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Recently, the demand for quality and food safety has become more pressing, with a consequent requirement for unequivocal geographical identification of agri-food products. Moreover, the requirement for eco-friendly and human healthy practices is a key issue for the agriculture of the future. In this framework, this work aims at investigating soil, leaves and olives from two areas in the Emilia-Romagna Region (Italy), Montiano (MN) and San Lazzaro (SL), where three different foliar treatments were carried out for each site to protect plants from environmental stress and pests. Geochemical analysis of REE and trace elements were performed to 1) univocally determine the locality of provenance and 2) evaluate if the different foliar treatments can affect the geochemical fingerprint of leaves and olives. the effect of different foliar treatments (no treatment, dimethoate, and alternating of natural zeolitite and dimethoate in MN; Spinosad+Spyntor fly, natural zeolitite and NH4+-enriched zeolitite in SL). Principal Component Analysis (PCA) and Partial Least Square-Discriminant Analysis (PLS-DA, including Variable Importance in the Projection analysis) were used to discriminate between localities and different treatments. PCA of leaves and olives highlighted that different foliar treatments can be identified based on different geochemical contents (total variance: 95.64% and 91.08% in MN; 71.31% and 85.33% in SL of leaves and olives, respectively). Slightly lower, although still quite acceptable, results are given by PCA applied to area discrimination (87.46% and 80.43% of total variance). The PLS-DA analysis gave the largest contribution to the discrimination of different treatments and geographical identification. VIP analyses provided to identify which elements could be considered as potential discriminators in the model in order to correlate leaves and olives from the same area: i) Sm and Dy in MN site and ii) Rb, Zr, La and Th in SL field; in order to discriminate different areas Rb and Sr were the best identifiers. Based on REE and trace element analyses, it can be highlighted that 1) the geographical origin could be discriminated and 2) different foliar treatments applied for crop protection can be recognized, which means, reversing the reasoning that each farmer can develop a method to pinpoint his own product.

There is a widely recognized need to reduce human activity's impact on the environment. Many industries of the leather and textile sector (LTI), being aware of producing a significant amount of residues (Keßler et al. 2021; Liu et al. 2021), are adopting measures to reduce the impact of their processes on the environment, starting with a more comprehensive characterization of the chemical risk associated with the substances commonly used in LTI. The present work contributes to these efforts by compiling and toxicologically annotating the substances used in LTI, supporting a continuous learning strategy for characterizing their chemical safety. This strategy combines data collection from public sources, experimental methods and in silico predictions for characterizing four different endpoints: CMR, ED, PBT, and vPvB. We present the results of a prospective validation exercise in which we confirm that in silico methods can produce reasonably good hazard estimations and fill knowledge gaps in the LTI chemical space. The proposed protocol can speed the process and optimize the use of resources including the lives of experimental animals, contributing to identifying potentially harmful substances and their possible replacement by safer alternatives, thus reducing the environmental footprint and impact on human health.

Both nitrogen (N) and phosphorous (P) are essential for life and their supply sustain the global population growth, thus, the question about “how correctly manage nutrient-rich wastewaters?” is a primary issue for many countries. The storage and the subsequent thoughtless use of these materials, as breeding farm and biogas plants wastewaters, has enormous impacts on the environment, causing eutrophication of water bodies and greenhouse gas emissions. The development of low-cost, low environmental impact and high yield treatment technologies is thus necessary to incentivize the circularity of resources, promoting their reuse and encouraging recycling in agri-food systems.The recovery of N and P by struvite precipitation (MgNH4PO4·6H2O) is a promising strategy, but these technologies are in general too expensive, energy-demanding, or they alter the treated wastewaters, making them not suitable for agricultural purposes unless additional treatments are carried out.This work investigates an innovative wastewater treatment processes that foresee the use of a natural chabazite-rich zeolitite (rock containing more than 50 % of zeolite minerals) in combination with struvite chemical precipitation. The adsorption batch (phase 1) is intended to improve the NH4+/Mg2+ and NH4+/PO43- molar ratios, to enhance struvite yield (phase 2) with fewer amounts of reagents required, thus to improve both the efficiency and the cost-effectiveness of struvite production. For the 1st phase, both natural zeolitite (NZT) and the K+-enriched (KZT) zeolitite were tested. KZT was intended to counteract any possible interference for struvite precipitation, which could instead happen with NZT due to the input of Ca2+ ions in solution.In the 2nd phase (struvite precipitation), 2 different Mg:NH4:PO4 molar ratios were tested, in particular a condition of NH4+ excess (MR1) and a condition with Mg2+ in excess (MR2).Treatments in which NZT (NZT-S) and KZT (KZT-S) were added prior to struvite precipitation were compared to a conventional struvite precipitation method without the use of zeolitites (CNTR).NZT-S_MR1 was found to be the most feasible strategy because of the highest NH4+-N removal efficiency, highest struvite precipitation efficiency (less waste of reagents), and less unwanted alterations of the treated wastewater. The precipitate obtained was 89.9 mass % composed of struvite with 3.5 % N, poor in hazardous heavy metals.The NH4+-N removal efficiency was in order: NZT-S > KZT-S > CNTR, with the highest reduction of 84.8 % recorded by NZT-S_MR1 and the lowest recorded by the CNTR (67.2 and 75.0 % for MR1 and MR2 respectively).The addition of a “zeolite phase” in struvite precipitation process thus represents i) a valuable method for improving the efficiency of struvite production ii) a method for saving chemical reagents in struvite production and iii) an efficient way to recover and recycling N in agriculture.

