Title: Residui farmaceutici nei reflui civili e negli ecosistemi acquatici: il caso di Roma e del fiume Tevere

Transcript

1 Monitoraggio e controllo dei microinquinanti prioritari nelle acque e tecniche di rimozione negli impianti di trattamento delle acque destinate al consumo umano e delle acque reflue. A cura di Irsa Cnr, Istituto Superiore di Sanità, INCA, Setac, Utilitalia, CTS Ecomondo Title: Toxicity of single human pharmaceuticals and their mixtures to Aliivibrio fischeri. Comparison among experimental data and predictive models Valeria Di Nica*, Sara Villa and Antonio Finizio Dept. of Earth and Environmental Sciences, University of Milano Bicocca, Piazza della Scienza 1, Milano, Italy In this study toxicity effects of three pharmaceuticals (PhCs), widely found in WWTPs effluents and in surface water bodies, were investigated, by using the bioluminescent bacterium Aliivibrio fischeri as non-target organism (Microtox test). The selected chemicals were two PhCs of human use (diclofenac sodium [DCF] and carbamazepine [CBZ]) and a chemical commonly used as a tracer of human contamination (caffeine [CFF]). Toxicity was measured for each compound and for two binary mixtures (DCF-CBZ; DCF-CFF), in which the components were mixed in a ratio of their individual IC50 values (equitoxic ratio). For the individual chemicals toxicity effects were moderate (15.9 mg/l, 94.0 mg/l and mg/l for DCF, CBZ and CFF respectively). However, according to the Global Harmonized System of Classification and Labelling of Chemicals (GHS) classification, DCF and CBZ fall in the category of harmful substances for the aquatic ecosystems. Comparison between the experimental IC50 and the baseline toxicity for each PhC indicated that the tested chemicals behave as narcotic (polar and non polar) towards A. fischeri. The toxicity of the mixtures was measured experimentally and the results were compared with those obtained by using two predictive models commonly used in aquatic toxicology: Concentration Addition (CA) and Independent Action (IA). Results indicated that for these combination of chemicals CA and IA models predicted quite correctly the observed mixture toxicity (59.2 and mg/l for DCF-CBZ and DCF-CFF respectively). The nature of the PhCs interactions were, also, determined by using the Combination Index (CI) method (Chou, 2006) commonly applied in pharmacology (synergistic, additive and antagonisic effects are indicated by values of CI <1, =1 and >1 respectively). Application of this method confirmed the additive behaviour of the tested mixtures (CI values near 1 for the entire concentration-response relationships). 1

2 Residui farmaceutici nei reflui civili e negli ecosistemi acquatici: il caso di Roma e del fiume Tevere Nicoletta Ademollo, Silvio Capri, Jasmin Rauseo, Luisa Patrolecco Istituto di Ricerca sulle Acque, Consiglio Nazionale delle Ricerche, Area della Ricerca RM1, Via Salaria km 29,300, 00015, Monterotondo Scalo (Roma). Le indagini ambientali sulla presenza di principi farmaceutici negli ecosistemi acquatici hanno messo in evidenza alcune criticità: 1. la crescente diffusione di nuove molecole associate all ampio utilizzo di farmaci tra la popolazione; 2. la mancanza in molti casi di metodi analitici sufficientemente sensibili ed accurati per l identificazione di farmaci e loro metaboliti presenti spesso in ultra tracce nel comparto acquatico; 3. la difficoltà di rimozione di tali microinquinanti nei sistemi di trattamento delle acque reflue. Tuttavia, i farmaci, ad oggi, non sono considerati sostanze pericolose né prioritarie; fanno eccezione l estrogeno naturale 17-β-estradiolo, l estrogeno sintetico, 17-α-etinilestradiolo e l antinfiammatorio Diclofenac, inclusi dalla UE come osservati speciali in una Watch List (Direttiva 2013/39/UE), per i quali è obbligatorio raccogliere dati di monitoraggio per facilitare i futuri esercizi di definizione delle priorità di intervento per la salvaguardia delle acque. Questo studio fornisce dati sulla presenza, in stagioni diverse, di 12 farmaci (antinfiammatori non steroidei, regolatori lipidici, antiepilettici, ormoni steroidei) negli influenti/effluenti dei principali impianti di depurazione di Roma e nelle acque dei corpi idrici riceventi: il tratto urbano del fiume Tevere e del fiume Aniene. I risultati indicano che durante il trattamento delle acque di scarico, la maggior parte dei farmaci non viene eliminata completamente (efficienze di rimozione comprese tra il 14 e il 100%). I livelli riscontrati, variano nell intervallo ng/l negli influenti e negli effluenti. Carbamazepina, Diclofenac, Ibuprofen e Gemfibrozil mostrano la maggior resistenza alla rimozione. Le concentrazioni nei fiumi recettori sono di circa un ordine di grandezza inferiori rispetto agli effluenti, con una tendenza ad aumentare progressivamente nel tratto urbano del fiume Tevere. E stata inoltre eseguita un analisi di rischio ambientale che ha mostrato che Carbamazepina, Gemfibrozil e estrone possono costituire un rischio elevato per l ambiente acquatico alle concentrazioni rilevate negli effluenti e un rischio medio nelle acque fluviali. 2

