25 research outputs found

    Environmentally Friendly Tools for the Removal of Emerging Pollutants from Natural Matrices

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    In this work of thesis are contained four different projects on sustainable remediation techniques for the decontamination of natural matrices have been developed and valued. The original intent shared by these projects is to develop innovative solutions for emerging pollution cases. Porous synthetic silica materials, commonly used in catalysis, have been studied, valued and adapted for use in pollutant decontamination. In the first project, synthetic high silica faujasite used for antibiotics sorption from waste waters was tested for regenerability and its reuse after solvent desorption or thermal regeneration. The tested high silica Y has been regenerated with thermal treatments; the most effective (and less costing) temperature and treatment time was determined and the regenerated zeolite was successfully reused. Another successful option, solvent desorption, was also validated. In the second project, mineral oil contamination of recycled paper and paperboard – with particular attention to food-contact paperboard – was accounted. A hydrocarbon-specific sorbent material was developed, suitable to be used during industrial processes of paper recovery and recycling. The material, capable to retain up to 184% of its dry weight, was a modified mesoporous silica. Its capacity to adsorb and retain hydrocarbons from highly wet pulp were successfully tested in a pilot-scale plant, and the utilization of the said material was patented. In the third project, a mild sediment washing technique in order to remove Cu and Zn from a contaminated sediment of a land reclamation consortium canal. In the study presented the treatment efficacy to remove heavy metals is assessed, as well as an aggregate structural stability evaluation post-treatment. In conclusion, a multidisciplinary project on humic substances is introduced. Humic substances have been chemically grafted onto silica gel, in order to exploit their sorbent capacity to retain pollutants, or facilitate their degradation in water solutions

    Effect of the Growing Season, Trichoderma, and Clinoptilolite Application on Potentially Toxic Elements Uptake by Cucumis melo L

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    The extent to which different agricultural strategies may affect the uptake of potentially toxic elements (PTEs) by cropped plants is not entirely understood at a field scale. This study addresses the effect of seasonality, Trichoderma inoculation alone, or combined with different applications of commercial-grade clinoptilolite (i.e., foliar action, fertigation, and pellet) on the PTE content of early- and late-ripening cultivars of Cucumis melo L. Two similar field experiments were performed in spring and summer. For each cultivar/treatment combination, the input of PTEs [namely, chromium (Cr), copper (Cu), and lead (Pb)] into the soil-crop system through irrigation water, fertilizers, pesticides, and treatment products (i.e., Trichoderma and clinoptilolite products), as well as the PTE content of melon stem, leaves, and fruit, were measured through inductively coupled plasma-optic emission spectrometry (ICP-OES). Neither Trichoderma alone nor with clinoptilolite had a visible effect on PTE uptake by plants, whereas early season cultivation was strongly associated with reduced uptake of Cu and Pb. The high correlation of Cu and Pb content with stem and leaf calcium (Ca) content (used as a proxy for different transpiration rates under different growing seasons) indicated a possible uptake of these metals through Ca nonselective cation channels as a defense against drought stress. Reduced Cu and Pb concentrations were found in early-ripening fruit cultivated in spring. Concerning Cu and Pb risk management, in case of significant contamination in Mediterranean calcareous soils, early-ripening Cucumis melo L. cultivars are suggested instead of lateripening ones

    Toluene Adsorption by Mesoporous Silicas with Different Textural Properties: A Model Study for VOCs Retention and Water Remediation

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    In this work, dierent mesoporous silicas were studied as potential sorbents for toluene, selected as a model molecule of aromatic organic fuel-based pollutants. Three siliceous materials with dierent textural and surface properties (i.e., fumed silica and mesoporous Santa Barbara Amorphous (SBA)-15 and Mobil Composition of matter (MCM)-41 materials) were considered and the eect of their physico-chemical properties on the toluene adsorption process was studied. In particular, FT-IR spectroscopy was used to qualitatively study the interactions between the toluene molecule and the surface of silicas, while volumetric adsorption analysis allowed the quantitative determination of the toluene adsorption capacity. The combined use of these techniques revealed that textural properties of the sorbents, primarily porosity, are the driving forces that control the adsorption process. Considering that, under real conditions of usage, the sorbents are soaked in water, their hydrothermal stability was also investigated and toluene adsorption by both the gas and aqueous phase on hydrothermally pre-treated samples was studied. The presence of ordered porosity, together with the dierent pore size distribution and the amount of silanol groups, strongly aected the adsorption process. In toluene adsorption from water, SBA-15 performed better than MCM-41

