Notwithstanding the widespread use of natural and pre-exchanged zeolites for zootechnical effluent treatment, little attention has been dedicated to the variation in the chemical composition of the treated slurries, besides the effects on their NH4+ content. This paper aimed at elucidating the compositional variations in terms of major and trace elements of a raw pig-slurry (PS) after three sequential treatment cycles (TC) with three different grain sizes of natural and Na-exchanged zeolite-rich volcanic tuffs (natural ZTs and NaZTs). A series of laboratory batch experiments revealed that all ZTs had profoundly influenced the final PS chemical composition. As expected, the NaZTs were more efficient in terms of NH4+ removal than the natural ZTs, reaching almost 60% reduction of the initial content after three TCs. A parallel effect of this efficient removal was the remarkable increase in Na+. The Na-forms of ZTs led also to stronger competition with K+ ions, resulting in adsorption of this macronutrient and hence in a reduction of the fertilization value of the PS. In terms of heavy metals and other trace elements, all the treatments with ZTs had significantly increased the Li, Ba, Rb, Sr, Ga, and U content in the PS.
The search for safer and sustainable management of animal manure is a global and topical challenge, in particular for the reduction of nitrogen (N) content. The use of natural adsorbents as zeolite-rich tuffs is recognized as a valid method to recover N, in the form of ammonium (NH4+), from animal manure. While the scientific literature is rich in studies performed on synthetic solutions and using clinoptilolite zeolites as adsorbent, it lacks information concerning adsorption in real liquid manure and using other types of zeolite-rich tuffs (e.g., chabazite). This work aims at exploring the NH4+ adsorption process from raw liquid swine manure, using a chabazite-rich zeolite tuff as adsorbent. The effects of temperature, contact time, and grain size have been assessed. Isotherms, kinetic models, and thermodynamic parameters have been investigated. Harkins-Jura isotherm correlates well with the observed data, in accordance with the formation of an adsorption multilayer. Kinetic data have been explained by intraparticle diffusion and pseudo-second-order models. In conclusion, the natural chabazite tuff has proven to be a valid material for NH4+ adsorption from raw liquid swine manure. In particular, to reach the highest adsorption capacities and adsorption rates, it is recommended to use it at a fine particle size and with dosages < 6 %.
In order to improve the sustainability and productivity of modern agriculture, it is mandatory to enhance the efficiency of Nitrogen (N) fertilizers with low-impact and natural strategies, without impairing crop yield and plant health. To achieve these goals, the ZeOliva project conducted an experiment using a zeolite-rich tuff as a soil amendment to improve the efficiency of the N fertilizers and allow a reduction of their inputs. The results of three years of experimentation performed in three different fields in the Emilia-Romagna region (Italy) are presented. In each field, young olive trees grown on zeolite-amended soil (−50% of N-input) were compared to trees grown on unamended soil (100% N-input). Soils and leaves were collected three times every year in each area and analyzed to monitor the efficiency of the zeolite treatment compared to the control. Vegetative measurements were performed along with analysis of pH, Soil Organic Matter and soluble anions in soil samples, whereas total C and N, C discrimination factor and N isotopic signature were investigated for both soils and leaves. Besides some fluctuations of nitrogen species due to the sampling time (Pre-Fert, Post-Fertilization and Harvest), the Total Nitrogen of leaves did not highlight any difference between treatments, which suggest that plant N uptake was not affected by lower N input in the zeolite treatment. Results, including vegetative measurements, showed no significant differences between the two treatments in all the observed variables, although the control received twice the N-input from fertilization. Based on these results, it is proposed that zeolite minerals increased the N retention time in the soil, allowing a better exploitation by plants which led to the same N uptake of the control notwithstanding the reduction in the N inputs. The use of zeolite-rich tuff in olive growing thus allows a reduction in the amount of fertilizer by up to 50% and improves the N use efficiency with many environmental and economic benefits.
The aim of this study was to investigate the efficiency of removing Cr6+ from aqueous solutions using two exfoliated vermiculite: (1) heated abruptly at 1000 °C and (2) irradiated with microwave radiation. The effects investigated were contact time, adsorbate concentration and initial Cr6+ concentration. The adsorption with both exfoliated vermiculites was well described by the DKR isotherm, indicative of a cooperative process and with the pseudo second order kinetic model. The Kd value for the two exfoliated vermiculites was similar, 0.2 ·1010 μg/Kg. The maximum adsorption capacity of Cr6+ with thermo-exfoliated vermiculite, 2.81 mol/g, was much higher than with microwave irradiated vermiculite, 0.001 mol/g; both values were obtained with 0.5 g of vermiculite in contact with distilled water enriched with 1 ppm of Cr6+ for 24 h. Factors such as ion chemistry, the solution pH and ionic strength, influence the values of capacity, adsorption energy and initial adsorption rate values of the exfoliated vermiculite. In addition, these values depended on the exfoliation process, being the adsorption capacity highest with abrupt heating of vermiculite, while the adsorption energy and rate values showed just a slight increase with microwave irradiation. This aspect is important to select the most suitable vermiculite modification treatment to use it as an adsorbent.
<p>Vitis vinifera L. cultivar &#8220;Cannonau&#8221; (Magnoliopsida Vitaceae) has been grown for years in the Italian regions to produce a fine wine, with Controlled Designation of Origin (DOC) and Denomination of Controlled and Guaranteed Origin, (DOCG). The International Organization of Vine and Wine (OIV) defined the &#8220;terroir&#8221; as &#8220;a concept which refers to a specific area in which the interactions between the physical and biological environment and applied vitivinicultural practices develops. Whereas, from a geological point of view, the terroir has been defined as the geochemistry of soil, surface and ground water. Recent studies, regarding vitis vinifera, based on geochemical characterization have clearly shown the connection among geological origin, vineyard soil and grape berries. Another way to trace geographical origin can be through the identification of Rare Earth Elements (REEs) in the soil-plant system. However, the study of REEs is also important to define the petrological characterization and the relations between soil and plants.</p> <p>We evaluated the relationship among the concentrations of rare earth elements (REE) in soil and in &#8220;Cannonau&#8221; grape berries in vineyards belonging to two different vineyards located in the valleys Pardu and Pelau in Sardinia (Italy) and one in Susegana in the Veneto Region (Northern Italy). The concentration of REE in samples of soil and juice or solid residues of grape berries was determined by inductively coupled plasma mass spectrometry (ICP-MS) and the data were elaborated with multivariate statistics (Linear Discrimination Analysis).The concentration of REEs in soil and grape berry samples allowed an identification of each locality examined . Moreover, the geochemical and statistical analyses allowed to discriminate the vineyard soils and grape berries according to geo-lithological characteristics of each area and to identify possible geochemical markers for the cultivar &#8220;Cannonau&#8221; .These markers, suitable as terroir fingerprintings, may be useful to avoid fraudulent use of the denomination label and falsification of the Made in Italy trademark.</p>
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