Claudio Cocozza

Characterization of solid and aqueous phases of a peat bog profile using molecular fluorescence spectroscopy, ESR and FT-IR, and comparison with physical properties

Abstract A peat core (10×10×100 cm) was removed from Etang de la Gruere, an ombrotrophic peat bog in the Jura Mountains of Switzerland. The core was sliced into 3 cm sections and the samples characterized with respect to ash content, bulk density, moisture content, and concentrations of C and H. Solid peat residues were freeze-dried, milled very finely and analyzed using Fourier transform infrared (FT-IR) and electron spin resonance (ESR) spectroscopy. Pore waters expressed from the peat slices were collected, filtered (0.2 μm membrane filters) and analyzed using fluorescence emission, excitation and synchronous-scan spectroscopy, in addition to pH. Taken together, the physical properties of the core and the ESR measurements of solid peats appear to record the variation in humification of refractory organic matter (peat). The fluorescence and FT-IR data, on the other hand, appear to characterize the extent of recent decomposition of labile organic matter. In fact, these data indicate the presence of two distinct zones in the bog: (i) the acrotelm, or zone of active decay, which may be oxygenated, depending on the season and the depth to the water table, and (ii) the catotelm which is always anoxic, and where organic matter decomposition rates are negligible.

Temperature dependence of goethite dissolution promoted by trihydroxamate siderophores

This article reports an investigation of the temperature dependence of goethite dissolution kinetics in the presence of desferrioxamine B (DFO-B), a trihydroxamate siderophore, and its acetyl derivative, desferrioxamine D1 (DFO-D1). At 25 and 40°C, DFO-D1 dissolved goethite at twice the rate of DFO-B, whereas at 55°C, the behavior of the two ligands was almost the same. Increasing the temperature from 25 to 55°C caused little or no significant change in DFO-B or DFO-D1 adsorption by goethite. A pseudo-first-order rate coefficient for dissolution, calculated as the ratio of the mass-normalized dissolution rate coefficient to the surface excess of siderophore, was approximately the same at 25 and 40°C for both siderophores. At 55°C, however, this rate coefficient for DFO-D1 was about half that for DFO-B. Analysis of the temperature dependence of the mass-normalized dissolution rate coefficient via the Arrhenius equation led to an apparent activation energy that was larger for DFO-B than for DFO-D1, but much smaller than that reported for the proton-promoted dissolution of goethite. A compensation law was found to relate the pre-exponential factor to the apparent activation energy in the Arrhenius equation, in agreement with what has been noted for the proton-promoted dissolution of oxide minerals and for the complexation of Fe3+ by DFO-B and simple hydroxamate ligands in aqueous solution. Analysis of these results suggested that the siderophores adsorb on goethite with a only single hydroxamate group in bidentate ligation with an Fe(III) center.

Fulvic acid–like organic compounds control nucleation of marine calcite under suboxic conditions

Intracrystalline organic compounds, enclosed within in situ–precipitated marine microcrystalline calcite (automicrite), might represent either an inclusion or the catalyst of such precipitation. We use evidence from a Lower Cretaceous deep-water carbonate mound to show (1) the original source, (2) the degree of condensation, (3) the redox conditions involved, and (4) the catalytic role of natural organic matter for the precipitation of automicrite. Fluorescence spectrometry of the intracrystalline organic fraction extracted from these carbonates identifies a marine fulvic acid–like organic compound with a low degree of polycondensation. This finding points to a temporal correlation of the initial stage of geopolymer formation with the precipitation of automicrite. Furthermore, the rare earth element (REE) distribution patterns in the mineral show a consistent positive Ce anomaly, suggesting an episode of reductive dissolution of iron-manganese oxyhydroxides during automicrite formation. In general, a relative enrichment of middle-weight REEs is observed, resulting in a convex distribution pattern typical for, e.g., phosphate concretions or humic acid material. By merging the results of spectrometry and REE geochemistry we thus conclude that the marine calcite precipitation was catalyzed by marine fulvic acid–like compounds during the early stages of humification under suboxic conditions. This indicates that humification, driven by the presence of a benthic biomass, is more important for calcite authigenesis than any site-specific microbial metabolism. The Neoproterozoic rise of carbonate mounds supports this hypothesis; there is molecular evidence for early metazoan divergence then, but not for a major evolutionary episode of microorganisms.

