Characterization of Volcano-Sedimentary Rocks and Related Scraps for Design of Sustainable Materials.

This work started as a joint academia and company research project with the aim of finding new applications for domestically sourced volcanic products and related waste (pumice, lapillus, zeolitic tuff and volcanic debris from Tessennano and Arlena quarry) by creating a database of secondary volcanic raw materials and their intrinsic characteristics to help industry replace virgin materials and enhance circularity. In this context, accurate chemical, mineralogical, morphological, granulometric and thermal characterizations were performed. Based on the results presented, it can be concluded that due to their lightness, these materials can be used in the design and preparation of lightweight aggregates for agronomic purposes or in the construction field. Furthermore, due to their aluminosilicate nature and amorphous fraction, pumice and lapillus can play the role of precursor or activator for geopolymer preparation. With its porous nature, zeolitic tuff can be exploited for flue gas treatment. Due to the presence of feldspathic phase (sanidine), these materials can be used in tile production as a fluxing component, and with their pozzolanic activity and calcium content, they have application in the binder field as supplementary cementitious material or as aggregates.

Valorization of coffee wastes as plant growth promoter in mulching film production: A contribution to a circular economy.

Food waste valorization, considered as energy and/or chemicals source, via biorefinery or biotechnology, gained great attention in recent years, because of the fast depletion of primary resources, increased waste generation and landfilling worldwide. Coffee by-products for example (i.e. coffee pulp, coffee husks, silver skin, spent coffee, etc.) have been investigated in different forms either as a source of antioxidant and valuable chemicals and as a filler in composites. A new valorization route for coffee silver skin (CSS), up to now just sent to damping, is here investigated: particulate bio-composites based on poly(butylene succinate-co-adipate) (PBSA), an aliphatic biodegradable polyester commercially available, have been formulated with up to a 30 wt% of CSS, in order to prepare mulching films for agriculture. The bacterial analysis of the filler indeed, has underlined the presence of potential Plant Growth-Promoting Bacteria species, mainly ascribed to the Bacillus genus, which can survive both the roasting and the compounding processes. The obtained composites have been characterized mechanically and thermally and their hydrophilic nature has been investigated by measuring their contact angle. Eventually, the bacteria release from the composite films has been examined by means of in-vitro tests. The plant growth promoting capability of the films was preliminarily evaluated in pot experiments using lettuce as a model crop. The composite films were able to release the endogenous bacteria in the soil and to stimulate plant and root growth of the assayed crop. The possibility to produce functionalized biodegradable mulching films by recycling agricultural wastes can thus be forecast, highlighting potential multiple advantages in terms of soil preservation/fertilization, decrease of polymeric materials in mulching products, exploitation of a waste.

Ants associate with microlepidoptera galleries in leaves of Acrostichum danaeifolium Langsd. & Fisch

ABSTRACT Acrostichum danaeifolium, a Neotropical fern, occurs preferentially in marshy areas or at the margins of lakes and mangroves. Microlepidoptera larvae burrow through the petioles of the fern, preferentially on the non-expanded leaves. The galleries in the petiole create a new microhabitat, harboring a rich fauna of arthropods. The aim of the present study was to assess the richness of ants associated with its petiole. The study was conducted in a population of A. danaefolium from the Atlantic Forest in Rio de Janeiro state, Southeastern Brazil. Six collections were carried out every two months (2009-2010), three in the dry and three in the rainy season. The leaves were divided into three development stages: non-expanded leaves (NEL), expanded leaves (EL) and senescent leaves (SL). Seven leaves from each phase were randomly collected from seven individuals. A total of fifteen ant species were recorded. The species with the highest frequency and density in fern petioles were Camponotus crassus and Crematogaster curvispinosa. The highest ant richness and abundance was found in senescent leaves. The high number of ants found in the petioles of Acrostichum danaefolium qualifies it as a potential key species in the marshes and flooded areas where it occurs.