The olive fruit fly is worldwide considered a major harmful pest of the olive agroecosystem. In Italy, the fruit fly infestation is traditionally countered by spraying chemical insecticides (e.g., dimethoate), but due to the recent ban of dimethoate by the Reg EU2019/1090 and the increasing awareness of consumers of food sustainability, the interest in developing chemical-free alternatives to pesticides, such as the use of particle-films, is rising. A field experiment was conducted to assess the effect of different particle films (kaolin-base and zeolitite-base) on leaf gas exchanges and leaf optical properties. Results showed that with the dust accumulation on the leaves’ surface, photosynthesis, stomatal conductance, transpiration and water use efficiency were significantly lower in kaolin-treated olive trees compared to those treated with zeolitite and to the control, while olive trees treated with zeolitite showed physiological parameters similar to the untreated plants. Microstructural differences of different particle film on the leaf and olive surfaces emerged by ESEM observations also influenced leaf optical properties. Oils produced by zeolitite-treated plants show higher intensities of gustatory and olfactory secondary flavors compared to kaolin and test oils.

During the growing season, the use of foliar treatments based on fine grained geomaterial to reduce the negative impact of environmental stresses and protect the olives from insect pests is a well-known approach; however, while kaolin powders have been widely employed, zeolitite-based materials are much less known and exploited.The aim of this study is to assess the effect of the two different treatments (zeolitite and kaolin) on the chemical and sensory qualities of the oils produced.The study was carried out during two consecutive crop seasons in a 15 year old commercial olive orchard (Olea europaea), cv Correggiolo, located on the Appennine hills near Bologna (Italy). Foliar treatments were distributed during summer, until olive harvest. Ripening index, weight, oil and water content were measured on olive fruits. Olive productions were transformed in oils using a low scale continuous mill, quality parameters (free acidity, peroxide numbers, K232, K270, total phenols, fatty acids) were evaluated according to the official methods described in Regulation EC 2568/91 and subsequent amendments. Phenolic compounds, vitamins and pigments were determined by HPLC-DAD. Sensory analysis was performed by the panel of Agency for Agrofood Sector Services of Marche region (ASSAM), a fully-trained analytical taste panel recognized by the International Olive Oil Council (IOC) of Madrid, Spain, and by the Italian Ministry for Agriculture, Food, and Forestry Policy.Olives treated with zeolite showed higher oil contents with respect to the other treatments. Oils produced by plants treated with zeolite particle film exhibited higher contents of total phenols, tyrosol, oleuropein and secoiridoids than to the oils produced by other treatments. Oils produced from olives treated with kaolin had sensory profiles characterized by sweet notes ascribable to ripe fruits, the tasters perceived notes of berries that are not typical of the Correggiolo cultivar.The sensory taint test revealed a statistically significant difference between oils produced from olives treated with kaolin and the control, whereas no difference emerged between oils obtained from olives treated with zeolite and the control.Particle film can influence some physiological plant parameters (photosynthesis, transpiration, water use efficiency) and, by consequence, it has also an influence on olive and oil quality. Olive plants treated with zeolite produced oils with higher antioxidant endowment, while oils produced from plants treated with kaolin were characterized by lower phenolic contents. Moreover, the kaolin treatment significantly affected the organoleptic properties of oils.

The investigation of noble gases (He, Ne, Ar) and CO2 in fluid inclusions (FI) of mantle-derived rocks from the Sub Continental Lithospheric Mantle (SCLM) is crucial for constraining its geochemical features and evolution as well as the volatiles cycle, and for better evaluating the information arising from the study and monitoring of volcanic and geothermal gases. Eastern Transylvanian Basin in Romania is one of the places in Central-Eastern Europe where mantle xenoliths are brought to the surface by alkaline magmatism, offering the opportunity for applying the above-mentioned approach. Moreover, this locality is one of the few places on Earth where alkaline eruptions occurred contemporaneously with calc-alkaline activity, thus being a promising area for the investigation of subduction influence on the magma sources and volatiles composition.In this work, we studied petrography, mineral chemistry and noble gases in FI of mantle xenoliths found in Perşani Mts. alkaline volcanic products. Our findings reveal that the local mantle recorded two main events. The first was a pervasive, complete re-fertilization of a previously depleted mantle by a calc-alkaline subduction-related melt, causing the formation of very fertile, amphibole-bearing lithotypes. Fluids involved in this process and trapped in olivine, opx and cpx, show 4He/40Ar* ratios up to 1.2 and among the most radiogenic 3He/4He values of the European mantle (5.8 ± 0.2 Ra), reflecting the recycling of crustal material in the local lithosphere. The second event is related to a later interaction with an alkaline metasomatic agent similar to the host basalts, that caused slight LREE enrichment in pyroxenes and crystallization of disseminated amphiboles, with FI showing 4He/40Ar* and 3He/4He values up to 2.5 and 6.6 Ra, respectively, more typical of magmatic fluids.Although volcanic activity in the Perşani Mts. is now extinct, strong CO2 degassing (8.7 × 103 t/y) in the neighbouring Ciomadul volcanic area may indicate that magma is still present at depth (Kis et al., 2017; Laumonier et al., 2019). The gas manifestations present from Ciomadul area are the closest to the outcrops containing mantle xenoliths for comparison of the noble gas composition in FI. 3He/4He values from Stinky Cave (Puturosul), Doboşeni and Balvanyos are up to 3.2, 4.4 and 4.5 Ra, respectively, indicating the presence of a cooling magma (Vaselli et al., 2002 and references therein). In the same area and more recently, Kis et al. (2019) measured 3He/4He ratios up to 3.1 Ra, arguing that these values indicate a mantle lithosphere strongly contaminated by subduction-related fluids and post-metasomatic ingrowth of radiogenic 4He. Our findings consider more likely that magmatic gases from Ciomadul volcano are not representative of the local mantle but are being released from a cooling and aging magma that resides within the crust. Alternatively, crustal fluids contaminate magmatic gases while they are rising to the surface. Kis et al. (2017). Journal of Volcanology and Geothermal Research 341, 119–130.Kis et al. (2019) Geochem. Geophys. Geosyst. 20, 3019-3043.Laumonier et al. (2019) Earth and Planetary Science Letters, 521, 79-90.Vaselli et al. (2002) Chemical Geology 182, 637–654.