3 Behaviour and fate of priority micropollutants in wastewater treatment plants and surface water Sara Castiglioni*, Ettore Zuccato, Enrico Davoli Department of Environmental Health Sciences, IRCCS Istituto di Ricerche Farmacologiche Mario Negri, Via La Masa 19, Milan, Italy. * contact: Several classes of micropollutants are discharged in urban wastewater after human consumption or are released directly from manufactured products and enter the environment mainly through wastewater treatment plants (WWTPs). The present work aimed at studying occurrence, sources and fate of several classes of priority pollutants (i.e. pharmaceuticals, personal care products, disinfectants, illicit drugs) in the river Lambro basin, north of Italy. A mass balance of the emissions was performed to evaluate the impact of metropolitan areas and identify the sources of contamination. Specific analytical methods based on solid phase extraction and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) were developed and validated. Pharmaceuticals were the most abundant compounds in urban wastewater and the amounts entering wastewater treatment plants (WWTPs) in the city of Milan were up to 10 kg/day. Removal rates were variable among the different classes of chemicals, they were generally higher than 70% for pharmaceuticals, illicit drugs, disinfectants, but were very low for some UV filters. Removal rates were affected by the type of advanced treatment adopted (i.e. disinfection, UV treatment) and by the nature of each substance. The levels of contaminats in surface water ranged from few ng/l to µg/l and increased from north to south in the river basin. Widespread sources of contamination were found all over the area investigated. Finally, groundwater resulted also affected by contamination, and the concentrations found in the first layers were higher in wells closer to rivers, suggesting a possible contribution of surface water to the contamination. The results clearly indicate that for developing remediation approaches in a highly urbanized area a complex picture made up of scattered and heterogeneous sources of contamination should be considered. 3

4 Metodologie portatili, per indagini speditive atte a valutare le potenziali contaminazioni direttamente in campo: XRF (spettroscopia a Fluorescenza a Raggi X) sui sedimenti fluviali ed GC-MS (gascromatografia Massa) per acque superficiali Nicolodi Francesco1 e Stelian Nicula2 1Geologo, Foldtani srl, francesco.nicolodi@foldtani.it 2Fisico, QuantAnalitica srl, stelian.nicula@quantanalitica.com Nell ambito dell intervento previsto dall AQST Contratto di Fiume Lambro denominato Riqualificazione tratto terminale della Bevera di Naresso, Valle della Molera alla confluenza con il Lambro e politiche attive per la riduzione dell'inquinamento, è stata condotta una campagna di indagine su metalli nei sedimenti fluviali e di controlli analitici delle acque presso zone di scarico fognario abusivo. Per l analisi sui suoli è stata utilizzata una nuova tecnica spettrofotometrica a raggi x, direttamente in campo, con strumentazione portatile. Sono stati presi oltre 70 campioni di sedimenti, sia in alveo che lungo le sponde. Successivamente si sono integrati & confermati i valori riscontrati, con anche indagini su Idrocarburi Pesanti (C>12) ed Amianto. Infine su tali sedimenti è stato effettuato, in alcuni casi, Test di Cessione ai sensi del DM 5 Febbraio 1998 e s.m.ei. L analisi XRF è stata condotta, come primo screening, su sedimenti tal quali, passanti al setaccio 2 cm. Successivamente si è approfondita su materiale più fine, ripassando i precedenti campioni al setaccio da 1mm. Il metodo XRF ha permesso di valutare rapidamente il tenore di metalli contenuti nella frazione fine dei sedimenti. Si è evidenziata la contaminazione generale dell asta torrentizia, con particolare focalizzazione su un persistente inquinamento da metalli pesanti (quali Cu, Cd, Cr, Zn) lungo un affluente. Per l analisi acque è stato usato un Gas Cromatografo Massa portatile, presso 5 punti d indagine vicino a zone di scarico abusive lungo il corso d acqua, il tutto direttamente in campo, valutando immediatamente il carico inquinante. 4

5 The monitoring programme for the chemical status of the Venice Lagoon according to the European Water Framework Directive (2000/60/CE) Castellani C. 1, Carrer S. 1, Bidinotto P. 2, Zito M.A. 3 1 Thetis Spa 2 Consorzio Venezia Nuova 3 Ministero delle Infrastrutture e dei Trasporti Provveditorato Interregionale alle OO.PP. del Veneto Trentino Alto Adige Friuli Venezia Giulia The monitoring programme of the chemical status of the Venice Lagoon according to the European Water Framework Directive (2000/60/CE) has been conducted during the period Samples of water (20 stations, monthly sampling), sediment (up to 48 stations, annual sampling) and biota (14 stations, annual sampling of bivalves and fishes) of the lagoon have been collected and analysed for priority chemical compounds. The survey revealed (in ) the presence of 4-nonilphenol in water, with annual average concentration levels higher than the Water Quality Standard and with maximum concentration levels higher than the Maximum Permissible Concentration. Standards are exceeded in five water bodies of the lagoon revealing the presence of diffuse sources of alkylphenols, which are used in several industrial and agricultural applications. All other monitored substances resulted in concentration lower than the established standards for the good chemical status of the water bodies. As for sediments (upper layer of 5 cm), the survey highlighted the presence of several priority substances exceeding the Sediment Quality Standards: mercury, lead, cadmium, PAH and, in the last monitoring year, also Tributyltin. Pesticides have never been detected. The chemical with the largest number of exceeding is mercury, mainly distributed in the sediments of the central-northern lagoon. Mercury is also an element of concern for biota (Mytilus galloprovincialis, Tapes philippinarum, Zosterisessor ohiocephalus, Dicentrarchus labrax and Sparus aurata) which accumulate it in their tissues. Tissue residues of mercury are frequently higher than 20 µg/kg ww (the national standard for biota) in all the sampled organisms, with upper levels in fish than molluscs, revealing the process of biomagnification also at low levels of the trophic web. However tissue residues are lower than the limit of 500 µg/kg ww imposed by European Community (Reg. 1881/2006) for the commercialization of fish products. 5

