Chemical Composition, Biomolecular Analysis, and Nuclear Magnetic Resonance Spectroscopic Fingerprinting of Posidonia oceanica and Ascophyllum nodosum Extracts.

A detailed analysis of the elemental and molecular composition of Posidonia oceanica (PO) and Ascophyllum nodosum (AN) is presented. In particular, an in-depth study of the molecular identification via NMR spectroscopy of aqueous and organic extracts of PO and AN was carried out, exploiting 2D COSY and pseudo-2D DOSY data to aid in the assignment of peaks in complex 1D proton NMR spectra. Many metabolites were identified, such as carbohydrates, amino acids, organic acids, fatty acids, and polyphenols, with NMR complementing the characterization of the two species by standard elemental analysis, HPLC analysis, and colorimetric testing. For PO, different parts of the live plant (roots, rhizomes, and leaves) were analysed, as well as the residues of the dead plant which typically deposit along the coasts. The combination of the various studies made it possible to recognize bioactive compounds naturally present in the two plant species and, in particular, in the PO residues, opening the door for their possible recycling and use in, for example, fertilizer. Furthermore, NMR is proven to be a powerful tool for the metabolomic study of plant species as it allows for the direct identification of specific biomarkers as well as providing a molecular fingerprint of the plant variety.

Microplastics in water surface and in the gastrointestinal tract of target marine organisms in Salento coastal seas (Italy, Southern Puglia).

Microplastic pollution is a major global environmental threat that has attracted increasing interest from the scientific community over the past decade. The semi-closed and highly urbanized Mediterranean Sea has been investigated since 2012, in several specific studies that have identified it as a target hotspot for microplastic contamination. The marine coastal zone of the Salento peninsula (Apulia, Italy) has peculiar geographical and hydrodynamic features, although there are few published data detailing the level of microplastics present in this area. The present manuscript contains both data on the concentration of microplastics in surface waters and the level of microplastics ingested by selected marine organisms in the Salento coastal zone. Microplastics floating on the water surface were monitored during Autumn 2020 and Spring 2021 using neuston Manta net at three different distances from the coasts (Lizzano, Gallipoli and Otranto). The level of microplastic ingestion was monitored in fish species (Sardina pilchardus, Boops boops, Mullus barbatus) and in mussels (Mytilus galloprovincialis). Episodic peaks of microplastic concentrations were found on the sea surface during transects performed in the 3 nautic miles from the seashore. High values of ingested microplastics were found in S. pilchardus. and B. boops (5.4 and 4.6 items/individual respectively). A higher concentration of microplastics was detected in the Adriatic Sea than in the Ionian Sea by comparing the gastrointestinal tract of S. pilchardus and B. boops, in the monitored areas. These results are correlated with the concentration of floating microplastics, although this last result is not validated by statistical analysis. These results support the effectiveness of S. pilchardus and B. boops used as targets in monitoring activity for these pollutants. Results show a worrying increase in the concentration of microplastics on the sea surface and in the gastrointestinal tract of the target species compared to data reported in the literature.

Biochar effect on crop performance and Pb and Zn uptake of tomato (Solanum lycopersicum, L.) plants grown on heavy metals contaminated Kosovo soils.

A greenhouse pot experiment was conducted to evaluate the effect of biochar on the growth and uptake of Pb and Zn by tomato plants (Solanum lycopersicum, L.) cultivated in two highly contaminated Kosovo soils, A and B. Plants were cultivated in the biochar amended and unamended soils. As expected, the biochar addition to the two polluted soils has contributed to significantly improve the crop yields, in terms of both fresh and dry weight. Further, results indicated that the effect of biochar on metal mobility is closely related, besides its properties, to soil's native characteristics. In fact, the addition of biochar to soil B had also beneficial effects on the uptake of both metals, halving in some cases the values of the biological accumulation and transfer coefficients, while it did not show the same efficacy on soil A.

Nitrogen Distribution in Annual Growth of 'Italia' Table Grape Vines.