In this study the geochemical composition of the fluids belonging to the geothermic reservoir of Casaglia is presented. The site is located few kilometers northward of Ferrara, probably the only city in Italy whose heating system is fed by the geothermal heat near the top of the Dorsale Ferrarese, a structural anticline raising the Mesozoic limestones up to few hundred meters below the surface. Measurements of the chemical and isotopic composition of the gas phase (e.g., CO2 and noble gas) were carried out, together with a full characterization of the physico-chemical parameters and the chemistry of the water phase.Fluids derive from a well at a depth of about 322+15meters and the temperature of the emerging water is of 78,6 °C, pH of 6.29 and Eh of -470 mV. Salinity is up to 115.6 mS/cm with a TDS varying between 71024 mg/L and 73718 mg/L. The hydrochemical facies is identified as clorurato-alkaline and the Cl/Br ratio suggest mixing with fossil brines. dD and d18O vary from 4.70 to 5.02 and from -12.0 to -12.2 respectively. The volatile phase is mainly composed of N2 (24.9-40.5 %),CH4 (21.1-29.5 %) and CO2 (37.1-18.6 %), with d13C(CO2), d13C(CH4) and dD(CH4) varying from -4.4 to -3.7 ‰, from -41.7 to 41.2 ‰ and from -152 to -171 ‰, respectively. The He amounts are extraordinary high (up to 3956 ppm) with a 3He/4He of 0.02Ra unequivocally pointing to a crustal origin (e.g., Caracausi & Sulli, 2019). The 40Ar/36Ar ratios span the range 300-374, being very close to the same ratio in atmosphere.Such high He concentration cannot be explained by a simple steady-state crustal degassing, taking into account the Th and U contents of the sedimentary cover and the metamorphic basement (Coltorti et al. 2011) which lead also to consider that the thermal state of the Casaglia reservoir involve the entire crustal thickness and not only the Mesozoic carbonate succession that hosts the reservoir itself.It is inferred that under an active tectonic regime, as it is that where Casaglia is located, the formation of micro-fracturation, due to the field of stress generated by the local seismicity, increases the He release from the rocks and can contribute to the observed He excess in the geothermal reservoirs (e.g., Buttitta et al., 2020). In this respect, the fault system of Dorsale Ferrarese contributes to generate a preferential pathway for rising fluids with consequent mixing phenomena and provides a reasonable explanation about the presence of this high He content in the reservoir.References:Buttitta D. et al. (2020). Continental degassing of helium in an active tectonic setting (northern Italy): the role of seismicity. Scientific Reports, 10(1), 1–13.Caracausi A. & Sulli A. (2019). Outgassing of Mantle Volatiles in Compressional Tectonic Regime Away From Volcanism: The Role of Continental Delamination. Geochemistry, Geophysics, Geosystems, 20(4), 2007–2020.Coltorti M. et al. 2011. U and Th content in the Central Apennines continental crust: a contribution to the determination of the geo-neutrinos flux at LNGS. Geoch. Cosmoch. Acta 75, 2271-2294.