Comparative management of offshore posidonia residues: Composting vs. energy recovery

Residues of the marine plant posidonia (Posidonia oceanica, PO) beached in tourist zones represent a great environmental, economical, social and hygienic problem in the Mediterranean Basin, in general, and in the Apulia Region in particular, because of the great disturb to the bathers and population, and the high costs that the administrations have to bear for their removal and disposal. In the present paper, Authors determined the heating values of leaves and fibres of PO, the main offshore residues found on beaches, and, meantime, composted those residues with mowing and olive pruning wood. The final composts were characterized for pH, electrical conductivity, elemental composition, dynamic respiration index, phytotoxicity, fluorescence and infrared spectroscopic fingerprints. The aim of the paper was to investigate the composting and energy recovery of PO leaves and fibres in order to suggest alternative solutions to the landfill when offshore residues have to be removed from recreational beaches. The fibrous portion of PO residues showed heating values close to those of other biofuels, thus suggesting a possible utilization as source of energy. At the same time, compost obtained from both PO wastes showed high quality features on condition that the electrical conductivity and Na content are lowered by a correct management of wetting during the composting.

Variability in As, Ca, Cr, K, Mn, Sr, and Ti concentrations among humic acids isolated from peat using NaOH, Na4P2O7 and NaOH+Na4P2O7 solutions

Sphagnum peat has been found to efficiently remove heavy metals, oil, detergents, dyes, pesticides and nutrients from contaminated waters since its major constituents, i.e., unesterified polyuronic acids, cellulose, and fulvic and humic acids (HA), show functional groups (e.g., alcohols, aldehydes, carboxylic acids, ketones and phenolic hydroxides) which may adsorb pollutant species. The influence of the extractant on the analytical characteristics of HA is an old but still open topic that should be studied in relation to the nature of the matrix from which they originate. While a number of works have been published on the effects of different reagents on the extraction yields and structural properties of HA from soils, relatively little attention has been devoted to peat HA. In this work, the contents of some major and trace elements (As, Ca, Cr, K, Mn, Sr, and Ti) in five Sphagnum-peat samples and in their corresponding HA fractions isolated using three common extractant solutions, i.e., 0.5M NaOH, 0.1M Na(4)P(2)O(7), and 0.5M NaOH+0.1M Na(4)P(2)O(7), where investigated by X-ray fluorescence spectroscopy. In general, Cr, Mn, and Ti concentrations of bulk peat samples were higher than those of the corresponding HA fractions regardless of the extractant used. Arsenic, Ca, K, and Sr concentrations in the HA fractions were affected by the extraction procedure, although at different extents depending on the extractant utilized. In particular, compared to both NaOH and NaOH+Na(4)P(2)O(7), the Na(4)P(2)O(7) extractant yielded HA generally richer in As, Ca, K, and Sr, and poorer in Ti. These results may be related to both the nature of each HA fraction and the physical and chemical form of each element supplied to the studied bog via atmospheric deposition.

Elemental characterization of wild edible plants from countryside and urban areas

Thirteen elements (Na, K, Ca, Mg, Fe, Mn, Cu, Zn, Cr, Co, Cd, Ni and Pb) in 11 different wild edible plants (WEP) (Amaranthus retroflexus, Foeniculum vulgare, Cichorium intybus, Glebionis coronaria, Sonchus spp., Borago officinalis, Diplotaxis tenuifolia, Sinapis arvensis, Papaver rhoeas, Plantago lagopus and Portulaca oleracea) collected from countryside and urban areas of Bari (Italy) were determined. B.officinalis and P.rhoeas could represent good nutritional sources of Mn and Fe, respectively, as well as A.retroflexus and S.arvensis for Ca. High intake of Pb and Cd could come from P.lagopus and A.retroflexus (1.40 and 0.13 mg kg(-1) FW, respectively). WEP may give a substantial contribution to the elements intake for consumers, but in some cases they may supply high level of elements potentially toxic for human health. Anyway, both ANOVA and PCA analyses have highlighted the low influence of the harvesting site on the elements content.

Posidonia oceanica (L.) based compost as substrate for potted basil production

BACKGROUND Peat is the main component of growing media but is also a non-renewable resource; therefore European policy strongly encourages the use of peat alternatives such as compost. Posidonia is a Mediterranean seagrass that produces very conspicuous onshore deposits that can be composted. In this study, a commercial green compost and a Posidonia residue-based compost were tested in order to assess their potential use as substitutes or complements to peat. RESULTS All macro and micro-element concentrations of the substrates were positively and significantly related to the percentage of composts in the growing media. Plant grown on peat showed higher content of P, Ca, K, Na, Cu, Mn, Zn and Fe, and a slightly higher biomass production in comparison to compost-based growing media. In contrast, plants grown on compost-based substrates showed lower uptake of Cd and Cr than peat. CONCLUSION The results indicate that both composts can be used as a complement to the peat for substrate preparation, especially at a rate of 30%. The Posidonia-based compost showed better productive results in comparison to the green one. Basil grown on the two compost-based media showed reduced absorption level of potentially toxic metals in comparison to peat.

