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.
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.
Volcanic tuffs rich in chabazite zeolites have been extensively examined for their potential to enhance soil properties and increase fertilizer efficiency, both in their natural state and when enriched with nitrogen (N). However, there is a scarcity of data regarding their utilization in acidic sandy soil, particularly when used alongside organic fertilizers. This paper presents the findings of a 50-day laboratory incubation study that investigated the dynamics of N pools in an acidic sandy-loam agricultural soil treated with various N sources. These sources included urea, N-enriched chabazite zeolite tuff, and pelleted composted manure applied at a rate of 170 kg N/ha. Additionally, the N sources were tested in combination with chabazite zeolite tuff mixed into the soil to assess its role as a soil conditioner. The results revealed distinct behaviours among the tested N sources, primarily impacting soil pH and N dynamics. Soil fertilized with manure exhibited slow N mineralization, whereas N-enriched zeolite displayed a more balanced behaviour concerning net NO3−-N production and NH4+-N consumption. Both N-enriched zeolite and urea temporarily altered the soil pH, resembling a “liming” effect, while pelleted manure facilitated a prolonged shift towards neutral pH values. Considering the water adsorption capacity of zeolite minerals, caution is advised when adjusting water content and employing combustion methods to measure soil organic matter in zeolite-treated soil to avoid potential inaccuracies. In summary, N-enriched chabazite zeolite tuff emerged as a valuable N source in acidic sandy-loam soil, offering a promising alternative to synthetic fertilizers and showcasing a sustainable means of N recycling.