Zeolitites (ZTs) are rocks containing more than 50% of zeolite minerals and are known to be a suitable material for agricultural purposes by improving soil physicochemical properties and nitrogen (N) use efficiency. However, little is known about their effects on soil microbial biomass. This study aimed to evaluate short-term effects of different chabazite-rich ZT (CHAZT) amendments on soil microbial biomass and activity. A silty-clay agricultural soil was amended in three different ways, including the addition of natural (5% and 15%) and NH+4-enriched (10%) CHAZT. Soil dissolved organic carbon (C), total dissolved N, NH+4, NO−3, NO−2, microbial biomass C and N, and ergosterol were measured periodically over 16 d in a laboratory incubation. To verify the microbial immobilization of the N derived from NH+4-enriched CHAZT, a high 15N source was used for enriching the mineral to measure the microbial biomass δ15N signature. An increase in the ergosterol content was observed in the soil amended with 5% natural CHAZT. However, no similar result was observed in the soil amended with 15% natural CHAZT, suggesting that the fungal biomass was favored at a lower CHAZT application rate. In the soil amended with NH+4-enriched CHAZT, microbial biomass N was related to NO−3 production over time and inversely related to NH+4, suggesting high nitrification process. Isotopic measurements on microbial biomass confirmed immediate assimilation of N derived from NH+4-enriched CHAZT. These results suggested that the NH+4-enriched CHAZT used in this study supplied an immediately available N pool to the microbial biomass.

In this paper we report an overview of the main outcomes of a 3-years experimental cultivation carried out in an Italian reclaimed agricultural field amended with different types of zeolitites (rock containing > 50% of zeolites), under cereals cultivation (Sorghum vulgare Pers, Zea mays and Triticum durum). The aim of the experiment was to exploit the properties of zeolite-rich volcanic rocks (zeolitites) for reducing the excessively high NO3− content in the soil and in waters flowing out the sub-surface drainage system of the field and flushing into the surface water system, reducing concomitantly also chemical fertilization application rates (up to 50%). Zeolitites were tested both in their natural state and in a NH4+-enriched form, obtained through an enrichment process with NH4+-rich zoo-technical effluents (pig slurry). NO3− content in soils and in waters discharged through SSDS were periodically monitored during the experimentation and crop yield quantified. Results showed that, for three consecutive cultivation cycles, the overall NO3− concentrations in water extracts was reduced by 45% in the zeolitite treated soils, while in SSDS waters the reduction reached the 64%. Notwithstanding the lower N input from chemical fertilizers, crop yield was not negatively affected in the zeolitite amended soils with respect to the control. Zeolitite addition increased thus soil NH4+ retention and probably influenced several pathways of N losses, allowing a better fertilizer use efficiency by plants and a reduction of the overall NO3− concentrations in the surface waters.

Reducing the effects of climate change is a key-point to achieve sustainable development. It is known that fertilizer application stimulates soil gaseous N losses, especially immediately after their application. In this shortterm incubation experiment, the effects of different chabazite zeolite amendments on soil gaseous emissions (CO2, N2O, NOx and NH3) were evaluated in high resolution as potential mitigation strategy for agricultural soils. Different soil-zeolite mixtures, including both natural and NH4 +-enriched chabazite zeolites, were incubated for 24 h both immediately after the application of urea fertilizer and without a further N input in order to carry out a high resolution investigation of soil CO2, N2O, NOx and NH3 fluxes, in comparison to an unamended soil. Immediate CO2, N2O, NOx and especially NH3 emissions after fertilizer application were generally reduced in soils amended with zeolites at natural state, indicating a potential valuable material for reducing soil C-N gaseous losses. On the other hand, the application of NH4 +-enriched zeolites lowered CO2 and N2O emissions, but very high NOx fluxes occurred during the first 24 h even without applying any further N input. NH3 emissions were higher in NH4 +-enriched zeolites amended soil, but if the amendment is performed without further N inputs, the emissions can be significantly lowered with respect to a conventional urea fertilization. Reducing the effects of climate change is a key-point to achieve sustainable development. It is known that fertilizer application stimulates soil gaseous N losses, especially immediately after their application. In this short-term incubation experiment, the effects of different chabazite zeolite amendments on soil gaseous emissions (CO2, N2O, NOx and NH3) were evaluated in high resolution as potential mitigation strategy for agricultural soils. Different soil-zeolite mixtures, including both natural and NH4+-enriched chabazite zeolites, were incubated for 24 h both immediately after the application of urea fertilizer and without a further N input in order to carry out a high resolution investigation of soil CO2, N2O, NOx and NH3 fluxes, in comparison to an unamended soil. Immediate CO2, N2O, NOx and especially NH3 emissions after fertilizer application were generally reduced in soils amended with zeolites at natural state, indicating a potential valuable material for reducing soil C-N gaseous losses. On the other hand, the application of NH4+-enriched zeolites lowered CO2 and N2O emissions, but very high NOx fluxes occurred during the first 24 h even without applying any further N input. NH3 emissions were higher in NH4+-enriched zeolites amended soil, but if the amendment is performed without further N inputs, the emissions can be significantly lowered with respect to a conventional urea fertilization.

In this paper we present an elemental and isotopic investigation of carbon and nitrogen in the soil-plant system. Plants grown in an unamended soil were compared to plants grown in a soil amended with natural and NH4+-enriched zeolitites. The aim was to verify that zeolitites at natural state increase the chemical fertilization efficiency and the nitrogen transfer from NH4+-enriched zeolitites to plants. Results showed that plants grown on plots amended with zeolitites have generally a δ15N approaching that of chemical fertilizers, suggesting an enhanced nitrogen uptake from this specific N source with respect to the unamended plot. The δ15N of plants grown on NH4+-enriched zeolitites was strongly influenced by pig-slurry δ15N (employed for the enrichment process), confirming the nitrogen transfer from zeolitites to plants. The different agricultural practices are also reflected in the plant physiology as recorded by the carbon discrimination factor, which generally increases in plots amended with natural zeolitites, indicating better water/nutrient conditions.