Ants associated with fronds of the tropical bracken fern Pteridium esculentum subsp. arachnoideum / Formigas associadas às frondes da samambaia Pteridium esculentum subsp. arachnoideum

Abstract: Pteridium is a cosmopolitan genus of ferns that possess nectaries on its fronds (fern leaves), thereby attracting ants. Foliar (or extrafloral) nectaries are nectar-producing glands that are not related to pollination, but rather attract ants and other arthropods. Foliar nectaries are found in 101 fern species, belonging to 11 genera and six families. The aim of the study is to characterize the community of ants that visit the fronds of Pteridium esculentum subsp. arachnoideum, as well as daily and seasonal ant abundance in different frond development stages. The study was conducted in the Atlantic Forest of Rio de Janeiro state, Brazil. Bimonthly collections were established, where 30 expanding fronds and 30 fully expanded fronds were randomly marked. In each 1-hour shift starting at 8:30 am and ending at 5:30 pm, the fronds were observed for the presence of ants. Thirty three ant species were recorded on the Pteridium esculentum subsp. arachnoideum fronds, distributed into six subfamilies and 13 genera. The most abundant species were Solenopsis sp.1 and Ectatomma tuberculatum. Eight ant species were observed foraging the nectaries of tropical bracken fern fronds. Ectatomma tuberculatum has been observed feeding on the nectaries and patrolling the fronds. Ant activity peak was on mid-day during the rainy season. The tropical bracken fern Pteridium esculentum subsp. arachnoideum has a rich (the highest recorded until now on Pteridium species) and diverse ant community on its fronds, mainly on the expanding fronds. The presence of generalist predatory ants (Ectatomma tuberculatum and Solenopsis sp.1) during the entire study period suggests a positive interaction between ants and Pteridium esculentum subsp. arachnoideum.

Resumo: Pteridium é um gênero cosmopolita de samambaias que possui nectários em suas frondes (folhas de samambaias), atraindo formigas. Nectários foliares (ou extraflorais) são glândulas produtoras de néctar que não estão relacionadas com a polinização, mas podem atrair formigas e outros artrópodes. Nectários foliares já foram registrados em 101 espécies de samambaias, pertencentes a 11 gêneros e seis famílias. O objetivo do estudo é caracterizar a comunidade de formigas que visitam as frondes de Pteridium esculentum subsp. arachnoideum, bem como a abundância diária e sazonal das formigas em diferentes estágios foliares. O estudo foi realizado na Mata Atlântica do estado do Rio de Janeiro, Brasil. Foram estabelecidas coletas bimestrais, onde foram marcadas aleatoriamente 30 frondes em expansão e 30 frondes totalmente expandidas. Em cada turno de 1 hora com início às 8h30 e término às 17h30, as frondes marcadas foram observadas quanto à presença de formigas. Trinta e três espécies de formigas foram registradas nas frondes do Pteridium esculentum subsp. arachnoideum, distribuídas em seis subfamílias e 13 gêneros. As espécies mais abundantes foram Solenopsis sp.1 e Ectatomma tuberculatum. Foram registradas oito espécies de formigas forrageando os nectários foliares da samambaia. Ectatomma tuberculatum foi observada se alimentando nos nectários e patrulhando as frondes. As formigas tiveram o pico de atividade ao meio-dia e na estação chuvosa. A samambaia tropical Pteridium esculentum subsp. arachnoideum tem uma elevada riqueza (a maior já registrada até o momento para espécies de Pteridium) e diversidade de formigas em suas frondes, com maior frequência nas frondes não totalmente expandidas. A presença de formigas predadoras generalistas (Ectatomma tuberculatum e Solenopsis sp.1) durante todo o período de estudo sugere uma interação positiva entre as formigas e Pteridium esculentum subsp. arachnoideum.

The Effect of Fibrous Reinforcement on the Polycondensation Degree of Slag-Based Alkali Activated Composites.