    Monitoraggio di residui di pesticidi in ortofrutta in pre-raccolta (Serie storica 2007-2016) Focus sull’Emilia-Romagna

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    La valutazione del rischio ambientale e alimentare hanno rappresentato un ruolo centrale nel raggiungimento degli obiettivi stabiliti dalla strategia della Commissione Europea nel programma Europa 2020 e costituiscono uno dei capisaldi dell’attuale strategia Horizon Europe. La collaborazione fra enti pubblici, società scientifiche e privati rappresenta il core delle nuove strategie per raggiungere l’obiettivo della sicurezza ambientale e alimentare con un focus sulla salute, come anche indicato dalla FAO e dall’OMS. Accanto ai numerosi e stringenti controlli sulla qualità dei prodotti ortofrutticoli alla vendita, oltre 10000 campioni anno in Italia, esistono i controlli dei produttori e delle catene della grande distribuzione organizzata (GDO) che non sono mai pubblici. Questo report, edito dal Dipartimento di Scienze Tecnologie Agro-alimentari dell’Università di Bologna, presenta proprio questi dati, in gergo chiamati “grigi”. Questa trattazione rappresenta un primo passo, un unicum, grazie alla collaborazione tra una società scientifica, il GRIFA, e una società privata, Conserve Italia, che mette a disposizione milioni di dati residuali di prodotti fitosanitari in derrate alimentari in pre-raccolta per fare una valutazione statistica dell’andamento nazionale del loro utilizzo in un arco temporale molto ampio, che permetta di comprendere come l’agricoltura si sia adattata ai cambiamenti normativi, di costume e climatici. Un lavoro complesso che gli autori hanno affrontato con tenacia e dedizione, trovando la chiave scientifica per una corretta e oggettiva interpretazione

    POTENTIALLY TOXIC ELEMENTS ALONG SOIL PROFILES IN AN URBAN PARK, AN AGRICULTURAL FARM, AND THE SAN VITALE PINEWOOD (RAVENNA, ITALY) ELEMENTS POTENTIELLEMENT TOXIQUES LE LONG DES PROFILS DU SOL DANS UN PARC URBAIN, UNE EXPLOITATION AGRICOLE ET DANS LA PINE