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 &lt, 6 %.

Combined application of induced MAP (Magnesium Ammonium Phosphate) precipitation and adsorption through natural zeolites for reducing NH4+ and PO43- in swine wastewatersNicola Tescaro*1, Giulio Galamini1, Giacomo Ferretti1, Barbara Faccini, Negar Eftekhari, Massimo Coltorti * Corresponding author1) Department of Physics and Earth Science, University of Ferrara, Ferrara Via Saragat 1 44122, Italy. Modern agriculture, in response to the constantly increasing need of high crop production, requires application of high levels of N and P fertilizers to soil. These substances are mainly composed by nutrients such as NH4+ and PO43- and are often applied in strong excess in order to assure high crop yield. The nutrients applied through fertilizers and not exploited by crops (estimated on average around 50%) can considerably impairs environmental quality through nitrogen losses in atmosphere (N2O, NOx, NH3) and eutrophication of water bodies.In this work, a new method for reducing NH4+ and PO43- in swine wastewaters (commonly used as organic fertilizer) was studied. The aim is to reduce their environmental impact and concomitantly create a new slow-release fertilizer.Two techniques have been combined: the induced MAP precipitation (magnesium ammonium phosphate) and natural zeolite ammonium adsorption for removing the NH4+ excess that generally remains in solution after MAP precipitation. Given the complexity of working with real wastewaters, in this preliminary phase a synthetic analogue was used in order to better evaluate the efficiency of this method. Two synthetic wastewaters with different Mg2+ : NH4+ : PO43- molar ratio were tested: MR1 (1:1,5:1) and MR2 (2:1:1), which according to the literature give the best reductions of NH4+ and PO43-. Since swine wastewater are naturally rich of both NH4+ and K+, isotherm studies were conducted on natural zeolites for evaluating their adsorption capacity of NH4+ under different levels of K+ competition. Results showed that the potential in NH4+ adsorption decreased while competition with K+ increased. The combination of MAP precipitation and NH4+ adsorption by natural zeolite has been tested in 2 ways: 1) zeolite was added before inducing MAP precipitation 2) zeolite was added after inducing MAP precipitation. These two treatments were compared to a blank in which only MAP precipitation technique was used.The amount of NH4+ and PO4+ was monitored in various steps during the experiments as well as SEM observations were conducted on precipitated obtained. Results showed that adding zeolites before MAP precipitation induce a variation in the Mg2+ : NH4+ : PO43- ratio due to cation exchange processes before MAP precipitation which introduce interfering ions such as Ca2+ favoring calcium phosphates precipitation instead of MAP. The best test conditions, which produced the 75,1% of NH4+ and 99,9% of PO43- reductions, occurred when zeolites have been added after MAP precipitation using the MR2. This new material obtained combines good N and P concentration and have therefore potentialities to be a high-quality slow-release fertilizer.

Application of natural zeolitites (ZTs, rock with > 50% of zeolites) as a soil amendment is recognized as a suitable method for increasing substrate quality. ZT is used at natural state or pre-enriched with specific cations (e.g., NH4+) to slow-release nutrients. ZT at natural state has been shown to mitigate gaseous N losses and favor crop yield, while NH4-enriched ZT has been reported to show quick NO3− production and relatively high gaseous N losses. The use of nitrification inhibitors (NIs) could alleviate these losses. In this work, the sorption behavior of a synthetic NI 3,4-dimethylpyrazole phosphate (DMPP) on different soil-ZT mixtures as well as on pure ZTs (natural and NH4-enriched) was tested. High sorption of NI can reduce its inhibitory effects and consequently the nitrogen use efficiency (NUE). Results show that natural ZTs had a deficient capacity for DMPP sorption and thus decreased the possibility to retain DMPP once applied to the soil. The sorption capacity strongly positively correlated to soil organic C content, supporting that sorption was mainly driven by soil organic matter. Any types of ZT added to the soil, notably that at natural state, have decreased the potential sorption of DMPP principally because of a dilution of the total organic C which reduced substrate hydrophobicity. A lower DMPP sorption in the substrate can mean higher availability of DMPP to soil microbial biomass and thus a higher potential in inhibiting nitrification. These beneficial effects may result in an advantageous strategy for increasing NUE.

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.