Alternative cementitious binders, based on industrial side streams, characterized by a low carbon footprint, are profitably proposed to partially replace Portland cement. Among these alternatives, alkali-activated materials have attracted attention as a promising cementitious binder. In this paper, the chemical stability of the matrix, in fiber-reinforced slag-based alkali-activated composites, was studied, in order to assess any possible effect of the presence of the reinforcement on the chemistry of polycondensation. For this purpose, organic fiber, cellulose, and an inorganic fiber, basalt, were chosen, showing a different behavior in the alkaline media that was used to activate the slag fine powders. The novelty of the paper is the study of consolidation by means of chemical measurements, more than from the mechanical point of view. The evaluation of the chemical behavior of the starting slag in NaOH, indeed, was preparatory to the understanding of the consolidation degree in the alkali-activated composites. The reactivity of alkali-activated composites was studied in water (integrity test, normed leaching test, pH and ionic conductivity), and acids (leaching in acetic acid and HCl attack). The presence of fibers does not favor nor hinder the geopolymerization process, even if an increase in the ionic conductivity in samples containing fibers leads to the hypothesis that samples with fibers are less consolidated, or that fiber dissolution contributes to the conductivity values. The amorphous fraction was enriched in silicon after HCl attack, but the structure was not completely dissolved, and the presence of an amorphous phase is confirmed (C-S-H gel). Basalt fibers partly dissolved in the alkaline environment, leading to the formation of a C-N-A-S-H gel surrounding the fibers. In contrast, cellulose fiber remained stable in both acidic and alkaline conditions.

Alkali Activation of Metallurgical Slags: Reactivity, Chemical Behavior, and Environmental Assessment.

Alkali-activated materials (AAMs) represent a promising alternative to conventional building materials and ceramics. Being produced in large amounts as aluminosilicate-rich secondary products, such as slags, they can be utilized for the formulation of AAMs. Slags are partially crystalline metallurgical residues produced during the high temperature separation of metallic and non-metallic materials in the steelmaking processes. In the present study, the electric arc furnace carbon or stainless steel slag (EAF) and secondary metallurgical slag such as ladle furnace basic slag (LS) were used as precursors in an alkali-activation process. EAF slag, with its amorphous fraction of about 56%, presented higher contents of soluble Si and Al species with respect to ladle slag R (35%). However, both are suitable to produce AAM. The leaching behavior shows that all the release values are below the regulation limit. All the bivalent ions (Ba, Cd, Cu, Ni, Pb, and Zn) are well immobilized in a geopolymeric matrix, while amphoteric elements, such as As and Cr, show a slight increase of release with respect to the corresponding slag in alkaline and aqueous environments. In particular, for Sb and As of AAM, release still remains below the regulation limits, while Mo presents an increase of leaching values that slightly exceeds the limit for landfill non-dangerous waste.

Preliminary Study on Sustainable NPK Slow-Release Fertilizers Based on Byproducts and Leftovers: A Design-of-Experiment Approach.

In this study, an organic nitrogen-based coating was developed based on black soldier fly (BSF) prepupae reared on poultry dejections and deposited on ceramic lightweight aggregates (LWAs), containing phosphorous (P) and potassium (K) from agroresidues, leading to a complete nitrogen, phosphorus, and potassium (NPK) fertilizer. To obtain a resistant coating with good adhesion to LWAs, different plasticizing agents were tested (e.g., glycerol, cellulose, and polyethylene glycol). The coating formulation was optimized through a design-of-experiment (DoE) approach to correlate the effect of each mixture component on the coating's performance. BSF biomass was characterized through chemical and thermal routes, as well as the final coated LWAs, confirming their general agreement to fertilizer's requirements. Release tests in static conditions highlighted the barrier action of the coating, preventing uncontrolled release of potassium and phosphorus contained in the LWAs as well as the release of nitrogen after 21 days (near to 20%). Germination and growth tests indicated a valuable increase of the growth index, whereas the germination process is limited by the coating barrier effect. This work proposes a new product in the field of slow-release fertilizers designed by rational methodologies and innovative materials based on waste valorization, fully in agreement with a circular economy perspective.