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    Abstract Potentially toxic elements (PTEs) abundances in top soil and along the soil profiles from areas affected by different anthropogenic inputs were investigated.. The study area is located within the Ravenna Municipality, a complex territorial system highly affected by industrial (a large petrolchemical complex) agricultural activities. Three zones with distinct environmental features were identified: the San Vitale Pinewood affected by atmospheric deposition pollutans from the industrial complex (PW1, PW4, PW6 and PW8 soil profiles); a public garden within the Ravenna city center, mainly affected by traffic pollution (GP1 soil profile); the "Luigi Perdisa" farm located immediately northwards Ravenna was selected due to the use of fertilizers as well as atmospheric deposition (PER2 soil profile). The total concentration of PTEs (Ba, Cr, Cu, Cr, Ni, Pb, Zn) was determined by X ray fluorescence spectrometry (XRF), and the pseudo-total concentration with aqua regia digestion (AR) and ICP-OES quantification in order to evaluate the extractability of the elements. Results showed a significant increase of some PTEs (Cu, Pb, Zn) in the top soil compared to the pedological substrate. In the Ravenna urban park (GP1 station), Pb and Zn concentrations exceeded the threshold values established by current Italian laws for soils from "public, residential and private areas" (D. Lgs 152/2006). The correlation between top soil and the subsoil highlighted that some PTEs, such as Cu, Pb and Zn, are anthropogenic and they are mainly associated to the deposition of airborne pollutants, whereas other elements (Cr and Ni) are lithologenic. Key-words: heavy metals; enrichment factor; soil profiles; Pinewood San Vitale; ICP-OES;XRF Résumé Le but de cette étude est d'évaluer le taux de concentration d'éléments potentiellement toxiques (EPT) dans les horizons supérieurs et le long du profil de sols intéressés par les différents impacts anthropiques. Les études ont été conduites dans la zone qui englobe la commune de Ravenne, caractérisée par un système territorial complexe en raison de la présence d'un pôle pétrochimique mais aussi d'une agriculture très productive. Trois zones avec des impacts différents pour l'environnement ont été identifiées : la Pinède de San Vitale touchée par des dépôts atmosphériques dérivant de l'activité de l'industrie pétrolochimique (profils pédologiques PW1, PW4, PW6 et PW8) ; un jardin public qui se trouve dans le centre historique de la ville de Ravenne et qui subit une pollution due à la circulation automobile (profil pédagogique GP1). Pour finir, l'entreprise agricole "Luigi Perdisa" située immédiatement au nord-est de Ravenne a été choisie aussi bien à cause de la contamination possible par des produits chimiques utilisés en agriculture que pour les différents types de dépôts atmosphériques (profil pédologique PER2). Les études ont permis de déterminer les concentrations totales en spectrométrie de fluorescence aux rayons X (XRF) mais aussi pseudo-totales avec solubilisation dans l'eau régale (AR) de certains métaux lourds (Ba, Cr, Cu, Cr, Ni, Pb, Zn), à la suite de quoi a eu lieu la lecture en ICP-OES dans le but d'évaluer dans quelle mesure ces éléments peuvent être extraits. Les déterminations effectuées démontrent un enrichissement significatif de certains EPT (Cu, Pb, Zn) dans les horizons de surface par rapport au substrat pédologique. Riassunto Scopo di questo studio è la valutazione del grado di anomalia di elementi potenzialmente tossici (EPT) negli orizzonti superficiali e subsuperficiali di suoli soggetti a differenti iuput antropogenici. L'area di studio ha interessato il comune di Ravenna, caratterizzata da un sistema territoriale complesso per la presenza di un polo petrolchimico, ma anche soggetta ad un'attività agricola intensa ed altamente produttiva. Sono state identificate tre zone potenzialmente impattate da differenti attività antropiche: la Pineta di San Vitale interessata da deposizioni EQA -Environmental quality/Qualité de l'Environnement/Qualità ambientale, 2 (2009) 1-14 DOI: 10.6092/issn.2281-4485/3822 3 atmosferiche derivanti dall'attività dell'industria petrolchimica (profili pedologici PW1, PW4, PW6 e PW8); un giardino pubblico presente nel centro storico della città di Ravenna, interessato da inquinamento da traffico veicolare (profilo pedologico GP1); l'azienda agricola "Luigi Perdisa" collocata immediatamente a nord-est di Ravenna scelta sia per la possibile contaminazione da prodotti chimici usati in agricoltura sia per i diversi tipi di deposizioni atmosferiche (profilo pedologico PER2). Di alcuni metalli pesanti (Ba, Cr, Cu, Cr, Ni, Pb, Zn) sono state determinate sia le concentrazioni totali in spettrometria di fluorescenza a raggi X (XRF), sia quelle pseudo totali con solubilizzazione in aqua regia (AR) e successiva lettura in ICP-OES con lo scopo di valutare il livello di estraibilità di tali elementi. Le determinazioni effettuate mostrano un significativo arricchimento di alcuni EPT (Cu, Pb, Zn) negli orizzonti di suolo superficiale rispetto al substrato pedologico; nel parco urbano di Ravenna (GP1), le concentrazioni di Pb e Zn sono superiori ai limiti previsti dalla legislazione italiana (D. Lgs 152/2006) per le aree residenziali e di verde pubblico. La correlazione tra i valori di concentrazione di alcuni EPT, quali Cu, Pb e Zn, riscontrati negli orizzonti superficiali e di profondità evidenzia chiaramente la loro origine antropica per lo più dovuta a deposizioni di contaminanti presenti in atmosfera, mentre per altri elementi (Cr e Ni) la loro provenienza risulta litologenica. Parole chiave: EPT; fattore di arricchimento; profili del suolo; Pineta di San Vitale; ICP-OES; XRF