Little information is available about nitrogen (N) content and its concentration in table grape vines. Knowledge of the quantity of N accumulated by the vine organs during the season could support sustainable fertilization programs for table grape vineyards. The aim of the present study was to determine the N content and its concentration in different annual organs, including summer and winter pruning materials, clusters at harvest, and fallen leaves at post-harvest. Specifically, biomass and N were analyzed at six phenological growth stages (flowering, berry-set, berry growth, veraison, ripening, and harvest) from 2012 to 2015. Nitrogen concentration was highest (>40 g/kg d.w.) in the leaves of the secondary shoots at flowering, whereas values >30 g/kg were measured in the leaves of the primary shoots. Nitrogen concentration in the clusters at harvest was 5.3-7.6 g/kg with an accumulation of 18.6-25.4 g/vine in the seasons. The decrease of N content in the primary leaves after flowering indicated a remobilization toward the clusters, which acted as a stronger sink. Later in the season (veraison-ripening), leaves translocated N to permanent organs and primary stems. Pruned wood and fallen leaves accounted for the largest N removal from the vine after clusters, 6.0-7.9 and 9.2-10.2 g/vine, respectively. With regard of the vine annual biomass, the growth followed a sigmoidal model reaching 7300-7500 g of d.w./vine at harvest. Vine leaf area, including both primary and secondary leaves, peaked at veraison (17-21 m2). Vines accumulated ≅35 g/vine of N at harvest, not considering the N removed with the intense summer pruning practices (≅7 g/vine) and the fraction mobilized toward the storage organs (10-15 g/vine). The overall N required by the vine was around 50-55 g/vine, which corresponded to ≅80 kg of N/ha in a vineyard with 1500 vines and a yield of 40 t/ha. Summer and winter pruning practices removed 29-31 g/vine of N which will be partly available (to be considered in the fertilization schedule) for the vine in the successive years if pruned residues were incorporated and mineralized in the soil.

How can the role of leachate on nitrate concentration and groundwater quality be clarified? An approach for landfills in operation (Southern Italy).

Where the unique natural water resource is groundwater, the attention and the susceptibility of local communities and authorities to groundwater quality degradation risks can be so high to determine relevant problems to waste management, especially for landfills in operation or to be realised. A multi-methodological approach was suggested with the purpose to clarify the role of landfill leakage on groundwater quality degradation. The selected study area (SSA) hosts some landfills in a narrow portion of a wide and deep coastal karstic aquifer, for these characteristics to be considered a case of high hydrogeological complexity and vulnerability. News concerning nitrate and secondly iron groundwater concentration anomalously high caused concern in the population and strong local opposition to landfills. The multi-methodological approach includes: the hydrogeological site characterization; the chemical study and the multi-isotope characterization of groundwater and leachate; the land use analysis and the estimation of nitrogen contributions deriving from fertilizers; the mineralogical study of groundwater suspended particles to define the role of natural soil substances. The hydrogeological site characterisation highlighted the local peculiarities of the aquifer. The chemical study was used to define geochemical features, groundwater and leachate characteristics and their macroscopic mixing. The environmental isotopes of hydrogen, carbon, nitrogen, and oxygen were used to investigate the groundwater origin, the most relevant geochemical reactions, the existence of groundwater-leachate mixing, and the sources of anthropogenic NO3-. The land use analysis highlighted quantity and type of used fertilizers permitting to compare these with groundwater in terms of isotopic signature. The mineralogical study demonstrated the role of suspend natural particles due the presence of terre rosse (red or residual soils) in groundwater. The approach confirmed that there are not the groundwater quality degradation effects of landfills, contributing to reassure population and institutions, simplifying the waste management.

Assessment of addition of biochar to filtering mixtures for potential water pollutant removal.

Green roofs are used increasingly to alleviate peaks of water discharge into the sewage systems in urban areas. Surface runoff from roofs contain pollutants from dry and wet deposition, and green roofs offer a possibility to reduce the amounts of pollutants in the water discharged from roofs by degradation and filtering. These pollutants would otherwise enter wastewater treatments plants and ultimately end up in sewage sludge that is spread on agricultural soils. The most common substrates used in green roofs have limited capacity for filtration and sorption. Also, more sustainable alternatives are sought, due to the high carbon footprint of these materials. Biochar is a carbon-rich material produced by pyrolysis of biomass, and several types of biochar have been described as good sorbents and filter materials. Biochar is also a light and carbon negative material, which may fulfill other desired criteria for new green roof substrates. We here report on an experiment where two types of biochar, produced from olive husks at 450 °C or from forest waste at 850 ° C were mixed with volcanic rock or peat, and tested for retention capacity of phenanthrene and six heavy metals in a column experiment with unsaturated gravimetric water flow lasting for 3 weeks. The results suggest that biochar as a component in green roof substrates perform better than traditional materials, concerning retention of the tested pollutants, and that different types of biochar have different properties in this respect.