Submarine methane emissions in the Tuscan Archipelago have been studied since the 1960s, both for economic and research purposes. Offshore gas seepage is mainly concentrated southward and westward of Elba island, along N–S faults related to recent extensional activity in the Tuscan shelf and N–S trending positive magnetic anomalies, which have been interpreted as serpentinites associated with ophiolitic rocks due to their very high magnetic susceptibility. This study focuses on the gas chemistry of a new emission site corresponding to a shallow water mud volcano in the Scoglio d’Affrica area. The Scoglio d’Affrica seep has a gas composition typical of mud volcanoes, with methane as the prevalent component (95 vol%) and minor gases which include carbon dioxide, nitrogen and trace amounts of helium. The combined stable C and H isotope composition of CH4 (δ13C and δ2H) and the enrichment in heavy carbon isotopes of CO2, highlight a prevalent secondary microbial origin for these fluids (δ13C~−35.8‰ vs VPDB; δ2H~−166‰ vs VSMOW; δ13CCO2 up to + 21.7‰ vs VPDB). Thus, in spite of the occurrence of positive magnetic anomalies, a possible abiotic origin of methane is excluded. Moreover, the gas from the mud volcano is extremely depleted in 3He and presents typical 3He/4He ratios of a geological setting in which radiogenic crustal helium is strongly predominant. A photo-mosaic of the mud volcano is also reported. A possible connection with other submarine methane emissions in the Tuscan Archipelago is limited to emissions located few kilometers from the Scoglio d’Affrica area. Recent emissions in the area suggest that gases similar in composition from distinct reservoirs, find their way to the surface from Eocene deposits in different time intervals and through different faults and fractures, placed along the Elba-Pianosa ridge.

Abstract: Cr6+ adsorption by modified vermiculite Valeria Medoro- University of Ferrara , Department of Physics and Earth Sciences, ItalyCelia Marcos Pascual-University of Oviedo, Department of Geology, SpainGiacomo Ferretti- University of Ferrara , Department of Physics and Earth Sciences, ItalyGiulio Galamini- University of Ferrara , Department of Physics and Earth Sciences, ItalyMassimo Coltorti- University of Ferrara , Department of Physics and Earth Sciences, Italy This work aimed at investigating the adsorption of Cr6+ in water by exfoliated vermiculite. The adsorbant tested in this experiment was a vermiculite (from China) which has been subjected to heating at 1000 °C for 1 minute, resulting in an exfoliated vermiculite.Three effects were studied: 1) contact time; 2) initial concentracion of Cr6+; 3) adsorbent mass. Samples were analysed by X Ray Fluorescence (XRF), X Ray Diffraction (XRD) and the solutions with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to quantify the adsorbed Cr6+ by the vermiculite.Results from XRD diffraction showed a conversion of vermiculite into flogopite after heating at 1000°C for 1 minute because of: 1) high content of potassium, 2) dehydration and 3) structural re-ordering; after the contact of vermiculite with Cr6+, the mineral structure did not change. The adsorption of Cr6+ was studied by Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich (DKR) isotherm models. DKR model, indicative of a cooperative process, described adsorption equilibrium better than the other two models and the maximum adsorption capacity obtained was of 2.81 mol/g. Kinetic was studied using pseudo-first and pseudo-second order kinetic models, with a better description of the process by pseudo-second order model with correlation coefficient almost unitary (R2=0.9984; other kinetic parameters were k2=0.0015 and the absorption initial rate of 0.2x10-8 mg g-1 h-1). The present study demonstrates the effectiveness of modified vermiculite adsorbents for the treatment of hexavalent chromium-contaminated waters and that its adsorption depends on the experimental conditions (such as contact time, initial concentracion of Cr6+ and adsorbent mass).

The use of natural sorbent geomaterials, like zeolitites (rocks containing > 50% of zeolites) is recognized as a valid method to recover N in the form of ammonium ions (NH4+) from Zootechnical Wastewaters (ZoWs).Using zeolite-rich tuff as N sorbent from ZoWs lead to varius advantages like the decrease in environmental impact of ZoWs (decreased N content) and the subsequent creation of a high-value soil amendment employable also in organic agriculture (NH4-charged zeolite-tuff).In order to understand the characteristics of NH4-charged zeolites (CZ) as sorbent, it is mandatory a deep investigation on their sorption dynamics when they react with ZoWs. Scientific literature is rich of studies about sorption in sintetic solutions (especially NH4CL) while it lacks studies about sorption in real ZoWs.The aim of this work was therefore to characterize the NH4 sorption dynamics of a chabazite zeolite tuff from swine manure. In particular, two grain sizes were selected, a micronized (< 125 µm, CHAµ) and a granular one (0.7-2.0 mm, CHAg). A series of batch experiments were performed to investigate the effects of temperature, contact time and grain size on sorption of NH4. Equilibrium data were fitted with appropriate isothermal models; kinetic models were also investigated to characterize the kinetik sorption reactions and the thermodinamic parameters like change in free energy (ΔG), enthalpy (ΔH) and entropy (ΔS).Results have shown a significant grain size effect with respect to the equilibrium loading (qe), with better performances for CHAµ in all the temperatures investigated; the isothermal data showed that the influence of temperature is less for CHAµ with respect to CHAg.The kinetic data differs from the two grain size investigated, in particular CHAg showed an initial external surface adsorption and macropore diffusion during the first 60 minutes of contact, then the diffusion occurs also inside the micropores. The Intraparticle Diffusion model (ID) for CHAµ showed that the diffusion in the macropores are much more fast than CHAg and the intercept indicates the formation of a boundary layer thicker than CHAg. Pseudo-second-order kinetic model well explained CHAg behavior but not that of CHAµ. Both grain sizes were well explained by Elovich equation wich is a model used to explain the sorption kinetics for energetically heterogeneous solids surfaces (as likely the surface of the zeolite-tuff employed).Thermodinamic data showed that the energy in the liquid-solid adsorption surfaces increased during adsorption (ΔH ˃ 0), thus the cation exchange reaction needs energy from the liquid phase.The free standard entropy change (ΔS) is also positive, indicating that the NH4 sorption is a directional process with no significant differences with respect to the tested temperatures and that the randomness at the solid-solution interface increased during adsorption.The negative values of Gibbs free energy (ΔG) indicates that the NH4 sorption is an exergonic process (spontaneous reaction).