    Assessment of metal accumulation capacity of Dittrichia viscosa (L.) Greuter in two different Italian mine areas for contaminated soils remediation

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    The study aimed at assessing the capacity of Dittrichia viscosa (L.) Greuter to absorb and accumulate in its tissues some potentially harmful elements (PHEs), as Cd, Cu, Fe, Ni, Pb and Zn, in order to verify its possible use as phytoremediation in polluted mine soils. Plants from two different Italian mine areas, Montevecchio and Libiola, were considered and compared with plants from unpolluted areas. In each site (n = 21), both rhizospheric soil materials and D. viscosa plants were sampled, suitably prepared and analyzed. Soil samples were examined for both total composition (XRF) and bioavailable fractions (DTPA-extraction). Dittrichia viscosa roots, stems and leaves were analyzed separately to quantify the metal presence in the different plant parts. The root/soil ratio values calculated on the basis of the total soil concentrations, displayed a generally scarce capacity of D. viscosa to absorb soils PHEs, especially those more concentrated in the substrata. Concerning the root/soil ratio calculated on the basis of DTPA-extractable soil metals, values displayed instead a greater capacity of D. viscosa to absorb metals in the roots thus behaving as a potential phytostabilization plant in both mine areas. Regarding the leaf/root ratio, this species also displayed a greater capacity, in sub alkaline mine areas, to shift PHEs from roots to aboveground tissues, along with Ca transfer, revealing interesting characteristics for phytoextraction. In sub acid mine areas, this tendency was instead weaker and PHEs tended to be accumulated in all plant parts. Dittrichia viscosa seems to be appropriate for mine soil stabilization in both sub acid and sub alkaline environments and also for phytoextraction in the latter