6 Identification of potential environmentally hazardous pharmaceuticals by QSAR modeling Alessandro Sangion 1, Stefano Cassani 1, Ester Papa 1.2, Paola Gramatica 1 1 University of Insubria, via J.H.Dunant 3, Varese (Italy) 2 ITODYS, Université Paris Diderot, 75013, Paris contact: a.sangion@hotmail.it In the recent years pharmaceuticals have been reported to be ubiquitously present in aquatic and terrestrial environment with the possibility to interact and manifest their biological activity on the wildlife. Little is known about pharmaceuticals environmental behaviour and ecotoxicity so that EMEA (European Medicines Agency) released a guideline for the environmental risk assessment of human pharmaceuticals. As part of hazard assessment we propose the characterization of the intrinsic hazard potential of pharmaceuticals by application and development of QSAR (Quantitative Structure-Activity Relationship) models. First of all we screened more than 400 pharmaceuticals for their potential for persistence in the environment, bioaccumulation and toxicity to fish (i.e. PBT behaviour), also taking into account information on potential for biotransformation to highlight chemicals which have the highest intrinsic potential of being found in the environment. Then we characterized these chemicals for their ecotoxicity, by searching data for algae, Daphnia and fish toxicity to represent a simplified aquatic ecosystem at different trophic levels. The available experimental data were filtered and used to build ad hoc QSAR and QAAR (Quantitative Activity-Activity Relationships) models, which were applied to predict the missing toxicological information. Finally, Principal Component Analysis (PCA) was applied to combine predictions by the different models to screen the most environmentally hazardous pharmaceuticals according to their toxicological profile in the different organisms. This study showed how in-silico models can be applied in the hazard assessment procedure to perform preliminary screening and prioritization of chemicals, and how structural based models can maximize the information contained in existing experimental data. Moreover the identification of the structural features mainly associated with the potential PBT behaviour of the prioritized pharmaceuticals is particularly relevant to perform the rational design of new, environmentally safer, pharmaceuticals. 6

7 Pharmaceuticals ecotoxicity: data curation and QSAR modeling Alessandro Sangion, Stefano Cassani, Paola Gramatica University of Insubria, via J.H.Dunant 3, Varese (Italy) contact: Pharmaceuticals have become a class of emerging pollutants since they are increasingly present in environmental compartments. The European Medicines Agency (EMA), published, in 2006, a guideline for the environmental risk assessment of human pharmaceuticals that shall accompany the application for marketing authorisation. This guideline requires, for each chemical, a large amount of data as logkow, ecotoxicity, environmental fate, consumption and so on. Unfortunately ecotoxicological data are available only for a little percent of human pharmaceuticals in literature and databases; modeling approaches like those based on quantitative structure activity relationships (QSARs) are valuable tools to maximize the information contained in existing experimental data and to predict missing information. However the quality and predictivity of a model depends on the quality of the data input. We checked big online databases like ECOTOX or OASIS and literature datasets looking for consistent ecotoxicological data on a set of more than 400 pharmaceuticals finding, in addition to good quality data, thousands of values for unspecified species, unspecified measured effect, unspecified time of exposure, undefined test condition and often with a wide range of experimental responses (even more than three order of magnitude) for the same chemical. In this study we present an example of data curation to prepare consistent datasets of pharmaceuticals with a clearly defined end-point according to the first OECD principle for QSAR modeling, verifying every chemical identifier and structure, organizing data for different end-point, effect measured, time of exposure and filtering inconsistent multiple different experimental data. Then we used these refined dataset to develop specific QSARs for different species representatives of a simplified aquatic ecosystem at different trophic levels in a preliminary aquatic toxicity study. Finally, predictions by different models were combined by Principal Component Analysis (PCA) to verify the toxicity trend and to screen and prioritize the most environmentally hazardous pharmaceuticals. 7

8 PBT assessment of Personal Care Products Stefano Cassani, Alessandro Sangion, Francois Marzetta, Paola Gramatica University of Insubria, via J.H.Dunant 3, Varese (Italy) contact: Recently, organic ingredients in Personal Care Products (PCPs) became compounds of increasing concern, mainly because they are detected in the environment. PCPs are widely used in order to obtain benefits and to improve the quality of everyday life. However, there is limited understanding of how these emerging contaminants may affect aquatic wildlife communities. Some of these PCPs contain also endocrine disrupting compounds, and many of their other adverse effects are unknown. In fact, data on persistence, bioaccumulation and toxicity are lacking and their environmental behavior need to be further investigated. Moreover, the determination of all the dangerous properties, required by REACh and Cosmetics Directive, is a long and difficult task and thus it is very important to have tools to quickly highlight the most hazardous compounds, focusing the experiments only on the prioritized compounds. Quantitative Structure-Relationship (QSAR) models, can predict missing data for the unknown activities and properties necessary to prioritize chemicals. Using QSAR models, in this study we have screened the potential PBT (persistence, bioaccumulation, toxicity) behavior, the persistence and the (eco)toxicity of hundreds of PCPs. 538 chemicals such as fragrances, hair dyes, parabens and sunscreen agents have been screened with different models and tools. The PBT assessment has been carried out with the Insubria PBT Index and the US-EPA PBT Profiler. The PCPs identified as PBTs in agreement by the two methods have been evaluated for their persistence by the Global Half-Life Index (GHLI) model included in QSARINS and for toxicity by a specific QSAR model, developed ad-hoc for personal care products, for the prediction of acute toxicity in Pimephaes promelas. Concluding, the potential environmental hazard of a big number of PCPs has been studied assessing their potential PBT behavior, persistence and fish toxicity. A priority list is therefore proposed, including the potentially most hazardous PCPs. 8

