Stearate-Coated Biogenic Calcium Carbonate from Waste Seashells: A Sustainable Plastic Filler.

Waste seashells from aquaculture are a massive source of biogenic calcium carbonate (bCC) that can be a potential substitute for ground calcium carbonate and precipitated calcium carbonate. These last materials find several applications in industry after a surface coating with hydrophobic molecules, with stearate as the most used. Here, we investigate for the first time the capability of aqueous stearate dispersions to coat bCC powders from seashells of market-relevant mollusc aquaculture species, namely the oyster Crassostrea gigas, the scallop Pecten jacobaeus, and the clam Chamelea gallina. The chemical-physical features of bCC were extensively characterized by different analytical techniques. The results of stearate adsorption experiments showed that the oyster shell powder, which is the bCC with a higher content of the organic matrix, showed the highest adsorption capability (about 23 wt % compared to 10 wt % of geogenic calcite). These results agree with the mechanism proposed in the literature in which stearate adsorption mainly involves the formation of calcium stearate micelles in the dispersion before the physical adsorption. The coated bCC from oyster shells was also tested as fillers in an ethylene vinyl acetate compound used for the preparation of shoe soles. The obtained compound showed better mechanical performance than the one prepared using ground calcium. In conclusion, we can state that bCC can replace ground and precipitated calcium carbonate and has a higher stearate adsorbing capability. Moreover, they represent an environmentally friendly and sustainable source of calcium carbonate that organisms produce by high biological control over composition, polymorphism, and crystal texture. These features can be exploited for applications in fields where calcium carbonate with selected features is required.

Pot experimental trial for assessing the role of different composts on decontamination and reclamation of a polluted soil from an illegal dump site in Southern Italy using Brassica juncea and Sorghum bicolor.

A pot experiment was carried out to evaluate the remediation potential of Brassica juncea and Sorghum bicolor in the decontamination of soil polluted with heavy metals such as copper, lead, tin, and zinc along with polychlorinated biphenyls, polycyclic aromatic hydrocarbons, and heavy hydrocarbons. Two composts obtained from different composting processes were tested as biostimulating agents. At the end of the trial, the effect of plant/compost combinations on soil microbial composition, contaminant removal, biochemical indicators, and plant biomass production was determined. The results highlighted that compost addition improved plant biomass despite slowing down plants' removal of organic and inorganic contaminants. In addition, compost partially enhanced the soil biochemical indicators and modified the relative abundance of the rhizosphere microorganisms. Sorghum showed better mitigation performance than Brassica due to its higher growth. The soil fertility level, the choice of plant species, and microbial richness were found fundamental to perform soil remediation. In contrast, compost was relevant for a higher crop biomass yield.

The ground beetle Pseudoophonus rufipes gut microbiome is influenced by the farm management system.

Intensive conventional farm management, characterized by high agrochemicals input, could alter the composition of microbial communities with potential negative effects on both functional traits and the ecosystem services provided. In this study, we investigated the gut microbial composition of a high ecological relevance carabid Pseudoophonus rufipes, sampled in two fields subjected to conventional and organic management practices. Carabids' gut microbiota was analyzed via qPCR and NGS. Profound differences between the microbial composition of organic and conventional samples were detected: the abundance of Tenericutes and Proteobacteria was significant higher in organic and conventional samples, respectively. Spiroplasmataceae and Bifidobacteriaceae families were significantly more abundant in samples from organic management, while Enterococcaceae, Morganellaceae and Yersiniaceae were more abundant in samples from conventional management. The diverse gut microbial composition of insects between the two management systems is related to the pressure of environmental stressors and it may representing an important bioindication of ecological functions and services provided by a carabid species.

A non-lethal method to assess element content in the endangered Pinna nobilis.