Effects of the main extraction parameters on chemical and microbial characteristics of compost tea.

The rising popularity of compost tea as fertilizer or foliar spray against pathogens has encouraged many researchers to evaluate its performance without standardizing its quality, so obtaining inconsistent and controversial results. The fertilizing and pesticide-like effects of compost tea are due to its chemical and microbiological properties. Therefore, this study aimed to identify the best combination of the compost tea extraction parameters for exalting both chemical and microbiological features. A factorial design was adopted to evaluate the effects of compost/water ratio, extraction time, storage duration and storage temperature in different combination on physical, chemical and microbiological characteristics of compost tea, and the results were elaborated through different statistical analyses. Compost tea nutrients and microorganisms were influenced by compost/water ratio and extraction time. In addition, the storage duration affected the microbial populations, whereas the storage temperature influenced only the fungal population of compost tea. Results suggested that the best combination of the studied parameters was: 1:2.5 compost/water ratio, 2days of extraction time and the compost tea should be utilized immediately after the extraction, since the storage reduced the microbial populations.

Short-Term Effects of Different Organic Amendments on Soil Properties and Organic Broccoli Growth and Yield

ABSTRACT The aim of this study was to evaluate the effects of different organic fertility sources on organic broccoli (Brassica oleracea var. italica) growth and yield, and on soil properties. The fertilization was designed to supply the crop with about 100 kg ha−1 of N using two amendments: a municipal solid wastes-based compost (CC), and a manure based compost (CB). The former was used alone (T1), in combination with its own water extract (CT) in fertigation (T2), and in combination to CT applied in fertigation and as foliar spray (T3). Other treatments resulted from the application of (i) CC and CB (T4); (ii) CB alone (T5); and (iii) the exhausted compost (EX) resulting from the extraction of CT (T6). Unamended plots were used as control (T7). Selected soil properties were determined at the beginning and at the end of the trial in order to estimate the effects of the various treatments on these parameters. The best yields were obtained with T4 and T5 (16.95 and 18.46 t ha−1, respectively). The application of CC alone (T1) showed slightly better growing parameters in comparison to its application in combination to CT (T2 and T3), even though the yields were not significantly different from each other. T6 showed the lowest yield of broccoli (7.03 t ha−1) among the treatments, superior only to the unfertilized control (5.38 t ha−1, T7). The different fertilizations showed a general soil enrichment of available phosphorous and organic matter, even if the latter could be only transitory. Finally, the high production costs and the low yields obtained apparently dissuade the use of compost tea and exhausted compost for the fertilization of broccoli crop.

Effect of hydrolyzed protein-based mulching coatings on the soil properties and productivity in a tunnel greenhouse crop system

Polymeric protein-based biocomposites were used in this work as water dispersions to generate, in situ, biobased mulching coatings by spray technique, as alternative to low density polyethylene films for soil mulching. At the end of their lifetime, these biodegradable coatings degrade in soil thank to the microbial community that mineralizes them. Protein hydrolysates (PH) were derived from waste products of the leather industry, while poly(ethylene glycol) diglycidyl ether (PEG) and epoxidized soybean oil (ESO) were used to make the biodegradable spray coatings. A study under greenhouse condition was carried out using seedling test plots in order to investigate the performance of the spray coatings and their possible influence on some aspects of leaf growth, functionality and nutritional quality of lettuce (Lactuca sativa L., Mortarella selection Romanella variety Duende) and on soil properties. The biodegradable coatings showed the same good agronomic performances comparable with the ones of a commercial low density polyethylene mulching film, maintaining the mulching effect for the requested cultivation period and ensuring at the same time a similar rate of plant growth and dry matter accumulation. The research showed that 2 months after the tillage carried out at the end of the cultivation the amount of coating residues present in the soil was <5% of the initial weight of the biodegradable coatings. At the end of the field test, the soil mulched with the polyethylene film recorded an electrical conductivity value lower with respect to the soil mulched with the sprayed coatings, which release nutrients in the soil during their decomposition.