9 Identification of biological parameters for monitoring the quality of olive oil mill waste waters after purification and recovery of bioactive compounds Giorgetti Lucia 1, Longo Vincenzo 1, Cardinali Angela 2, D Antuono Isabella 2, Linsalata Vito 2 Nazzaro Filomena 3, Fratianni Florinda 3, Coppola Raffaele 3 1 Istituto di Biologia e Biotecnologia Agraria, IBBA, CNR, Via Moruzzi 1, Pisa, Italy 2 Istituto di Scienze delle Produzioni Alimentari, ISPA,CNR, Via Amendola 122/O, Bari, Italy 3 Istituto di Scienze dell Alimentazione, ISA,CNR, Via Roma 64, Avellino, Italy Olive oil mill waste waters (OMWWs), a polluting byproduct of the olive oil production process, contain large amount of organics and inorganics compounds (polyphenols, salts, etc) that, if inappropriately discharged, can cause environmental pollution. Polyphenols have several biological activity, but at high concentration they are toxic and their removal from OMWW is an important matter. In this work the detoxification of OMWW, performed by membrane filtration systems, was investigated with the dual aims, of reducing the organic load of OMWW and recovering polyphenols. The OMWWs were processed by ceramic and polymeric membranes with different porosity, to obtain three fractions: microfiltrate (MF, 100,000 Da), ultrafiltrate (UF, 5000 Da) and nanofiltrate (NF, 200 Da). The fractions were characterized by HPLC analysis, to quantify the main polyphenols present: Hydroxytyrosol, Tyrosol, Caffeic and Coumaric Acids, Verbascoside, Isoverbascoside, Secologanoside, and Comselogoside.MF and UF fractions exhibited antimicrobial activity against Escherichia coli, as well as against Pseudomonas aeruguinosa and Staphylococcus aureus pathogen strains. No activity was given by NF fraction. Thus, MF and UF might be considered as natural antibiotics, taking into account mainly their effect in inhibiting the growth of E. coli and S. aureus. Phytotoxic and genotoxic effects were analysed in Vicia faba L. plants germinated in MF, UF and NF fractions. The major phytotoxic effects were shown in seeds germinated in MF fraction. Genotoxicity analysis relied on mitotic activity (MI), aberration index (AI) and micronucleus frequency (MCN): MI was generally reduced, cytogenetic aberrations were found in all the treatments and MCN were mostly present in MF fraction. Results generally indicated the efficiency in polyphenols recovery and natural antibiotic activity of MF and UF fractions. Genotoxicity and phytotoxicity effects of filtrated OMWWs suggested the need of further treatments/ dilutions before their discharge in the environment. This work was supported by Ministero dell Istruzione dell Università e della Ricerca of Italy: Progetto Premiale 2012 Aqua 9

10 Cambiamenti nella struttura delle comunità microbiche di un ecosistema acquatico in relazione a differenti tipi di contaminazione Linking multiple stressors to microbial community structure for water quality assessment A. Barra Caracciolo 1, P. Grenni 1, V.E.V Ferrero 2, M. Di Lenola 1, N. Ademollo 1, L. Patrolecco 1, R. Loos 3, S. Tavazzi 3, M.L. Saccà 1 and T. Lettieri 3 1National Research Council, Water Research Institute Via Salaria km 29, Monterotondo (Rome) Italy, 2LGC, Queens Road Teddington Middlesex TW11 0LY, UK 3European Commission, Joint Research Centre, Institute for Environment and Sustainability Via E. Fermi, Ispra (VA) Italy, Freshwater quality assessment in Europe is established under the Water Frame Directive (WFD) based on measurements of chemical pollutants in sediments and water and biota (chemical status) and on the ecological indicators such as nutrients, temperature, species compositions etc. (ecological status). However in the current strategy a link between chemical and ecological status is missing. No biological indicators are foreseen to integrate the different anthropogenic pressures including chemical mixture, nutrients, temperature changes in order to provide a global scenario on the ecosystem and therefore on the water quality. In this context, MicroCokit FP7-PEOPLE-2012-IAPP project is focused on the identification of microbial community based indicators for monitoring and evaluating the complexity of multiple stressors (e.g. chemical pollutants, temperature, nutrients etc.) relevant to guide preventive and remediation actions by the water authorities. For this purpose the river Tiber has been chosen as a pilot case study and sampling sites were selected based on different anthropogenic pressures which they are exposed to. Water samples are being analyzed for both microbiological (FISH analysis and Metagenomic) and chemical analysis (organic and inorganic compounds, including emerging pollutants). Within the 4-years project, two campaigns are contemplated per year (Autumn and Spring). We report preliminary results of the chemical analyses (inorganic elements, DOC, PAHs, organochlorine, triazine, chloroacetamide pesticides, perfluorinated compounds, pharmaceuticals, etc.) and epifluorescence direct microscopy analyses (total microbial abundance and phylogenetic community characterization by FISH) regarding the first two campaigns. The preliminary results suggest that the microbial community structure reflects both natural environmental variations (river course and sesonality) and anthropogenic pressures. The same water samples are currently being processed for metagenomic analysis in order to obtain a broader description of the microbial community to be compared with the overall chemical results. 10

