Matteo Spagnuolo

Fractionation of sugar beet pulp into pectin, cellulose, and arabinose by arabinases combined with ultrafiltration

Incubation of beet pulp with two arabinases (alpha-L-arabinofuranosidase and endo-arabinase), used singularly or in combination at different units of activity per gram of beet pulp, caused the hydrolysis of arabinan, which produced a hydrolyzate consisting mainly of arabinose. Pectin and a residue enriched with cellulose were subsequently separated from the incubation mixture. The best enzymatic hydrolysis results were obtained when 100 U/g of beet pulp of each enzyme worked synergistically with yields of 100% arabinose and 91.7% pectin. These yields were higher than those obtained with traditional chemical hydrolysis. The pectin fraction showed a low content of neutral sugar content and the cellulose residue contained only a small amount of pentoses. Semicontinuous hydrolysis with enzyme recycling in an ultrafiltration unit was also carried out to separate arabinose, pectin, and cellulose from beet pulp in 7 cycles of hydrolysis followed by ultrafiltration. The yields of separation were similar to those obtained in batch experiments, with an enzyme consumption reduced by 3.5 times and some significant advantages over batch processes.

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg(-1). Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as mu-XRF, mu-XRD and mu-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 microm. The main Hg-species found in the soil samples were metacinnabar (beta-HgS), cinnabar (alpha-HgS), corderoite (Hg(3)S(2)Cl(2)), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 microm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution.

Bioaccessibility, bioavailability and ecotoxicity of pentachlorophenol in compost amended soils

The influence of compost on the bioaccessibility, bioavailability and ecotoxicity of pentachlorophenol (PCP) as a function of time was studied by means of different chemical and ecotoxicological methods. Experiments were conducted in both sterile and non-sterile microcosms and samplings carried out at 20, 60 and 120d from initial contamination. PCP bioaccessibility, assessed by means of Porapak resin extraction, was around 75% of the applied dose with no aging or compost effects. Two different methods were applied to assess the bioavailability of PCP, respectively, to bacteria and earthworms and linked to ecotoxicological assays (biosensor and earthworm coelomocytes assays). Water extraction was applied to assess the bioavailability to bacteria: results showed that this fraction was always below 50%, with significant decreases as a result of aging processes and compost addition. In non-sterile microcosms, compost amendment increased the amount of PCP biodegraded, while the ecotoxicological assay with the biosensor Pseudomonas fluorescens pUCD607 indicated a higher toxicity in the most degraded samples, thus suggesting the formation of more toxic metabolites. Earthworm body accumulation results were rather in accordance with water extractions data, with decreasing bioavailable amounts as a result of time and compost addition. No compost or aging effects were instead detected by coelomocytes assay. Results indicate how different methods must be applied altogether to assess the bioavailability and ecotoxicity of xenobiotics such as PCP in soil. The addition of compost was also proven as an effective strategy for the remediation of PCP contaminated soils, although issues related to the possible formation of toxic metabolites must be taken into account.

Effect of aging on catalytic properties in mechanochemical degradation of pentachlorophenol by birnessite.

Mechanochemistry, a technique concerning with milling contaminated samples for prolonged times, induces massive degradation of pollutants by grinding them in ball mills with different soil components or additives. In the present study, laboratory experiments were conducted to evaluate the effect of aging on the mechanochemical efficiency of the Mn-oxide birnessite in degrading pentachlorophenol (PCP). A comparative study on an aged birnessite (KBiA), used after 3years from synthesis, and a fresh birnessite (KBiF), employed immediately after synthesis, was carried out. The differences between the two birnessites, evidenced by spectroscopic and diffractometric techniques, are mainly relative to reduction of the Mn(IV) centered at the MnO₆ octahedra layers from the birnessite structure, which represent the most reactive sites for PCP degradation. The long term air drying at room temperature, by favouring reduction of Mn(IV) to Mn(III), produces an inorganic substrate that offers paucity of the less reactive sites for PCP degradation, thus reducing the oxidative potential of the KBiA. Accordingly, the more reactive fresh birnessite was employed in the experiment with a polluted soil. Adding a small amount of KBiF to soil only induces a light increase in PCP removal, probably due to the mechanically induced PCP adsorption and transformation onto clay minerals present in the soil. Besides, adding a higher dose of birnessite causes a stronger degradation of PCP.

Rank-based biomarker index to assess cadmium ecotoxicity on the earthworm Eisenia andrei.

A proper soil risk assessment needs to estimate the processes that affect the fate and the behaviour of a contaminant, which are influenced by soil biotic and abiotic components. For this reason, the measurement of biomarkers in soil bioindicator organisms, such as earthworms, has recently received increasing attention. In this study, the earthworm Eisenia andrei was used to assess the pollutant-induced stress syndrome after exposure to sublethal concentrations of Cd (10 or 100 μg g(-1)) in OECD soil, after 14 d of exposure. Cadmium bioaccumulation and potential biomarkers such as catalase (CAT), hydrogen peroxide (H2O2), glutathione-S-transferase (GST), malondialdehyde (MDA), phenoloxidase (PO), metallothioneins (MTs) and genotoxic damage were determined. Results suggested that the exposure to 10 and 100 μg g(-1) Cd significantly increased Cd bioaccumulation, MTs and MDA; 100 μg g(-1) Cd contamination evidenced significantly higher values of H2O2 content and PO activity; CAT activity was inhibited at the higher concentration while GST and Comet assay did not show any significant differences from the control. Rank-based biomarker index showed that both different contaminated soils had an effect on the earthworms and allowed to validate the ecotoxicological relevance of this battery of biomarkers for a promising integrated multi-marker approach in soil monitoring and assessment.

Mercury distribution in soils and plants surrounding an industrial area in the South of Italy.

Soil and plant samples, collected nearby an industrial site in the South of Italy, were investigated to monitor the presence and distribution of mercury (Hg). The Hg contamination in soils ranged from ca. 1.5 to 50 mg kg−1 and was limited to the first 0.5 m. In general, high spatial distribution heterogeneities were observed. The spontaneous flora analysed contained an average of 0.2 mg kg−1 of Hg, and the highest Hg concentration was found in the roots of Glicyrrhiza glabra (0.43 mg kg−1). Hg pollution can be possibly ascribed to a chlor-alkali plant operating in this area in the 1960s-1980s.

Heavy Metal Stabilization by Promoting Zeolite Synthesis in Soil

Zeolites are largely used in soil remediation technologies by exploiting their well-known high cation-exchange capacity. Besides this property, zeolites possess large pores and internal cavities. Such pores can be used to trap scarcely soluble HM precipitates, thus chemically reducing their solubility and physically isolating the contaminant at the microscopic level.

Alkaline hydrothermal stabilization of Cr(VI) in soil using glass and aluminum from recycled municipal solid wastes

Hexavalent chromium was stabilized in soil by using a mixture of glass and aluminum recovered from municipal solid wastes under alkaline hydrothermal conditions. Cr(VI) concentration was reduced by 94-98% already after 7days of treatment. After the same period, more than 90% of total Cr was stabilized in highly recalcitrant and scarcely mobile chemical forms, with 50% in the residual fraction (when the samples were treated at 1/10w/w mixture/soil ratio). Longer treatments increased Cr stabilization. X-ray microanalyses revealed that Cr was stabilized in geopolymeric structures within large aluminosilicate mineral aggregates (containing both amorphous and crystalline phases). 3D microstructural analyses showed a limited compaction of the soil with still a 20% internal porosity in the neoformed aggregates. Increased pH and salinity after the treatment can be restored by simple soil amendments and washing.