by exploiting the concept of confinement of Multiwall Carbon Nanotubes (MWCNTs) and reduced Graphene Oxide (rGO) in a three-dimensional percolated network through the use of a natural-rubber latex aqueous dispersion. The manufactured cement-based composites were characterized by means of Inelastic Neutron Scattering to assess the hydration reactions and the interactions between natural rubber and the hydrated-cement phases and by Scanning Electron Microscopy and X-Ray diffraction to evaluate the morphological and mineralogical structure, respectively. Piezo-resistive properties to assess electro-mechanical behavior in strain condition are also measured. The results show that the presence of natural rubber latex allows to obtain a three-dimensional rGO/MWCNTs segregate structure which catalyzes the formation of hydrated phases of the cement and increases the piezo-resistive sensitivity of mortar composites, representing a reliable approach in developing innovative mortar-based piezoresistive strain sensors.

Groundwater geochemistry and microbial community structure in the aquifer transition from volcanic to alluvial areas.

Groundwaters may act as sinks or sources of organic and inorganic solutes, depending on the relative magnitude of biochemical mobilizing processes and groundwater-surface water exchanges. The objective of this study was to link the lithological and hydrogeological gradients to the aquatic microbial community structure in the transition from aquifer recharge (volcanic formations) to discharge areas (alluvial deposits). A field-scale analysis was performed along a water table aquifer in which volcanic products decreased in thickness and areal extension, while alluvial deposits became increasingly important. We measured the main groundwater physical parameters and the concentrations of major and trace elements. In addition, the microbial community structure was assessed by estimating the occurrence of total coliforms and Escherichia coli, the prokaryotic abundance, the cytometric and phylogenetic community composition. The overall biogeochemical asset differed along the aquifer flow path. The concentration of total and live prokaryotic cells significantly increased in alluvial waters, together with the percentages of Beta- and Delta-Proteobacteria. The microbial propagation over a theoretical groundwater travel time allowed for the identification of microbial groups shifting significantly in the transition between the two different hydrogeochemical facies. The microbial community structure was intimately associated with geochemical changes, thus it should be further considered in view of a better understanding of groundwater ecology and sustainable management strategies.

Tailoring groundwater quality monitoring to vulnerability: a GIS procedure for network design.

Monitoring networks aiming to assess the state of groundwater quality and detect or predict changes could increase in efficiency when fitted to vulnerability and pollution risk assessment. The main purpose of this paper is to describe a methodology aiming at integrating aquifers vulnerability and actual levels of groundwater pollution in the monitoring network design. In this study carried out in a pilot area in central Italy, several factors such as hydrogeological setting, groundwater vulnerability, and natural and anthropogenic contamination levels were analyzed and used in designing a network tailored to the monitoring objectives, namely, surveying the evolution of groundwater quality relating to natural conditions as well as to polluting processes active in the area. Due to the absence of an aquifer vulnerability map for the whole area, a proxi evaluation of it was performed through a geographic information system (GIS) methodology, leading to the so called "susceptibility to groundwater quality degradation". The latter was used as a basis for the network density assessment, while water points were ranked by several factors including discharge, actual contamination levels, maintenance conditions, and accessibility for periodical sampling in order to select the most appropriate to the network. Two different GIS procedures were implemented which combine vulnerability conditions and water points suitability, producing two slightly different networks of 50 monitoring points selected out of the 121 candidate wells and springs. The results are compared with a "manual" selection of the points. The applied GIS procedures resulted capable to select the requested number of water points from the initial set, evaluating the most confident ones and an appropriate density. Moreover, it is worth underlining that the second procedure (point distance analysis [PDA]) is technically faster and simpler to be performed than the first one (GRID + PDA).