11 Valutazione del processo di biorisanamento di acque reflue di frantoio tramite indagini ecotossicologiche in Eisenia fetida e Gambusia affinis Campani T., Caliani I., Pozzuoli C., Pagano E., Beligni G., Fossi M.C., Casini Università degli studi di Siena Dipartimento di Scienze Fisiche della Terra e dell Ambiente Nei paesi mediterranei sono annualmente prodotti più di 30 mln di m 3 di sanse e acque di vegetazione con un elevato potenziale tossicologico e conseguenti problematiche di tipo ambientale ed economico legate al loro smaltimento. L obiettivo di questo studio era quello di migliorare la qualità delle acque reflue attraverso metodi innovativi di abbattimento della tossicità, controllando l efficacia del processo con test ecotossicologici su organismi bioindicatori. Tramite tecniche di bioremediation/bioaugmentation e compostaggio con altri materiali di scarto provenienti da attività agricole è stato possibile abbattere il contenuto di polifenoli, alzare il ph ed abbassare la salinità. I prodotti ottenuti dal trattamento sono stati sottoposti ad un innovativo controllo di processo per valutarne la sicurezza ambientale. Tramite l uso di biomarkers in organismi di acqua dolce e suolo (G. affinis e E. fetida) sono stati valutati i possibili effetti dell esposizione di queste due specie alle acque prima e dopo il trattamento di biorisanamento. Le risposte ottenute hanno mostrato una significativa riduzione degli effetti tossicologici nei reflui dopo il processo di biorisanamento come evidenziato dai test di genotossicità (comet assay, ENA essay), di stress ossidativo (perossidazione lipidica) e di neurotossicità (Acetilcolinesterasi). Questo studio finanziato tramite la Misura 124 del PSR , costituisce un primo passo per l applicazione di un approccio ecotossicologico finalizzato a supportare l applicazione di processi sostenibili nella filiera olearia in particolare il riutilizzo dei reflui come ammendanti per i suoli agricoli. 11

12 Trace metal background levels and pollution status assessment in line with the Water Framework EU Directive in waters from the Gulf of Trieste Alessandro Acquavita 1, Jari Falomo 1, Alessandro Felluga 1, Rossin Pietro 1, Denis Mazzilis 1, Elisa Piccoli 1, Anna Lutman 1, Giorgio Mattassi 1 Trace metals in the marine environment play a dual role, either as essential micronutrients or as toxic agents for living organisms through trophic transfer and bioaccumulation. In coastal areas the enrichment in metals is due to natural and anthropogenic sources. The Water Framework Directive (WFD/60/2000/EC) was introduced with the aim to protect, preserve and enhance the quality of aquatic ecosystems. The WFD establishes environmental quality standards (EQS) for priority substances in the dissolved phase with the aim to define two quality classes good/not good. The Gulf of Trieste and the adjacent Marano and Grado Lagoon (Northern Adriatic) are subjected to intense anthropogenic pressures with several point and non-point pollution sources such as wastewater treatment plant, marinas, touristic facilities and factories. These areas were evaluated for heavy metals contents and variability in sediments. It was highlighted that Hg contamination is widespread due to inputs of particulate matter enriched in microcrystalline cinnabar from the Idrija mercury mine (Slovenia) and, to a lesser extent, from the chlor-alkali plant discharge occurring in Torviscosa. Moreover, the intense maritime traffic caused the (TBT) pollution, which is restricted mainly to the harbour areas. On the other hand, there was a lack of data about heavy metals levels and distribution in the dissolved phase. The present work attempts to contribute the implementation of the EU WFD by determining trace metals background levels and chemical status for the first time in this marine area. In details, the work considers the following elements: As, Cr, Cd, Hg, Ni, Pb, TBT and its compounds. The results indicate that, for most of the metals studied, the Gulf of Trieste is classified as good or high (if a more refined assessment is considered). The main concerns is represented by TBT with values that often exceed the threshold level fixed by the WFD. 12