The use of zeolite-rich tuffs is a valid method for recovering nitrogen from wastewaters. This paper aims at describing the NH4+ adsorption processes of an Italian chabazite zeolite tuff used for the treatment of raw liquid swine manure. The effects of temperature, grain size and contact time were investigated. The isothermal analysis showed a multilayer adsorption behavior, well explained by the Harkins–Jura model, while kinetics was explained by pseudo-second-order, Elovich and intraparticle diffusion models. This study highlighted the complexity of the adsorption process from raw liquid manure, as well as the significant differences between tested particle sizes of the same zeolite tuff.

Calc-alkaline and alkaline magmatic activity is generally separated in space and/or in time. The Eastern Transylvanian Basin in Romania is one of the few places where, during Pleistocene, alkaline eruptions occurred contemporaneously with the calc-alkaline activity. Mantle xenoliths entrained in Persani Mts. alkaline volcanic products have been studied in order to investigate the interaction of metasomatic agents of different magmatic affinities with the mantle wedge. Based on mineral major and trace element and noble gases in fluid inclusions, two main events have been recognized. The first was a pervasive, complete re-fertilization of a previously depleted mantle by a calc-alkaline subduction-related melt, causing the formation of very fertile, amphibole-bearing lithotypes. This is shown by the a) increased amounts of modal clinopyroxene up to 21.9 % with Al2O3 contents up to 8.16 wt%, higher than what is expected for clinopyroxene in Primordial Mantle; b) 4He/40Ar* ratios up to 1.2, within the reported range for mantle production; c) 3He/4He in olivine, opx and cpx of 5.8 ± 0.2 Ra, among the most radiogenic values of European mantle, below the typical MORB mantle value (8 ± 1 Ra), reflecting recycling of crustal material in the local lithosphere. The second event is related to later interaction with an alkaline metasomatic agent similar to the host basalts that caused slight LREE enrichment in pyroxenes and disseminated amphiboles and precipitation of vein amphiboles with a composition similar to amphiboles megacrysts also found in the Persani Mts. volcanic deposits. This is highlighted by the 4He/40Ar* and 3He/4He values found in some opx and cpx, up to 2.5 and 6.6 Ra, respectively, more typical of magmatic fluids.

Na+ contamination of irrigation waters represents a global environmental issue for soil structure and plant production. Notwithstanding several techniques for the reduction of Na+ have been proposed in recent years, they generally exhibit disadvantages, including low recyclability and relatively high operational/maintenance costs. In this paper, we propose a natural and eco-friendly solution for the reduction of Na+ risk in coastal agricultural sandy soil (SS), vulnerable to salinity stress. A series of column leaching experiments have been conducted to assess the influence of Italian zeolite-rich tuff (natural zeolites, NZ) addition to soil (NZSS) on Na+ removal, SAR, and CROSS index, under three different salinity scenario. Result showed that the Na+ removal efficiency varied between 46.4 and 54.3% in soil amended with NZ, and analogously SAR index was significantly reduced from 7 to up 13 points. SAR and CROSS indexes resulted better correlated in SS rather than NZSS due to the influence of K+ released by NZ. In conclusion, soil amendment with NZ represents a natural and eco-friendly solution for increasing sandy soil resilience to Na+ risk.

Using saturated or enriched zeolites as slow release fertilizers (SRFs) is considered as an environmental-friendly strategy to enhance use of macronutrients in sandy soils. In this paper, two natural zeolites, clinoptilolite (CLI) and chabazite (CHA) were used as mineral precursors to prepare NH₄⁺/K⁺ saturated clinoptilolite (NH₄⁺/K⁺-CLI) and chabazite (NH₄⁺/K⁺-CHA) as zeolitic nutrient sources (ZNSs). Comparison between the nutrient retention capabilities of these ZNSs was one of the main objectives of this study. The NH₄⁺/K⁺-CLI and NH₄⁺/K⁺-CHA were prepared by soaking the zeolites in NH₄Cl and KCl solutions, respectively. Leaching tests were performed on a sandy soil amended with chemical fertilizers (CFs), NH₄⁺/K⁺-CLI and NH₄⁺/K⁺-CHA to evaluate the leaching properties of them. The results indicated that approximately 84% and 88% of the NH₄⁺ and K⁺ of soils fertilized with CFs were lost during the experiment, respectively. While, the NH₄⁺ and K⁺ losses from soils amended with NH₄⁺/K⁺-CLI and NH₄⁺/K⁺-CHA were 29%, 23%, and 14%, 24%, respectively. Despite of drastic changes in leaching behavior of CFs, nutrient losses from ZNSs were more uniform during the experiments. No significant difference was found between the two studied zeolites on reduction of K⁺ loss. However, CHA was more effective in preventing NH₄⁺ loss during leaching.