In situ evaluation of the fruit and oil characteristics of the main Lebanese olive germplasm.

BACKGROUND: Very little information is available on the characteristics of the Lebanese olive germplasm. Therefore, the aim of this work was to evaluate the fruit and oil characteristics of the main Lebanese olive varieties (Aayrouni, Abou chawkeh, Baladi, Del and Soury) from two successive crop seasons (2010-2011). RESULTS: All of the genotypes had medium-high oil content in the fruit, indicating their suitability for oil production; Aayrouni had particularly high values. The variety Abou chawkeh also had a high pulp/pit ratio, which is a very desirable trait in table olives. For all the varieties the values of free fatty acids, peroxide values, absorbances in ultraviolet, fatty acid composition, sterol content and composition and erythrodiol + uvaol content of the oils were within the requirements of the International Olive Council's Trade Standard for extra virgin olive oil. The only exception was for the values of Δ-7-stigmastenol in 2011 in Soury and, especially, in Baladi, which were higher than 0.5%. In some cases, stearic and arachidic acids fluctuated around the maximum values allowed. CONCLUSION: The findings of this study provide a first picture of the main characteristics of olives and oils currently produced in Lebanon. © 2015 Society of Chemical Industry.

Evaluation of Atriplex halimus, Medicago lupulina and Portulaca oleracea for phytoremediation of Ni, Pb, and Zn.

Suitable plant species are able to accumulate heavy metals and to produce biomass useful for non-food purposes. In this study, three endemic Mediterranean plant species, Atriplex halimus, Portulaca oleracea and Medicago lupulina were grown hydroponically to assess their potential use in phytoremediation and biomass production. The experiment was carried out in a growth chamber using half strength Hoagland's solutions separately spiked with 5 concentrations of Pb and Zn (5, 10, 25, 50, and 100 mg L(-1)), and 3 concentrations of Ni (1, 2 and 5 mg L(-1)). Shoot and root biomass were determined and analyzed for their metals contents. A. halimus and M. lupulina gave high shoot biomass with relatively low metal translocation to the above ground parts. Metals uptake was a function of both metals and plant species. It is worth noting that M. lupulina was the only tested plant able to grow in treatment Pb50 and to accumulate significant amount of metal in roots. Plant metal uptake efficiency ranked as follows: A. halimus > M. lupulina > P. oleracea. Due to its high biomass production and the relatively high roots metal contents, A. halimus and M. lupulina could be successfully used in phytoremediation, and in phytostabilization, in particular.

Effect of compost and manure amendments on zinc soil speciation, plant content, and translocation in an artificially contaminated soil.

The addition of organic matter in soil can modify the bioavailability of heavy metals. A greenhouse pot experiment was carried out using an edible plant species Eruca vesicaria L. Cavalieri grown on an artificially contaminated soil with Zn (665 mg kg(-1)). In this study, the effect of compost at 20 t ha(-1) (C20) and at 60 t ha(-1) (C60), manure at 10 t ha(-1) (M10) and at 30 t ha(-1) (M30), and chemical fertilizers (NPK) on Zn fate in a soil-plant system was evaluated. At the end of the experiment, the main growth parameters and Zn content in plants were determined. In addition, Zn speciation in the soil was assessed using the original Community Bureau of Reference sequential extraction and diethylene triamine pentaacetic acid extraction. Zinc, though an essential element for plant growth, caused toxicity effects in plants grown on control and manure treatments, while in the compost treatments, plants showed no visual toxicity symptoms. The concentrations of Zn in roots were similar for all treatments, while significant differences were observed for shoots. In fact, in the compost treatments, plants showed the lowest Zn concentration in shoots. Zinc speciation seems not to be affected by the applied treatments. Indeed, Zn plant content and translocation to shoots seems to be affected. Compost amendments significantly reduced Zn content and translocation in comparison to other treatments.