The fan shell Pinna nobilis is the largest bivalve endemic to the Mediterranean and is actually a strongly endangered species. Due to the biological, ecological, and historical relevance of this species, the research of a non-lethal method to relate the element content in organism's tissues and environment can provide information potentially useful to evaluate environmental pollution and organism physiological status. In this study, a screening on element concentration in the animal growing environment (seawater and sediments) and in four soft tissues (hepatopancreas, gills, mantle, and muscle), and two acellular tissues (calcite shell layer, and byssus) was performed. The comparison among these results was used to assess whether the no-lethal acellular tissue element concentration can be used to reveal the element presence in the environment and soft tissues. Elements, such as B, Ag, As, Mn, Mo, Pb, or Se, showed a possible relationship between their presence in the byssus and soft tissues. In the byssus Cr, Sb, Sn, and V have shown to be mostly related to the environment, more than the soft tissues, and might be used to draw a historical record of the exposure of the organism. The element concentration in the calcite shell layer did not relate with environmental element concentrations. Essential elements, like Cu, Fe, Ni, and Zn, were present in calcite shell layer and byssus and are likely related to their biological activity in the organism. The research also gave an overview on the presence of pollution and on the preferential intake route of the element. In summary, this study, performed on a limited number of specimens of this protected species, indicated that element concentration in the byssus can be applied as non-lethal method to monitor this endangered species and its interaction with the elements in the growing environment.

Fourteen years of compost application in a commercial nectarine orchard: effect on microelements and potential harmful elements in soil and plants.

The objective of this experiment was to valuate, after 14 years, the impact of annual compost applications on micronutrient and potentially toxic trace elements on nectarine tree uptake and soil fertility. The study was performed in the Po valley, Italy, on the variety Stark RedGold (grafted on GF677). Since orchard planting, the following treatments were applied, in a randomized complete block design, with four replicates: 1. unfertilized control; 2. mineral fertilization (N was supplied as NO3NH4 at 70-130 kg ha-1 year-1); 3. compost at 5 t DW ha-1 year-1; 4. compost at 10 t DW ha-1 year-1. The actual rate of application was 12.5 (LOW) and 25 (HIGH) t ha-1, since compost was concentrated in the tree row. Compost was made from domestic organic wastes mixed with pruning material from urban ornamental trees and garden management and stabilized for 3 months. The supply of compost HIGH induced an enrichment of soil total Cu, Zn and Cd, and a decrease of Fe and Co concentration; with values always below the European threshold limits for heavy metals in the soil. In addition, compost (at both rates) increased availability (DTPA-extractable) of Fe, Mn and Zn, Cd, Ni, and Pb in the top soil (0-0.15 m). Total micronutrient and trace element tree content was not affected by fertilization treatments; however, the recycled fraction returned to the soil at the end of the season through abscised leaves and pruned wood of Cu, Fe, Mn and Zn was increased by mineral fertilization; Fe and Zn also by compost HIGH. Our data show that the introduction of compost at both 12.5 and 25 t ha-1 year-1 in the row did not increase the risk of pollution related to potentially toxic trace elements and at the same time increased the bioavailability of Fe, Mn and Zn.

Metal ion removal using waste byssus from aquaculture.

Byssus is a thread-like seafood waste that has a natural high efficiency in anchoring many metal ions thanks to its richness of diverse functional groups. It also has structural stability in extreme chemical, physical and mechanical conditions. The combination of these properties, absent in other waste materials, has novelty suggested its use as matrix for water remediation. Thus, pristine byssus, upon de-metalation, was studied to remove metal ions from ideal solutions at pH 4 and 7, as model chemical systems of industrial and environmental polluted waters, respectively. The byssus matrix's uptake of metal ions was determined by ICP-OES and its surface microstructure investigated by SEM. The results showed that the byssus matrix excellently uptakes metal ions slightly reorganizing its surface micro-structure. As example of its efficiency: 50 mg of byssus absorbed 21.7 mg·g-1 of Cd2+ from a 10 mM solution at pH 7. The adsorption isotherm models of Freundlich and Langmuir were mainly used to describe the system at pH 7 and pH 4, respectively. In conclusion, we showed that the byssus, a waste material that is an environmental issue, has the potential to purify polluted industrial and environmental waters from metal ions.