Po River Delta is situated in the Padania Plain at the confluence with the Adriatic Sea. Since the second half of the nineteenth century, human activities have been focused on the reclamation of wetlands, in order to use them for agricultural purposes. Nowadays these reclaimed soils are mainly used to cultivate cereals and horticultural crops. The mail problem related to this kind of soils is their capability to retain heavy metals. These can be transferred to the cultivations and to the humans, being in some cases very dangerous. It is therefore fundamental to investigate the amount of heavy metals present in reclaimed soils and that which could be transferred to the plants. With this aim, a reclaimed soil that has been used for sorghum cultivation was chosen as test field. Heavy metal concentrations of the soil, the rhizosphere and the seeds, as well as the roots and some aerial parts of the sampled sorghum were measured, respectively. High Cr and Ni concentrations were detected in the soil and rhizosphere samples, related to their natural availability due to the presence of chlorite and serpentine in these soils. On the contrary in the seeds, micronutrients such as Zn and Cu have higher concentrations with respect to Cr and Ni, but all the metals (except Cd) are below the national admitted limits. Metals classified as non-essential for humans (As, Cd, Cr, Ni) are scarcely absorbed by the plant, and their average concentrations decreased according to this pathway: soil > rhizosphere > root > aerial parts > seed. Cd, Zn and As are richer in the rhizosphere with respect to the bulk soil. © 2017, Springer-Verlag GmbH Germany., This work has been supported by EC LIFE+ funding to ZeoLIFE project (LIFE + 10 ENV/IT/000321).

Reclaimed salt marshes are fragile environments where water salinization and accumulation of heavy metals can easily occur. This type of environment constitutes a large part of the Po River Delta (Italy), where intensive agricultural activities take place. Given the higher Ni background of Po River Delta soils and its water-soluble nature, the main aim of this contribution is to understand if reclamation can influence the Ni behavior over time. In this study, we investigated the geochemical features of 40 soils sampled in two different localities from the Po River Delta with different reclamation ages. Samples of salt marsh soils reclaimed in 1964 were taken from Valle del Mezzano while soils reclaimed in 1872 were taken nearby Codigoro town. Batch solubility tests and consecutive determination of Ni in pore-water were compared to bulk physicochemical compositions of soils. Bulk Ni content of the studied soils is naturally high, since these soils originated from Po River sediments derived from the erosion of ultramafic rocks. Moreover, it seems that Ni concentration increases during soil evolution, being probably related to the degradation of serpentine. Instead, the water-soluble Ni measured in the leaching tests is greater in soils recently reclaimed compared to the oldest soils. Soil properties of two soil profiles from a reclaimed wetland area were examined to determine soil evolution over one century. Following reclamation, pedogenic processes of the superficial horizons resulted in organic matter mineralization, pH buffer, and a decrease of Ni water solubility from recently to evolved reclaimed soil. © 2017, Springer International Publishing AG., This work has been supported by EC LIFE+ funding to ZeoLIFE project (LIFE+10 ENV/IT/000321) and by the project ALPIMED (PIE-CSIC-201530E082).

Summary Shallow lenses in reclaimed coastal areas are precious sources of freshwater for crop development, but their seasonal behaviour is seldom known in tile-drained fields. In this study, field monitoring and numerical modelling provide a robust conceptual model of these complex environments. Crop and meteorological data are used to implement an unsaturated flow model to reconstruct daily recharge. Groundwater fluxes and salinity, water table elevation, tile-drains’ discharge and salinity are used to calibrate a 2D density-dependent numerical model to quantify non-reactive solute transport within the aquifer–aquitard system. Results suggest that lateral fluxes in low hydraulic conductivity sediments are limited, while water table fluctuation is significant. The use of depth-integrated monitoring to calibrate the model results in poor efficiency, while multi-level soil profiles are crucial to define the mixing zone between fresh and brackish groundwater. Measured fluxes and chloride concentrations from tile-drains not fully compare with calculated ones due to preferential flow through cracks.

Agricultural practices can jeopardize soil and water quality, thus mitigation measures to reduce nutrient loss and to protect water resources have to be implemented in order to ensure a sound environmental quality and, at the same time, a high crop yield. Natural zeolites have been tested as soil conditioner to diminish nutrient leaching and increase irrigation efficiency. In this study, an experimental site of 6 ha was monitored for two years to assess whether amending the soil with natural zeolite may induce a considerable impact on the water balance. Three control parcels were cultivated and irrigated according to the traditional way; two parcels were amended with coarse-grained natural zeolite at different zeolite/soil ratio (5 and 15 kg/m2) and two parcels were amended with fine-grained zeolite (7 and 10 kg/m2). Soil electrical conductivity, temperature and volumetric water content were continuously monitored via TDR probes at different depths. Climatic variables for water balance calculation were obtained by a meteorological station installed on-site. Continuous monitoring highlighted an increase of soil water availability in the amended parcels with respect to the control ones. The parcel amended with 10 kg/m2 of fine-grained natural zeolite showed an average water content always higher than the control ones, in the upper soil horizon. In addition, after intense rainfall, this parcel showed an increased field capacity and a reduced percolation towards the deeper soil horizon. Finally, the residual water content was improved by 1.2 ± 0.4 % throughout the summer droughts.