13 Caratteristiche e dinamiche di ripartizione di microinquinanti emergenti in impianti di depurazione reflui civili Maria Rosaria Boni 1, Giancarlo Cecchini 2, Alessia Delle Site 3, Biagio Eramo 2 1. Università degli studi di Roma La Sapienza - DICEA - via Eudossiana, Roma; 2. Acea Elabori SpA - via Vitorchiano Roma; 3. Acea Ato 2 SpA piazzale Ostiense Roma Il comportamento ed il destino dei microinquinanti organici emergenti nei convenzionali impianti di depurazione è un tema di grande attualità ed interesse a causa dell effetto che queste sostanze possono esercitare sugli ecosistemi acquatici se scaricate in un corpo idrico superficiale. Rientrano nella definizione di microinquinanti organici emergenti i farmaci umani ad uso veterinario, le droghe d abuso, i prodotti industriali per la cura della casa e per l igiene personale, gli ormoni steroidei e tiroidei, i fitoestrogeni. Alcuni di questi composti sono considerati interferenti endocrini, cioè sostanze che interferiscono con il normale funzionamento del sistema endocrino e che possono alterare la normale crescita, lo sviluppo, la riproduzione e il comportamento degli organismi. Le fonti di rilascio dei microinquinanti organici emergenti sono molteplici, sia antropiche che naturali, sia puntuali che diffuse. Ad oggi non è noto il comportamento di tutte le sostanze che vengono classificate come microinquinanti organici emergenti all interno di un impianto di trattamento delle acque reflue urbane. Lo stato attuale delle conoscenze si basa su sperimentazioni a breve termine e non su un metodico monitoraggio sperimentale esteso nel tempo, in considerazione dell innovazione tecnologica strumentale ed esperienza necessaria per rilevare questi composti in traccia, dei costi analitici per un monitoraggio sistematico ed anche per la complessità di produrre bilanci di massa significativi, tenendo conto di tutti i flussi presenti in un impianto di depurazione. Nel presente lavoro sono stati analizzati i meccanismi di degradazione, adsorbimento, volatilizzazione e ossidazione, oltre che le proprietà chimico fisiche dei contaminanti, ed approfonditi per alcuni microinquinanti emergenti (interferenti endocrini e droghe d abuso), i livelli di concentrazione presenti in ingresso ad un impianto di depurazione reflui civili ed il destino che tali contaminanti subiscono all interno dell impianto, valutandone, attraverso bilanci di massa, la distribuzione nelle diverse fasi di trattamento. 13

14 MONITORAGGIO DEI MICROINQUINANTI ORGANICI IN LAGUNA DI VENEZIA CON CAMPIONATORE PRECONCENTRATORE PER ACQUE AD ALTI VOLUMI Loretta Gallocchio a, Claudio Carrer a, Francesco Sorrentino b a Thetis spa c/o Laboratorio Analisi Ambientali Ufficio Tecnico per l Antinquinamento Provveditorato Interregionale Opere Pubbliche San Polo 737 Venezia, Italy b Provveditorato Interregionale Opere Pubbliche San Polo 19 Venezia, Italy In laguna di Venezia oltre ai monitoraggi imposti dai recenti sviluppi normativi europei il Provveditorato Interregionale OO.PP., al quale è stato affidato il compito del monitoraggio dello stato ambientale della laguna, del controllo e vigilanza degli scarichi conferenti all interno del perimetro della conterminazione lagunare svolge attività di monitoraggio e controllo sulla base degli obbiettivi di qualità delle acque della laguna di Venezia di cui al Decreto del Ministero dell'ambiente, di concerto con il Ministero dei lavori pubblici, del 23 aprile Per alcune sostanze, quali PCDD/F, PCB, IPA, PBDE e Organo-Tin, presenti nell elenco della direttiva quadro 2000/60/CE, della nuova direttiva 2013/39/CE, dal Decreto Ministeriale n.56 del 14/04/2009 e del D.M. del 23 aprile 1999, pur ricorrendo a tecniche analitiche sofisticate e sensibili quali HRGC/HRMS per la loro determinazione non si riescono a raggiungere i limiti di sensibilità richiesti. Vista la presenza, nelle acque, di queste sostanze a livelli di ultratracce sarebbe necessario prevedere il campionamento di grandi volumi di acqua, o di predisporre di un sistema di campionamento in situ che preveda la preconcentrazione di grandi volumi di acqua. Il preconcentratore per acque ad alti volumi (CAV) permette di poter raggiungere bassi limiti di rilevabilità incrementando di volte il volume di campione rispetto ai metodi normati tradizionali, senza però dover trasportare e successivamente estrarre grandissimi volumi di acqua in laboratorio. Il CAV è uno strumento ad immersione che permette il campionamento automatizzato e risulta composto da una pompa controllata da un microprocessore, un misuratore di flusso, un sistema di filtrazione, una colonna di estrazione e degli accumulatori che forniscono l'energia di campionamento, in questo modo è possibile posizionale lo strumento sia in laguna aperta, che nelle vicinanze di uno scarico per campionare un elevato volume d acqua a flusso costante in un determinato intervallo di tempo. 14