The fertilising potential of manure-based biogas fermentation residues: pelleted vs. liquid digestate.

Spreading of manure on agricultural soils is a main source of ammonia emissions and/or nitrate leaching. It has been addressed by the European Union with the Directives 2001/81/EC and 91/676/EEC to protect the environment and the human health. The disposal of manure has therefore become an economic and environmental challenge for farmers. Thus, the conversion of manure via anaerobic digestion in a biogas plant could be a sustainable solution, having the byproducts (solid and liquid digestates) the potential to be used as fertilizers for crops. This work aimed at characterizing and assessing the effect of digestates obtained from a local biogas plant (Biogas Wipptal, Gmbh), either in the form of liquid fraction or as a solid pellet on: (i) the fertility of the soils during an incubation experiment; (ii) the plant growth and nutritional status of different species (maize and cucumber). Moreover, an extensive characterization of the pellet was performed via X-ray microanalytical techniques. The data obtained showed that both digestates exhibit a fertilizing potential for crops, depending on the plant species and the fertilizer dose: the liquid fraction increases the shoot fresh weight at low dose in cucumber, conversely, the solid pellet increases the shoot fresh weight at high dose in maize. The liquid digestate may have the advantage to release nutrients (i.e. nitrogen) more rapidly to plants, but its storage represents the main constraint (i.e. ammonia volatilization). Indeed, pelleting the digestates could improve the storability of the fertilizer besides enhancing plant nutrient availability (i.e. phosphate and potassium), plant biomass and soil biochemical quality (i.e. microbial biomass and activity). The physical structure and chemical composition of pellet digestates allow nutrients to be easily mobilized over time, representing a possible source of mineral nutrients also in long-term applications.

Organic wastes as alternative sources of phosphorus for plant nutrition in a calcareous soil.

Recycled organic wastes (OW) can be a valuable P source; however, their P-fertilising capacity is still poorly known. In this study, we selected three anaerobic digestates [wastewater sludge (D1), winery sludge (D2), and bovine-slurry/energy crops (BD)] and two animal effluents [bovine slurry (BS) and swine slurry (SS)] to test their P-release and P-fertilising capacities via sequential chemical extraction (SCE), X-ray diffraction (XRD), and 31P-nuclear magnetic resonance (31P NMR). Subsequently, the three digestates (30 mg P kg-1 of soil) were compared for the release of Olsen-P during a soil incubation and for plant-P apparent recovery (ARF) in a pot experiment using ryegrass (112 days) in a soil with poorly available-P (Olsen-P < 5 mg kg-1), under a non-limiting N environment. The amount of labile-P (H2O + NaHCO3), as determined from SCE, related well to the Olsen-P following OW addition to the soil. It was shown via 31P NMR spectroscopy that orthophosphate was the leading P-form in highly P-releasing OW. The amount of labile-P, however, was affected by soil adsorption, thereby reducing plant-P uptake. The plant-P ARF (%) showed that the recycled P-sources were clustered in highly (BD and SS: ≈20%), intermediately (D1 and BS: ≈15%), and poorly performing OWs (D2: ≈10%) vs. chemical P-source (P-chem: 20%). Therefore, only BD and SS were effective alternatives to P-chem; however, the other OW can be efficient P-sources in soils with higher Olsen-P. Thus, crop fertilisation can be tailored on a P-basis by SCE as a function of soil adsorption capacity and on an N-basis according to the demand.

Soil-plant nitrogen pools in nectarine orchard in response to long-term compost application.

