Water, sediment and soil physicochemical interactions in freshwater, brackish and saline systems

The physicochemical interactions between water, sediment and soil deeply influence the formation and development of the ecosystem. In this research, different freshwater, brackish and saline subaqueous environments of Northern Italy were chosen as study area to investigate the physicochemical processes which occur at the interface between water and sediments, as well as the effects of soil submergence on ecosystem development. In the freshwater system of the Reno river basin, the main purpose was to define the heavy metals hazard in water and sediments of natural and artificial water courses. Heavy metals partitioning and speciation allowed to assess the environmental risk linked to the critical action of dredging canal sediments, for the maintenance of the hydraulic safety of plain lands. In addition, some bioremediation techniques were experimented for protecting sediments from heavy metals contamination, and for giving an answer to the problem of sediments management. In the brackish system of S. Vitale park, the development of hydromorphic and subaqueous soils was investigated. The study of soil profiles highlighted the presence of a soil continuum among pedons subjected to different saturation degrees. This investigation allowed to the identification of both morphological and physicochemical indicators, which characterize the formation of subaqueous soils and describe the soil hydromorphism in transitional soil systems. In the saline system of Grado lagoon, an ecosystem approach was used to define the role of water oscillation in soil characterization and plants colonization. This study highlighted the close relationship and the mutual influence of soil submergence and aeration, tide oscillation and vegetation cover, on the soil development. In view of climate change, this study contribute to understand and suppose how soil and landscape could evolve. However, a complete evaluation of hydromorphic soil functionality will be achieved only involving physiological and biochemical expertise in these kind of studies.

Bioremediation of polychlorinated biphenyls (PCBs) polluted marine sediments: a study of the effectiveness of bioaugmentation and biostimulation via microbial electrochemical technologies and polyhydroxyalkanoates

Polychlorinated biphenyls (PCBs) are chemicals largely employed in the industry, banned at the end of the last century yet still persistent in the environment. Bioremediation, namely exploiting bacteria to reduce PCBs’ toxicity, is receiving attention as a promising approach to remediate polluted site in situ. Natural bioremediation is constrained by several factors as the low amount of the required growth substrates (e.g. electron donors, oxygen) and the scarcity of bacteria able to metabolize PCBs. In this regard, use of biodegradable polymers or applied potentials have been demonstrated effective in priming bioremediation of freshwater environments (e.g. river sediments) polluted by chlorinated solvents or PCBs. Yet, little is known regarding the application in marine sediments, where the abundance of anaerobic competitors (i.e. sulfate reducing bacteria) and the different sediment’s features might affect the bioremediation. In this study, polyhydroxyalkanoates (PHAs) and Microbial Electrochemical Technologies (METs) were applied for the first time to prime bioremediation of PCBs polluted marine sediments. The influence of PHAs was studied on the main anaerobic metabolisms and on the microbial community of the heavily polluted sediments coming from the Pialassa della Baiona, a micro-tidal coastal lagoon in Ravenna, and from Mar Piccolo, the marine basin aside Taranto. The impact of METs was deepened by monitoring the physical-chemical parameters and the main anaerobic metabolisms of the sediments coming from Ravenna. The effectiveness of biostimulating with PHAs depended on the features of the treated site, possibly due to the availability of the amendments and to the competition of the indigenous microbial communities. The bioelectrochemical stimulation inhibited the bioremediation process. In both cases, the presence of an inoculated bacterial community was required to perform bioremediation. The collected results led to a comprehensive analysis of the available literature, questioning what could be the further approaches for an effective in situ bioremediation.

Individuazione di tecniche di gestione idrica-agronomica e di ricarica dell’acquifero freatico costiero per limitare la salinizzazione delle acque sotterranee e dei suoli.

Nel Comune di Ravenna, oltre 6.800 ettari di terreni agricoli sono a rischio salinizzazione, a causa dell’alta salinità delle acque sotterranee presenti all’interno dell’acquifero freatico costiero. L'area è interessata da subsidenza naturale, per compattazione dei sedimenti alluvionali e antropica, causata dall’estrazione di gas e dall’eccessivo sfruttamento delle acque sotterranee. Ne deriva che la maggior parte di questo territorio è sotto il livello medio del mare e l'agricoltura, così come ogni altra attività umana, è possibile grazie ad una fitta rete di canali di drenaggio che garantiscono il franco di coltivazione. L’agricoltura è una risorsa importante per la zona, ma a causa della scarsa disponibilità di acque dolci e per l’aumento dei processi di salinizzazione dei suoli, necessita di un cambiamento. Servono pratiche agricole sostenibili, con idonei requisiti irrigui, di drenaggio del suolo, di resistenza alla salinizzazione e di controllo del suolo. Dopo un’analisi generale sulle condizioni dell’acquifero, è stato monitorato un transetto di 10km rappresentativo della parte costiera di Ravenna. Infine, con l'obiettivo di comprendere l'interazione tra un canale d'irrigazione e le acque sotterranee, una piccola area agricola (12 ettari), è stata monitorata nel corso del 2011 utilizzando metodi idrologici, geochimici e geofisici. I risultati di questo lavoro mostrano una diffusa salinizzazione della falda freatica, ma anche la presenza di una lente d'acqua dolce spessa 5m, a 400m dalla linea di riva, con caratteristiche chimiche (hydrofacies) tipici di acque continentali e con dimensioni variabili stagionalmente. Questa bolla di acqua dolce si è originata esclusivamente dalle infiltrazioni dal canale d’irrigazione presente, in quanto, il contributo dell’irrigazione superficiale è stato nullo. Sfruttando la rete di canali di drenaggio già presente sarebbe possibile estendere questo processo d’infiltrazione da canale in altre porzioni dell’acquifero allo scopo di ricaricare l’acquifero stesso e limitare la salinizzazione dei suoli.