    PESTICIDI SU COLTURE IN CAMPO IN ROMAGNA DAL 2007 AL 2016

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    Il settore dell\u2019ortofrutta in Romagna \ue8 fondamentale per le economie dirette (produzioni alimentari) e indirette (settore della trasformazione, imballaggio, conservazione e distribuzione) sia locali che nazionali che gravitano attorno ad essa. L\u2019inevitabile sfruttamento del suolo e l\u2019utilizzo di pesticidi, strumenti necessari all\u2019intensa attivit\ue0 agricola della Romagna, \ue8 di particolare interesse per le Societ\ue0 scientifiche come il Gruppo di Ricerca Italiano Fitofarmaci e Ambiente \u2013 GRIFA \u2013 che si occupano del monitoraggio delle condizioni di salute dell\u2019ambiente su cui impattano le attivit\ue0 agricole. Questo studio riporta i risultati dell\u2019elaborazione di dati residuali di pesticidi su campioni di ortofrutta di largo consumo (pomodoro, pianta di borlotto, pianta di pisello, pesca, pera, pianta di fagiolino, brattea di mais, susina e mela) in fase di pre-raccolta per il decennio 2007-2016 provenienti dalla Romagna (ca. 3200 campioni, quasi un milione di dati analitici su pesticidi) e, per confronto, dall\u2019Italia (ca. 5600 campioni, pi\uf9 di 1 milione e mezzo di dati analitici). I dati sono stati forniti dal Laboratorio Centrale di Analisi Chimiche, dotato delle certificazioni per l\u2019analisi dei pesticidi in autocontrollo, della Societ\ue0 Cooperativa Agricola Conserve Italia, cooperativa di riferimento per molte aziende ortofrutticole romagnole. Dal confronto dei campioni di ortofrutta in pre-raccolta provenienti dalla Romagna rispetto a quelli provenienti dall\u2019intero territorio nazionale si \ue8 osservato per la Romagna un quantitativo medio pi\uf9 elevato di residui di insetticidi e fungicidi per almeno otto anni di osservazione (2009-2016). Per lo stesso periodo, le quantit\ue0 di insetticidi e fungicidi che mediamente residuano nelle colture correlano con le vendite sia a livello locale che nazionale (fonte ISTAT). Al contrario, non sono state invece osservate correlazioni tra i residui di insetticidi e fungicidi nelle colture in pre-raccolta con le medie annue delle temperature massime e con le precipitazioni annue cumulative n\ue9 a livello locale n\ue9 nazionale per i dieci anni di osservazione. Il numero di pesticidi (principi attivi) osservati nei campioni romagnoli aumenta dal 2007 al 2016 ed \ue8 pi\uf9 elevato rispetto a quanto si osserva nei campioni nazionali. I principi attivi osservati con maggior frequenza nei campioni di ortofrutta in Romagna sono caratterizzati da tempi di carenza anche brevi, mettendo in evidenza la tendenza ad effettuare trattamenti a ridosso della vendita. Solo due dei pesticidi rilevati pi\uf9 frequentemente nelle colture in pre-raccolta coincidono con quelli ritrovati nelle acque superficiali e profonde (report ISPRA). Dal confronto del numero di residui di pesticidi nelle colture in pre-raccolta, sia locali che nazionali, con il numero di residui negli alimenti (monitoraggi del Ministero della Salute) negli anni 2007-2016 emerge che il maggiore numero di pesticidi nelle colture in pre-raccolta rispetto a quanto si osserva negli alimenti \ue8 coerente con lo scarto temporale tra i due monitoraggi. I dati analitici prodotti sulle colture in pre-raccolta possono essere uno strumento efficace per il monitoraggio della qualit\ue0 dei prodotti alimentari, fornire dati certificati per la valutazione del rischio all\u2019esposizione ambientale e dare informazioni dell\u2019utilizzo in campo dei pesticidi su singola coltura. Il maggiore ritrovamento di pesticidi sia per quantit\ue0 che per numero di principi attivi nell\u2019ortofrutta proveniente dalla Romagna rispetto ai campioni provenienti dal territorio italiano, se non contrastato, espone il settore produttivo romagnolo a perdere competitivit\ue0 in un mercato in espansione quale \ue8 quello delle produzioni di frutta e verdura a \u201cresiduo zero\u201d. Diverse importanti aziende agricole italiane stanno infatti gi\ue0 investendo in questo settore di ricerca per poter contrastare le patologie vegetali tramite la messa a punto di protocolli di difesa che utilizzino un minor quantitativo di pesticidi e principi attivi con bassi tempi di carenza

    Efficient dissipation of acetamiprid, metalaxyl, S-metolachlor and terbuthylazine in a full-scale free water surface constructed wetland in Bologna province, Italy: A kinetic modeling study

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    The study investigated the dissipation ability of a vegetated free water surface (FWS) constructed wetland (CW) in treating pesticides-contaminated agricultural runoff/drainage water in a rural area belonging to Bologna province (Italy). The experiment simulated a 0.1% pesticide agricultural water runoff/drainage event from a 12.5-ha farm by dissolving acetamiprid, metalaxyl, S-metolachlor, and terbuthylazine in 1000 L of water and pumping it into the CW. Water and sediment samples from the CW were collected for 4 months at different time intervals to determine pesticide concentrations by multiresidue extraction and chromatography-mass spectrometry analyses. In parallel, no active compounds were detected in the CW sediments during the experimental period. Pesticides dissipation in the wetland water compartment was modeled according to best data practices by fitting the data to Single First Order (SFO), First Order Multi-Compartment (FOMC) and Double First Order in Parallel (DFOP) kinetic models. SFO (except for metalaxyl), FOMC and DFOP kinetic models adequately predicted the dissipation for the four investigated molecules, with the DFOP kinetic model that better fitted the observed data. The modeled distribution of each pesticide between biomass and water in the CW highly correlated with environmental indexes as Kow and bioconcentration factor. Computed DT50 by DFOP model were 2.169, 8.019, 1.551 and 2.047 days for acetamiprid, metalaxyl, S-metolachlor, and terbuthylazine, respectively. Although the exact degradation mechanisms of each pesticide require further study, the FWS CW was found to be effective in treating pesticides-contaminated agricultural runoff/drainage water within an acceptable time. Therefore, this technology proved to be a valuable tool for mitigating pesticides runoff occurring after intense rain events
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