Comparison of Three Manufacturing Techniques for Sustainable Porous Clay Ceramics.

This study proposes different manufacturing techniques (manual pelletization, powder pressing, and "shell scaffold") to obtain lightweight clay ceramics containing recovery raw materials. The sintering in an electrical furnace (1000 °C, 1 h processing time) was conducted by traditional firing from room temperature, for pressed and shell-scaffold samples, while the flash heating (i.e., samples directly put at 1000 °C) was used only for the pellets. The porous materials (porosity 40-80%), functionalized with nutrients (K and P) in amounts to confer the fertilizer capability, gave suitable results in terms of pH (6.7-8.15) and electrical conductivity (0.29-1.33 mS/cm). Thus, such materials can be considered as feasible lightweight clay ceramics, with a positive effect on the soil. These findings permit us to hypothesize a potential use in green roofs or in agronomic applications.

Spent Coffee Grounds in the Production of Lightweight Clay Ceramic Aggregates in View of Urban and Agricultural Sustainable Development.

This paper presents an innovative application for spent coffee grounds (SCGs) used as filler for the formulation of lightweight clay ceramic aggregates (LWA). LWA can be used for urban and agricultural purposes as a sustainable solution. Spent coffee grounds were tested as a pore forming agent partially acting as a replacement for red clay in material formulation before firing. Substitutions of 10, 15, and 20 wt.% of red clay were tested. The properties of lightweight aggregates with 15 wt.% of SCGs were improved using a specifically tailored fertilizer glass due to its low pH and conductivity within the soil tolerance range. Packaging glassy sand, cattle-bone flour ash, and potassium carbonate were mixed and melted in order to obtain this glass, which when added to the clayey batch functionalized the aggregates by phosphorus and potassium nutrients. The results (in particular, porosity and bulk density) show that the lightweight aggregates obtained have interesting properties for possible uses both in urban (e.g., green roofs as a drainage layer) and agricultural purposes. Moreover, pH and conductivity are in line with the Italian Standard regarding soil amendment (D.lgs. 75/2010). In addition, several leaching tests were performed in a solution containing 2 vol.% citric acid (C6H8O7) to evaluate the release capacity not only of nutrients (P and K) but also to check the presence and release of heavy metals, such as lead (Pb), that may come from the glassy precursor. The results obtained showed that nutrients are efficiently released in 21 days (P = 87.73% and K = 25.74% of released percentage) and Pb release is under the standard threshold of 30 ppm.

Ant fauna associated with Microgramma squamulosa (Kaulf.) de la Sota (Polypodiaceae) fern galls

Abstract Galls are neoformed plant structures created by cell hyperplasia and hypertrophy induced by a number of organisms, especially insects. After adult insects hatch, senescent galls may remain on the host plant and be occupied by a succession of fauna, the most important and dominant being ants. This study aimed at characterizing the ant fauna successor of stem galls induced by microlepidoptera in Microgramma squamulosa (Kaulf.) de la Sota (Polypodiaceae). Four collections were carried out in the municipality of Nova Friburgo, Rio de Janeiro state, Brazil. The galls were packed in plastic bags and taken to the laboratory. Ants were euthanized and conserved in 70° GL alcohol and later identified. A total of 49 stem galls were collected and analyzed, 15 containing microlepidoptera galler larvae, one a parasitoid wasp and 33 without the microlepidoptera or parasitoid (67%). Twelve of these galls (39%) contained ants. Six ant species were recorded (Camponotus crassus, Crematogaster curvispinosa, Crematogaster sericea, Procryptocerus sampaioi, Tapinoma atriceps, and Wasmannia auropunctata), all native to Brazil. Ant occupation in M. squamulosa seems to be associated with senescent galls due to hatching of the galler insect, which leaves a hole that allows ants to colonize it, in other words, an opportunistic domatia. Senescent galls resulting from the death of galler insects do not seem to facilitate ant occupation.