Use of bioassays and biomarkers in Daphnia magna to assess the effect of pharmaceutical residuals in freshwater ecosystems

Widespread occurrence of pharmaceuticals residues has been reported in aquatic ecosystems. However, their toxic effects on aquatic biota remain unclear. Generally, the acute toxicity has been assessed in laboratory experiments, while chronic toxicity studies have rarely been performed. Of importance appears also the assessment of mixture effects, since pharmaceuticals never occur in waters alone. The aim of the present work is to evaluate acute and chronic toxic response in the crustacean Daphnia magna exposed to single pharmaceuticals and mixtures. We tested fluoxetine, a SSRI widely prescribed as antidepressant, and propranolol, a non selective β-adrenergic receptor-blocking agent used to treat hypertension. Acute immobilization and chronic reproduction tests were performed according to OECD guidelines 202 and 211, respectively. Single chemicals were first tested separately. Toxicity of binary mixtures was then assessed using a fixed ratio experimental design with concentrations based on Toxic Units. The conceptual model of Concentration Addition was adopted in this study, as we assumed that the mixture effect mirrors the sum of the single substances for compounds having similar mode of action. The MixTox statistical method was applied to analyze the experimental results. Results showed a significant deviation from CA model that indicated antagonism between chemicals in both the acute and the chronic mixture tests. The study was integrated assessing the effects of fluoxetine on a battery of biomarkers. We wanted to evaluate the organism biological vulnerability caused by low concentrations of pharmaceutical occurring in the aquatic environment. We assessed the acetylcholinesterase and glutathione s-transferase enzymatic activities and the malondialdehyde production. No treatment induced significant alteration of biomarkers with respect to the control. Biological assays and the MixTox model application proved to be useful tools for pharmaceutical risk assessment. Although promising, the application of biomarkers in Daphnia magna needs further elucidation.

Stream sediments analysis for geochemical mapping of Romagna Apennines (Northern Italy): monitoring and management tool of environmental resources at various scales

Geochemical mapping is a valuable tool for the control of territory that can be used not only in the identification of mineral resources and geological, agricultural and forestry studies but also in the monitoring of natural resources by giving solutions to environmental and economic problems. Stream sediments are widely used in the sampling campaigns carried out by the world's governments and research groups for their characteristics of broad representativeness of rocks and soils, for ease of sampling and for the possibility to conduct very detailed sampling In this context, the environmental role of stream sediments provides a good basis for the implementation of environmental management measures, in fact the composition of river sediments is an important factor in understanding the complex dynamics that develop within catchment basins therefore they represent a critical environmental compartment: they can persistently incorporate pollutants after a process of contamination and release into the biosphere if the environmental conditions change. It is essential to determine whether the concentrations of certain elements, in particular heavy metals, can be the result of natural erosion of rocks containing high concentrations of specific elements or are generated as residues of human activities related to a certain study area. This PhD thesis aims to extract from an extensive database on stream sediments of the Romagna rivers the widest spectrum of informations. The study involved low and high order stream in the mountain and hilly area, but also the sediments of the floodplain area, where intensive agriculture is active. The geochemical signals recorded by the stream sediments will be interpreted in order to reconstruct the natural variability related to bedrock and soil contribution, the effects of the river dynamics, the anomalous sites, and with the calculation of background values be able to evaluate their level of degradation and predict the environmental risk.

Bioremediation of PCB-contaminated marine sediments: From identification of indigenous dehalorespirers to enhancement of microbial reductive dechlorination

Marine sediments are the main accumulation reservoir of organic recalcitrant pollutants such as polychlorinated biphenyls (PCBs). In the anoxic conditions typical of these sediments, anaerobic bacteria of the phylum Chloroflexi are able to attack these compounds in a process called microbial reductive dechlorination. Such activity and members of this phylum were detected in PCB-impacted sediments of the Venice Lagoon. The aim of this work was to investigate microbial reductive dechlorination and design bioremediation approaches for marine sediments of the area. Three out of six sediment cultures from different sampling areas exhibited dechlorination activities in the same conditions of the site and two phylotypes (VLD-1 and VLD-2) were detected and correlated to this metabolism. Biostimulation was tested on enriched dechlorinating sediment cultures from the same site using five different electron donors, of which lactate was the best biostimulating agent; complementation of microbial and chemical dechlorination catalyzed by biogenic zerovalent Pd nanoparticles was not effective due to sulfide poisoning of the catalyst. A new biosurfactant-producing strain of Shewanella frigidimarina was concomitantly obtained from hydrocarbon-degrading marine cultures and selected because of the low toxicity of its product. All these findings were then exploited to develop bioremediation lab-scale tests in shaken reactors and static microcosms on real sediments and water of the Venice lagoon, testing i) a bioaugmentation approach, with a selected enriched sediment culture from the same area, ii) a biostimulation approach with lactate as electron donor, iii) a bioavailability enhancement with the supplementation of the newly-discovered biosurfactant, and iv) all possible combinations of the afore-mentioned approaches. The best bioremediation approach resulted to be a combination of bioaugmentation and bioremediation and it could be a starting point to design bioremediation process for actual marine sediments of the Venice Lagoon area.