Effect of organic matter release from natural cork used on bisphenol a removal from aqueous solution

The paper presents an experimental study aimed at investigating the mechanism responsible for Bisphenol A adsorption on natural cork, and the role played on process kinetics by the organic matter released from the cork. Obtained data show that natural cork has a good affinity toward Bisphenol A, with removal efficiency being as high as 75% in less than 24 h. The adsorption process is characterized by a fast-initial rate which tends to reduce progressively, and follows a pseudo second order model equation. Statistical physics analysis allows for obtaining a molecular description of the adsorption, which is shown to take place through a single anchorage point, perpendicularly to the adsorbent surface. Nuclear magnetic resonance spectroscopy and fluorescence analysis reveal that the colloidal organic matter released from the cork interacts with Bisphenol A; it also plays a relevant role in the slowing down of the adsorption rate, as it competes with cork adsorption sites for Bisphenol A. Organic matter is found to be highly heterogenous, presenting at the same time carbohydrates, aromatic and aliphatic domains. Such moieties interact stably with the contaminant in the solution probably due the establishment of dispersive forces (e.g. π-stacking) which sequestrate Bisphenol A into the inner hydrophobic core of the organic matter three-dimensional structure

Soil washing optimization, recycling of the solution, and ecotoxicity assessment for the remediation of Pb-contaminated sites using EDDS

This paper presents the results of an experimental study aimed at investigating the applicability of ethylenediamine-N,N′-disuccinic acid (EDDS) as a washing solution for the remediation of Pb-contaminated soil. All aspects of the treatment are analyzed and optimized, including the reuse and the final disposal of the EDDS spent solution. Different molar concentrations of the washing solutions and the efficiencies of varying solid/liquid ratio are tested at different pH values. More than 90% of the mobile Pb fraction is removed in about 24 h at pH 6. Accordingly, soil toxicity strongly decreases as a consequence of the treatment. The regenerated solution exhibits a reduced, but not negligible, extractive capacity. The total extraction of Pb is approximately 50% of the initial value after one regeneration cycle, and almost 20% after a second regeneration cycle. Respirometric tests, conducted using an activated sludge sampled in a municipal wastewater treatment plant, indicate that the spent solutions are not biodegradable, but they do not exert any toxic effect on the biomass. On the contrary, tests on regenerated solutions displayed the same biodegradability as the fresh one

Microaerobic Digestion of Low-Biodegradable Sewage Sludge: Effect of Air Dosing in Batch Reactors

The adoption of prolonged solid retention times during the biological treatment of urban wastewaters is a well-known strategy to reduce sewage sludge production. However, it also results in the production of a biological sludge with low percentages of biodegradable organic matter, also characterized by high humification degrees, which may hamper the anaerobic digestion treatment aimed at sludge stabilization. To accelerate the hydrolytic stage, the application of microaerobic conditions during the anaerobic digestion of low-biodegradable sewage sludge was investigated in this study. In particular, six bio-methanation tests of a real sewage sludge were carried out, introducing air in the bioreactors with doses ranging between 0 and 16.83 L air/kg VSin d, in order to evaluate the air dosage that optimizes the biomethane production and organic matter degradation. Notably, the lower air loading rates investigated in this study, such as 0.68 and 1.37 L air/kg VSin d, led to an increase in methane production of up to 19%, due to a higher degradation of total lipids and proteins. In addition, these microaerobic conditions also resulted in a decrease in the sludge humification degree and in lower volatile fatty acid accumulation

Immobilisation et transport colloidal des métaux lourds en concentrations traces dans les sols irrigués par des effluents urbains traités