The search for sustainable source of N, the need of soil organic matter restoration, along with the call for recycling of organic wastes has led to a rise of the use of organic fertilizers. The aim of the present experiment was to evaluate: the effectiveness of compost application as a N fertilizer, the impact on N distribution in soil and plant and on tree performances, in a long-term experiment (14 years). The study was carried out in the Po valley, Italy and, since orchard planting (2001), the following treatments were applied: 1. unfertilized control; 2. mineral fertilization; 3. compost at a rate of 5 t DW ha-1 yr-1; 4. compost at a rate of 10 t DW ha-1 yr-1. Soil total N, potentially mineralizable, microbial and extractable N were higher in compost in comparison to mineral (fertilizer). The effect was found both in the row and in the inter-row and the rise of N fractions was evident in the shallowest soil layer of the row. Soil mineral, potentially mineralizable N was increased by mineral (11.1 mg kg-1) and compost 10 (12.4 mg kg-1) fertilization compared with control (6.7 mg kg-1). Vegetative growth and yield were increased in trees treated with mineral and compost 10; moreover, these plants were able to recycle (66.1 and 70.5 kg ha-1 yr-1, respectively) and remobilize (41.5 and 48.7 kg ha-1 yr-1, respectively) a higher amount of N than those of control and compost 5. In conclusion, organic fertilization strategy promoted the buildup of soil N reserve, meaning a capacity of the ecosystem to sequestrate N. The application of compost 10 showed a similar effect on plant growth and production as mineral fertilization, but introduced the advantage of the use of a cheap, renewable waste material, providing a new insight on N fertilization management.

Delivery systems for agriculture: Fe-EDDHSA/CaCO3 hybrid crystals as adjuvants for prevention of iron chlorosis.

Fe-EDDHSA/CaCO3 hybrid crystals are synthesized and tested in vitro to determine their effect in treating iron chlorosis in kiwifruit plants, used as a proof of concept. Under the alkaline conditions provided by the calcareous substrate, plants release protons that dissolve the hybrids and trigger Fe uptake. These CaCO3 hybrids represent a new system for active molecule delivery in agriculture.

Effect of iron sulphate on the phosphorus speciation from agro-industrial sludge based and sewage sludge based compost.

Composting is considered a suitable process for organic waste management, providing stable products that can be safely utilized as fertilizers, but little is still known about the variation of phosphorous (P) extractability during the stabilization process. In this work, sequential chemical extraction (SCE) with increasing strength extractants (H2O; 0.5M NaHCO3 pH 8.5; 0.1M NaOH, 1M HCl) was applied for P speciation over 56days of composting of either agro-industrial or urban wastewater sludge with green waste treated (AICFe+; SSCFe+) or not (AICFe-; SSCFe-) with FeSO4 (2%v/v). Composting strongly reduced the H2O-P, promoting the organic-P (Po) mineralization from the labile fraction (H2O+NaHCO3 40%), in addition to the increases of NaHCO3- and HCl-extractable inorganic-P (Pi) in both AICFe- and SSCFe- (+20% on average). The FeSO4 treatment did not negatively affect the process, reducing the Po mineralization during composting by increasing the NaOH-P, also protecting this fraction from fixation in the sparingly soluble fraction. The final P fractionation (%) was in AICFe-: NaOH (41)=NaHCO3 (38)>HCl (18)>H2O (3); in AICFe+: NaOH (53)>NaHCO3 (24)=HCl (22)>H2O (2); in SSCFe-: NaOH (46)>NaHCO3 (29)>HCl (21)>H2O (4) and in SSCFe+: NaOH (66)>NaHCO3 (13)>HCl (20)>H2O (1). Composting reduced the more easily leachable fraction (labile-Po), reducing the risk of P loss by increasing the long-term available P fraction (NaOH-P). This was enhanced by the FeSO4 addition. Further investigation into soil behaviour and plant availability of P from this source is needed.

Relationships between stability, maturity, water-extractable organic matter of municipal sewage sludge composts and soil functionality.