Lead waste glasses management: Chemical pretreatment for use in cementitious composites.

This article investigates the effect of a low-impact chemical treatment based on a nitrilotriacetic acid chelating agent on the reactivity of funnel glass derived from discarded cathode ray tubes. Treated and untreated glass has been recycled either as a supplementary cementing material or as a fine aggregate in cementitious mortars. The effect of the treatment on the chemical and morphological properties of cullets, as well as on the solubility in an alkaline environment has been evaluated. Data so far collected underline a change in glass cullets characteristics that consequently affects their behaviour in cementitious mortars, reducing the pozzolanic activity as supplementary cementing material, but strongly decreasing the tendency towards alkali silica reactions when added as a fine aggregate. The leaching behaviour of lead on treated and untreated glass and on derived composites has been determined to verify the sustainability of the prepared materials.

Design of Inorganic Polymer Mortar from Ferricalsialic and Calsialic Slags for Indoor Humidity Control.

Amorphous silica and alumina of metakaolin are used to adjust the bulk composition of black (BSS) and white (WSS) steel slag to prepare alkali-activated (AAS) mortars consolidated at room temperature. The mix-design also includes also the addition of semi-crystalline matrix of river sand to the metakaolin/steel powders. The results showed that high strength of the steel slag/metakaolin mortars can be achieved with the geopolymerization process which was particularly affected by the metallic iron present into the steel slag. The corrosion of the Fe particles was found to be responsible for porosity in the range between 0.1 and 10 µm. This class of porosity dominated (~31 vol %) the pore network of B compared to W samples (~16 vol %). However, W series remained with the higher cumulative pore volume (0.18 mL/g) compared to B series, with 0.12 mL/g. The maximum flexural strength was 6.89 and 8.51 MPa for the W and B series, respectively. The fracture surface ESEM observations of AAS showed large grains covered with the matrix assuming the good adhesion bonds between the gel-like geopolymer structure mixed with alkali activated steel slag and the residual unreacted portion. The correlation between the metallic iron/Fe oxides content, the pore network development, the strength and microstructure suggested the steel slag's significant action into the strengthening mechanism of consolidated products. These products also showed an interesting adsorption/desorption behavior that suggested their use as coating material to maintain the stability of the indoor relative humidity.

Chromium liquid waste inertization in an inorganic alkali activated matrix: leaching and NMR multinuclear approach.

A class of inorganic binders, also known as geopolymers, can be obtained by alkali activation of aluminosilicate powders at room temperature. The process is affected by many parameters (curing time, curing temperature, relative humidity etc.) and leads to a resistant matrix usable for inertization of hazardous waste. In this study an industrial liquid waste containing a high amount of chromium (≈ 2.3 wt%) in the form of metalorganic salts is inertized into a metakaolin based geopolymer matrix. One of the innovative aspects is the exploitation of the water contained in the waste for the geopolymerization process. This avoided any drying treatment, a common step in the management of liquid hazardous waste. The evolution of the process--from the precursor dissolution to the final geopolymer matrix hardening--of different geopolymers containing a waste amount ranging from 3 to 20%wt and their capability to inertize chromium cations were studied by: i) the leaching tests, according to the EN 12,457 regulation, at different curing times (15, 28, 90 and 540 days) monitoring releases of chromium ions (Cr(III) and Cr(VI)) and the cations constituting the aluminosilicate matrix (Na, Si, Al); ii) the humidity variation for different curing times (15 and 540 days); iii) SEM characterization at different curing times (28 and 540 days); iv) the trend of the solution conductivity and pH during the leaching test; v) the characterization of the short-range ordering in terms of TOT bonds (where T is Al or Si) by (29)Si and (27)Al solid state magic-angle spinning nuclear magnetic resonance (ss MAS NMR) for geopolymers containing high amounts of waste (10-20%wt). The results show the formation of a stable matrix after only 15 days independently on the waste amount introduced; the longer curing times increase the matrices stabilities and their ability to immobilize chromium cations. The maximum amount of waste that can be inertized is around 10 wt% after a curing time of 28 days.