Reuse of treated wastewater for agricultural purposes is worldwide accepted and practiced to face water scarcity and save high quality resources. Although such practice has undoubtable advantages and is certainly more sustainable respect to the use of fresh water, it is not exempt from severe concerns related to the potential impact on the receiving soil and on the crops of potentially harmful pollutants contained in the reused water at trace levels. Among these pollutants, trace heavy metals (HMs) play a primary role due to their spread presence in the used water and to their persistence once released in the environment. The fate of HMs in the soils can be hardly predicted as mechanisms of mobility through soils are extremely diverse and related to highly complex simultaneous phenomena and chemical equilibria. HMs, in fact, as many other contaminants, are not only partitioned between the solid immobile and the water mobile phases. Indeed, colloids and nanoparticles act as a third mobile phase, with their own rheological properties and velocity. This latter aspect has been one of the main focus of the thesis. In details the thesis describes the results of several experiments conducted irrigating the OECD standard soil with real and/or synthetic wastewater, containing HMs in trace. For each test a specific soil (e.g. varying the organic matter content) and wastewater composition (e.g. varying the metals concentration, the salinity, the organic matter content, or testing real treated wastewaters) has been chosen in order to evaluate the effects of different conditions on the overall HMs fate. The increase of soil organic matter from 2,5 to 10% linearly enhanced the mobility of Cd, Cu and Ni up to a maximum mobility increase of 35.6, 43.7 and 49.19 % for Cd, Cu and Ni, respectively. In most experiments metals accumulated in the top soil layer (0.5 - 1 cm). Nevertheless peaks of contamination were detected at different depths in the soil deeper layers and at different leaching time in the leachates depending on the metal and on the soil and wastewater characteristics. Peaks of metals in the leachate appeared simultaneously with release of organic matter and/or release of silicates, demonstrating outstanding involvement of colloids in metals transport. Sodium concentration (20mM) decidedly reduced colloidal mobilization whereas more than 95 % of the influent metal was detected in the top layer despite the soil organic matter content. Salinity displayed different effects. The irrigation with real treated wastewater with quite high content of Ca and Mg (111 and 134 mg/L, respectively) resulted in higher average release of silicon from the soil inorganic matrix (8.2 mg/L) compared to the low salinity artificial wastewater (1.9 mg/L). Consequently higher mobilization of Cd, Cu, Ni and Zn was observed when the soil was irrigated with real treated wastewater. An advanced spectroscopical characterization of the leachates was performed to identify such colloidal aggregates. The observation of 3D excitation-emission matrix demonstrated in all the leachates samples the presence of fulvic (230-450 nm ex-em fluorescence area) and humic (330-445 nm ex-em) substances. In this context, a novel analytical method was developed to quantify phenolic substances in soil matrices allowing the monitoring of humic matter migration in soil profiles. The novel method was more accurate and more precise respect to the traditional one, allowing to obtain higher recovery of total phenols in peat soil (15.5 % increase) with a decrease of the coefficient of variation (30.1% decrease). Organic water soluble colloids were extracted from the peat used to prepare the OECD standard soil and characterized. Results of size exclusion chromatography highlighted the supramolecular structure of the extracted organic matter. Such structure was further confirmed through fluorescence and 1H-NMR spectroscopyLa réutilisation des eaux usées traitées pour l’irrigation est globalement acceptée et pratiquée pour faire face à la pénurie d'eau et économiser les ressources de haute qualité. Bien que cette pratique présente des avantages indéniables et contribue à un usage plus durable de l'eau douce, elle n’est pas exempt de problèmes liés à l'impact potentiel sur la qualité des sols récepteurs et sur les cultures de micropolluants contenus dans l'eau réutilisée. Parmi ces polluants, les métaux lourds (ML) en concentrations traces jouent un rôle primordial en raison de leur présence systématique dans l'eau utilisée et de leur persistance une fois libéré dans l'environnement. Le devenir des ML dans les sols peut difficilement être prédit parce que les mécanismes de mobilité à travers les sols sont extrêmement variés et liés à des phénomènes simultanés et très complexes impliquant différents équilibres chimiques. Les ML, comme beaucoup d'autres contaminants, ne sont pas seulement partagé entre la phase immobile (le sol) et les phases mobiles présentes dans l'eau. En effet, les colloïdes et les nanoparticules agissent comme une troisième phase mobile, avec leurs propres propriétés rhéologiques et des vitesses de migrations qui leur sont propres. Ce dernier aspect a été l'un des principaux objectifs d’étude de la thèse. Plusieurs essais expérimentaux ont été menés en irriguant un sol standard selon l'Organisation de coopération et de développement économiques (OCDE) avec une eau usés traités réel et / ou synthétiques, contenant des ML en concentrations traces. Pour chaque test, un sol spécifique (avec différentes teneurs en matière organique) et des eaux usées traitées de composition différente (avec différentes concentrations en métaux traces, de salinité, de la teneur en matière organique pour les eaux usées synthétiques, ou des eaux usées traitées réelles) ont été choisi afin d'évaluer les effets des conditions différentes sur le devenir global des ML. L'augmentation de la matière organique du sol de 2,5 à 10% a linéairement amélioré la mobilité des Cd, Cu et Ni avec une augmentation de la mobilité maximum de 35,6, 43,7 et 49,19% pour le Cd, Cu et Ni, respectivement. Pour la plupart des expériences, les ML ont été capturés dans la couche superficielle du sol (0,5 à 1 cm). Néanmoins, des pics de contamination ont été détectés à des profondeurs différentes dans les couches plus profondes du sol. L’étude de la composition des lixiviats montre des variations de concentrations fonction du métal étudié et des caractéristiques du sol et des eaux usées. Des pics de métaux dans le lixiviat sont apparus en même temps que la libération de la matière et / ou la libération de silicates organiques, ce qui démontre l'implication significative des colloïdes dans le transport des métaux. La concentration en sodium (20 mM) a été démontrée un impact fort sur la réduction de la mobilisation colloïdale et que plus de 95% du métal apporté a été détecté dans la couche superficielle du sol en dépit de sa teneur en matière organique. La salinité affiche donc des effets significatifs. L'irrigation avec des eaux usées traitées présentant une très haute teneur en Ca et Mg (111 et 134 mg / L, respectivement) a abouti à la libération moyenne plus élevée de silicium à partir de la matrice inorganique du sol (8,2 mg / L) par rapport à la faible salinité des eaux usées artificielle (1,9 mg / L). Par conséquent, la mobilisation ultérieure de Cd, Cu, Ni et Zn a été observée lorsque le sol a été irrigué avec des eaux usées traitées réelles. Une caractérisation spectroscopique avancée des lixiviats a été réalisée pour identifier les agrégats colloïdaux libérés par le sol dans le but d’en déterminer leur nature, leurs propriétés chimiques et leur état d'agrégatio