Compost capability of restoring or enhancing soil quality depends on several parameters, such as soil characteristics, compost carbon, nitrogen and other nutrient content, heavy metal occurrence, stability and maturity. This study investigated the possibility of relating compost stability and maturity to water-extractable organic matter (WEOM) properties and amendment effect on soil quality. Three composts from municipal sewage sludge and rice husk (AN, from anaerobic wastewater treatment plants; AE, from aerobic ones; MIX, from both anaerobic and aerobic ones) have been analysed and compared to a traditional green waste compost (GM, from green manure, solid waste and urban sewage sludge). To this aim, WEOMs were characterized through chemical analysis; furthermore, compost stability was evaluated through oxygen uptake rate calculation and maturity was estimated through germination index determination, whereas compost impact on soil fertility was studied, in a lab-scale experiment, through indicators as inorganic nitrogen release, soil microbial biomass carbon, basal respiration rate and fluorescein di-acetate hydrolysis. The obtained results indicated that WEOM characterization could be useful to investigate compost stability (which is related to protein and phenol concentrations) and maturity (related to nitrate/ammonium ratio and degree of aromaticity) and then compost impact on soil functionality. Indeed, compost stability resulted inversely related to soil microbial biomass, basal respiration rate and fluorescein di-acetate hydrolysis when the products were applied to the soil.

Ureic nitrogen transformation in multi-layer soil columns treated with urease and nitrification inhibitors.

The use of N-(n-butyl)thiophosphoric triamide (NBPT), as a urease inhibitor, is one of the most successful strategies utilized to increase the efficiency of urea-based fertilization. To date, NBPT has been added to the soil incorporated in fertilizers containing either urea or the inhibitor at a fixed percentage on the urea weight. The possibility of using NBPT physically separated from urea-based fertilizers could make its use more flexible. In particular, a granulated product containing NBPT could be utilized in soils treated with different urea-based fertilizers including livestock urine, the amount depending on soil characteristics and/or the urea source (e.g., mineral fertilizer, organo-mineral fertilizer, or animal slurry). In this study, a multilayer soil column device was used to investigate the influence of an experimental granular product (RV) containing NBPT and a garlic extract, combining the ability to protect NBPT by oxidation and nitrification inhibition activity, on (a) spatial variability of soil urease and nitrification activities and (b) timing of urea hydrolysis and mineral-N form accumulation (NO(2)(-), NO(3)(-), NH(4)(+)) in soil treated with urea. The results clearly demonstrated that RV can, effectively, inhibit the soil urease activity along the soil column profile up to 8-10 cm soil layer depth and that the inhibition power of RV was dependent on time and soil depth. However, nitrification activity is not significantly influenced by RV addition. In addition, the soil N transformations were clearly affected by RV; in fact, RV retarded urea hydrolysis and reduced the accumulation of NH(4)(+)-N and NO(2)(-)-N ions along the soil profile. The RV product was demonstrated to be an innovative additive able to modify some key ureic N trasformation processes correlated with the efficiency of the urea-based fertilization, in a soil column higher than 10 cm.

Characterisation of Ca- and Al-pectate gels by thermal analysis and FT-IR spectroscopy.

Thermal analysis (TG-DTA) and FT-IR spectroscopy have been performed on calcium-pectate membranes to investigate their structure and the consequent variation caused by aluminium sorption. Calcium-polygalacturonate (Ca-PG) membranes, model systems of the soil-root interface, were exposed to aluminium solutions at different concentrations (25-800 microM). Three different pHs (3.50, 4.00 and 4.50) were chosen to study the influence of different aluminium species, such as [Al(H2O)6]3+, [Al(OH)(H2O)5]2+ and [Al(OH)2(H2O)(4)]+, on the structure of the Ca-PG membrane. The DTA profiles and FT-IR spectra showed how aluminium sorption induces structural modifications leading to a reorganisation of the chain aggregates and a weakening of the structure. Higher pH, that is, 4.00 and 4.50, and thus hydrolytic aluminium species and related higher calcium content maintain a more regular structure than at pH 3.50. At pH 3.50, both the effect of [Al(H2O)6]3+ and a major calcium release had a greater impact and thus induced a greater weakening of the structure.