15 NUTRIENTS SEASONAL CYCLES IN THE VENICE LAGOON Francesca Scardia a, Silvia Esposito a, Claudio Carrer a,francesco Sorrentino b a Thetis spa c/o Laboratorio Analisi Ambientali Ufficio Tecnico per l Antinquinamento Provveditorato Interregionale Opere Pubbliche San Polo 737 Venezia, Italy b Provveditorato Interregionale Opere Pubbliche San Polo 19 Venezia, Italy In this study are presented and discussed the results of observations of seasonal cycles of nutrient levels in the Venice lagoon. The nutrients term has been applied to TDP, total dissolved phosphorous (P-PO4 and P organic ), and TDN, total dissolved nitrogen (N-NO3 -, N-NO2 -, N-NH4 +, N organic ). The Lagoon of Venice is a broad, shallow coastal basin, substantially modified through the actions of man. The lagoon is subjected to considerable pollutant loading through the drainage of land under cultivation, municipal sewage, and industrial effluents. In small amounts nutrients are beneficial to many ecosystems nevertheless in excessive amounts they cause a type of pollution called eutrophication. Eutrophication stimulates an explosive growth of algae that depletes the water of oxygen. The lagoon water may become hypoxic (oxygen poor) or anoxic (completely depleted of oxygen) from algal blooms. While hypoxia may cause animals to become physically stressed, anoxic conditions can kill them causing bad smell too. Sampling was performed in this study monitoring activity for the classification of chemical status of the Venice lagoon. Nutrients were analyzed by air-segmented flow analysis (SFA) with Uv lamp detection, total nitrogen and total phosphorous were determined through oxidative digestion using persulfate followed by quantitation of the nitrate and orthophosphate. In this study nutrients concentration have been estimated by monitoring monthly a number of stations located in the lagoon. By comparing this data collected during the last five years, a trend in nutrient concentration can be observed. 15

16 MONITORAGGIO DEI RITARDANTI DI FIAMMA NELLE ACQUE DI TRANSIZIONE (LAGUNA DI VENEZIA) Claudio Carrer a, Loretta Gallocchio a, Francesco Sorrentino b a Thetis spa c/o Laboratorio Analisi Ambientali Ufficio Tecnico per l Antinquinamento Provveditorato Interregionale Opere Pubbliche San Polo 737 Venezia, Italy b Provveditorato Interregionale Opere Pubbliche San Polo 19 Venezia, Italy La qualità delle risorse idriche e tutto ciò che vive al loro interno sono sempre più minacciate dalla presenza di molteplici forzanti dovute all interazione con l ambiente circostante, come la presenza e l accumulo di molti composti chimici spesso usati, soprattutto in passato, in modo esagerato e incontrollato. Recenti sviluppi normativi europei prevedono obblighi agli stati membri sempre più stringenti, chiedendo agli stessi il continuo monitoraggio dei composti classificati prioritari ed emergenti. Nel 2010 è stato adottato il Piano di Gestione del Distretto Idrografico delle Alpi in qui è compresa la sub-unità idrografica bacino scolante, laguna di Venezia e mare antistante. A completamento delle attività Istituzionali il Provveditorato OO.PP., già Magistrato alle Acque, avvia, attraverso il proprio concessionario, le attività per il Monitoraggio dei corpi idrici lagunari a supporto della loro classificazione e gestione (Direttiva 2000/60/CE e D.M. 56/2009 ) con lo scopo di coordinare e monitorare i corpi idrici della laguna di Venezia, attraverso un piano che ha previsto e prevede la determinazione, tra le sostanze prioritarie emergenti, dei ritardanti di fiamma (PBDE) I PBDE sono una classe di ritardanti di fiamma alogenati usati come additivi in diversi polimeri organici presenti, a partire dagli anni 70, in numerosi prodotti commerciali, quali componenti elettrici ed elettronici, materiali isolanti, tessuti ed equipaggiamenti per veicoli. A causa della loro natura lipofila tra i 209 possibili congeneri, otto (BDE-28, 47, 99, 100, 153, 154, 183 e 209) risultano di interesse primario per il ritrovamento nel comparto abiotico e nel biota. Sono inoltre identificati come sostanze prioritarie pericolose in materia di acque e compresi nell elenco presente nella direttiva quadro 2000/60/CE, mentre la nuova Direttiva 2013/39/CE prevede la determinazione degli stessi anche nel biota. 16

17 Deposizioni di microinquinanti organici ed inorganici in Laguna di Venezia Andrea Berton a, Claudio Carrer a, Francesco Sorrentino b a Thetis spa c/o Laboratorio Analisi Ambientali Ufficio Tecnico per l Antinquinamento Provveditorato Interregionale Opere Pubbliche San Polo 737 Venezia, Italy b Provveditorato Interregionale Opere Pubbliche San Polo 19 Venezia, Italy Le deposizioni atmosferiche assieme agli apporti del bacino scolante, dell area industriale e del centro storico di Venezia costituiscono le fonti di contaminazione più rilevanti in Laguna di Venezia. A partire dal 2003 è stata attivata una rete di monitoraggio che attualmente è costituita da 10 stazioni distribuite in modo da rappresentare le diverse tipologie presenti in laguna di Venezia: da aree fortemente industrializzate a quelle a basso livello di antropizzazione. Il programma prevede di stimare i flussi totali di ricaduta di dodici microinquinanti inorganici e settantasei composti organici tra PCDD/F, PCB, IPA e PBDE. La distribuzione dei flussi è eterogenea e presenta degli hot spot, legati ad emissioni locali. In tutti i casi l evoluzione temporale dei flussi di deposizione in laguna risulta negativo. Quindi, dalle stime effettuate, sembra ci sia una riduzione del carico atmosferico di contaminanti in laguna con conseguente miglioramento della qualità ambientale. 17