Chemical composition and in vitro activity of plant extracts from Ferula communis and Dittrichia viscosa against postharvest fungi.

F. communis and D. viscosa are perennial Mediterranean weeds that have been used for different therapeutic purposes in traditional pharmacopeia. Plant extracts were obtained from air dried D. viscosa young shoots (DvA) and F. communis aerial part (FcA) and roots (FcR) with n-hexane. The chemical compositions of the extracts were analyzed by HPLC-DAD, LC-MS (ESI) and LC-Q-TOF techniques. Two sesquiterpene lactones (inuviscolide, tomentosin) and three sesquiterpene acids (costic acid, hydroxycostic acid, ilicic acid) were identified from the D. viscosa extract, while in F. communis extracts three daucane sesquiterpenes (acetoxyferutinin, oxojaeskeanadioyl anisate, fertidin) and one coumarin (ferulenol) derivates were found. Biological activities of plant extracts were studied in in vitro experiments on the colonies and conidia of Botryotinia fuckeliana, Penicillium digitatum, P. expansum, Monilinia laxa, M. fructigena and Aspergillus spp. Extracts showed varying degree of antifungal activities on colony growth and conidia germination. The extract from FcA showed the least effect, while DvA extract had the strongest fungitoxic effects. FcR extract presented a fungitoxic effect on the colony growth, but it was not able to inhibit the conidia germination. These distinctions can be attributed to the differences in chemical composition of plant extracts.

Evolution of the fulvic acid fractions during co-composting of olive oil mill wastewater sludge and tree cuttings.

Fulvic acids (FAs) were isolated by a conventional procedure from two mixtures of the sludge residue obtained from olive oil mill wastewater (OMW) evaporated in open-air pond and tree cuttings (TC) at different stages of the co-composting process. The FAs were analyzed for elemental (C, H, N, S, O) and acidic functional group (carboxylic and phenolic) composition, and by ultraviolet/visible, Fourier transform infrared and fluorescence spectroscopies. At the initial stage of composting, FAs from the OMW sludge-TC mixtures were characterized by a prevalent aliphatic character, large contents of C, S-containing groups, proteinaceous materials and polysaccharide components, extended molecular heterogeneity, small O and acidic functional group contents, and small degrees of aromatic ring polycondensation, polymerization and humification. As composting proceeded, C, H and S contents, C/N ratio, and aliphaticity decreased, whereas N, O, COOH and phenolic OH contents, C/H and O/C ratios, and aromaticity increased. These results suggested that, with increasing the composting time, the chemical and structural properties of the FA components of the two OMW sludge-TC mixtures approached the characteristics typical of native soil FAs. Thus, co-composting of OMW sludge mixed with TC may represent a suitable treatment for enhancing the quality of organic matter in these materials when used as soil amendments.

Changes in the ascorbate system in the response of pumpkin (Cucurbita pepo L.) roots to aluminium stress.

The involvement of the ascorbate (AsA) system in the response of pumpkin (Cucurbita pepo L.) roots to aluminium stress was studied. The treatment of 5-day-old pumpkin seedlings with 50 microM aluminium sulphate resulted in approximately 60% inhibition of root growth within 48-60 h of treatment, while aluminium accumulated in the roots reaching a maximum within 48h. During the same period, the hydrogen peroxide content of the roots was strongly enhanced. The increased level of hydrogen peroxide was matched by both increased ascorbate peroxidase (APX) (EC 1.11.1.11) activity and ascorbate free radical reductase (AFRR) (EC 1.1.5.4) activity, while dehydroascorbate reductase (DHAR) (EC 1.8.5.1) and glutathione reductase (GR) (EC 1.6.4.2) did not change. The levels of AsA in the roots were also increased by the Al treatment. It was concluded that an oxidative burst is probably involved in the toxicity of Al in pumpkin roots and that plants react to the enhanced production of reactive oxygen species by expressing higher levels of scavenging systems such as the AsA-APX system.