18 Real time water quality monitoring network in the lagoon of Venice (Italy) Christian Badetti a, Claudio Carrer a, Sebastiano Carrer a, Francesco Sorrentino b a Thetis spa c/o Laboratorio Analisi Ambientali Ufficio Tecnico per l Antinquinamento Provveditorato Interregionale Opere Pubbliche San Polo 737 Venezia, Italy b Provveditorato Interregionale Opere Pubbliche San Polo 19 Venezia, Italy The Sezione Antinquinamento del OO.PP (Anti-Pollution Department of The Venice Water Authority, SAMA) is taking a series of measures to counteract the degradation of the lagoon, including dredging of contaminated sediments, clean-up of contaminated sites inside the lagoon, pollution prevention from the industrial discharges, wetlands reconstruction. In order to control the status of the ecosystem and to verify both the short and long term effects of such initiatives, the Venice Water Authority has set up a real-time monitoring network of the water quality parameters of the lagoon (WQPs). The monitoring system is composed by 10 stations placed in different part of the lagoon, in order to cover the most significant areas of the lagoon: the area surrounding the city of Venice; the part of the lagoon directly influenced by the industrial area of Porto Marghera; the area of the southern lagoon close to the city of Chioggia, an important economical center for fishing activities. All the stations are equipped with multiparameter probes measuring the following water parameters: depth of the water column, temperature, ph, salinity, dissolved oxygen, redox potential, turbidity and chlorophyll a. 18

19 Arsenic, Cadmium, Lead and Mercury in biota from Venice lagoon: from sources to human exposure Massimo Berti a, Sebastiano Bertini a, Claudio Carrer a, Francesco Sorrentino b a Thetis spa c/o Laboratorio Analisi Ambientali Ufficio Tecnico per l Antinquinamento Provveditorato Interregionale Opere Pubbliche San Polo 737 Venezia, Italy b Provveditorato Interregionale Opere Pubbliche San Polo 19 Venezia, Italy The Venice lagoon has been originated by the counteracting effect of the force of the sea and the solid transport of the river. In the middle of the lagoon lies the city of Venice, an important tourist city. At the north-west edge there is the industrial area of Porto Marghera, with important petrolchemical factories. In this study As, Cd, Pb and Hg concentrations in sediments and biota from Venice lagoon (Italy) are presented and discussed. The Venice lagoon is a sensitive area exposed to anthropogenic pollutants sources. The watershed of the lagoon is heavily populated supporting approximately 1 million inhabitants and many chemical companies were located on the western shore of the lagoon in Porto Marghera. The municipality of Venice also contributes with urban waste water sewage and runoff. As, Cd, Pb, Hg are chemical elements of great concern because of high toxicity and potential accumulation in the food chain. Sampling was performed in the framework of the monitoring activity for the classification of chemical status of the Venice lagoon according to European Directive n. 60 of 2000 and n. 39 of As, Cd, Pb and Hg in sediments were analyzed using atomic absorption spectroscopy, while concentrations of As, Cd, Pb and Hg in different species of bivalve molluscs (Mytilus galloprovincialis, Tapes philippinarum) and fishes (Zosterisessor ophiocephalus, Sparus aurata, Dicentrarchus labrax, Mugil cephalus) were checked by means of inductively coupled plasma mass spectrometry. The Venice lagoon is well known for its shellfish harvesting activity and fish breeding whose extensive production can be an easy target for chemical contamination. The results of the monitoring activity performed in 2014 and 2015 were used to assess the human exposure to these harmful pollutants due to the consumption of fishery products. 19

20 REMOVAL OF PESTICIDES AND ESTROGENS FROM A WASTEWATER AND ABATEMENT OF ITS PHYTOTOXICITY USING PLANT-DERIVED ADSORBENTS AND LIGNINOLYTIC FUNGI Elisabetta Loffredo, Giancarlo Castellana and Eren Taskin Dipartimento di Scienze del Suolo, della Pianta e degli Alimenti, Università degli Studi di Bari Aldo Moro, Bari, Italy In this study, adsorption and biodegradation were exploited sequentially to decontaminate a wastewater and reduce its phytotoxicity. We used potato dextrose agar (PDA), spent coffee grounds, almond shells and a biochar as plant-derived adsorbents and the fungi Bjerkandera adusta and Irpex lacteus as biodegrading agents. A municipal landfill leachate (MuLL) was artificially contaminated with a mixture of the herbicide fenuron, the insecticide carbaryl and the estrogens 17β-estradiol (E2) and 4-tert-octylphenol (OP), each at a concentration of 1 mg L -1. In a first step, the adsorbent was packed in a dialysis membrane and immersed in MuLL where, after 3 and 7 d, residual contaminants were measured. Then, untreated MuLL and 7-d treated MuLL were tested for phytotoxicity. In a second step, the adsorbent collected from MuLL after 7 d was added with PDA (substrate), not inoculated (control) or inoculated with the fungus, and incubated for 7 and 15 d. After only 3 d, any adsorbent removed from MuLL the whole amounts of E2 and OP, more that 95% of carbaryl, and averagely 62% of fenuron (81% after 7 d). In substrates not inoculated, after 15 d, almost all the amounts of adsorbed contaminants were still present. On the contrary, in substrates inoculated, a large percentage of each contaminant, especially the two estrogens, was degraded after 7 and, especially, 15 d, with a similar efficiency by the two fungi. Further, MuLL treatments with the adsorbents, except PDA, produced a significant abatement of MuLL phytotoxicity on flax and even stimulating effects on rapeseed, with marked increases of seedling elongation and fresh biomass. This work might provide a contribution to the development of inexpensive methods to detoxify a wastewater before its worthwhile recycling in agriculture. 20