Rapid screening of different chelating agents in the lead extraction from cathode ray tube (CRT) funnel glass.

The cathode ray tube (CRT) glass is one of the most important problem that afflicts the electronic waste disposal whose solution lies in the identification of efficient and ecofriendly processes to detoxify and reutilize lead-contained funnel glass. This study is focused on a rapid screening of different chemical and mechanochemical processes to reduce lead content in waste CRT glass downgrading the risk correlated to it. In particular, as a possibility to clean waste CRT glass, treatments of lead-containing glass with different chelating agents (EDTA, NTA, ATMP, EDTMP and HEDP) were performed to evaluate their extractive capabilities. Furthermore, the influence of the grinding, the chelating agent functional groups (polyamino-carboxylic acid, carboxylic acid, and polyamino phosphonic acid), and the time and the temperature on lead content reduction were analyzed. ESEM and EDS analysis were performed on all the samples to evaluate the lead amount before and after the treatments.

Alkali activation processes for incinerator residues management.

Incinerator bottom ash (BA) is produced in large amount worldwide and in Italy, where 5.1 millionstons of municipal solid residues have been incinerated in 2010, corresponding to 1.2-1.5 millionstons of produced bottom ash. This residue has been used in the present study for producing dense geopolymers containing high percentage (50-70 wt%) of ash. The amount of potentially reactive aluminosilicate fraction in the ash has been determined by means of test in NaOH. The final properties of geopolymers prepared with or without taking into account this reactive fraction have been compared. The results showed that due to the presence of both amorphous and crystalline fractions with a different degree of reactivity, the incinerator BA geopolymers exhibit significant differences in terms of Si/Al ratio and microstructure when reactive fraction is considered.

Management of agricultural biomass wastes: preliminary study on characterization and valorisation in clay matrix bricks.

In this work the feasibility of using woody agricultural biomass wastes as grapes and cherries seeds, sawdust, as pore forming agent, and sugar cane ash, as silica precursor, in bricks, were reported. Sawdust and grapes and cherries seeds, thanks to their organic substances content, during their combustion, bring an energetic support in the bricks firing phase and act as pore forming agent. Usually the addition of this kind of waste is limited to 10wt.% in order to reach an equilibrium between positive (weight and shrinkage decrease and porosity increase) and negative (increase of water absorption and mechanical resistance decrease) effects. The results show that grapes and cherries seeds, added in a percentage of 5wt.% to a brick formulation, have better influence with respect to the sawdust, maintaining the mechanical properties of the fired brick (950°C), showing modulus of rupture around 21-23MPa with a weight reduction of 3-10% (respect to the standard one). Regarding the sugar cane ash, the addition of 5wt.% improves the mechanical properties (modulus of rupture around 27MPa) and no weight decrease is observed. These results confirmed the role played by this kind of agricultural waste, which thanks to its high silica content (61wt.%) is capable to demonstrate a filler and plasticity reducing effect on the brick bodies. Tests carried out highlighted that the addition of these by-products (5wt.%) do not change negatively the main technological properties measured (water absorption, linear shrinkage, flexural resistance, etc.) and permit to hypothesize their use to obtain bricks with both insulating and higher mechanical properties using a pore agent forming or silica carrier alternative raw materials, respectively.

Chemical stability of geopolymers containing municipal solid waste incinerator fly ash.

Municipal solid waste incinerators every year produce tons of fly ashes which, differently from coal fly ashes, contain large amounts of toxic substances (heavy metals, dioxins, furans). The stabilization/solidification (S/S) technology known as geopolymerization is proposed with the purpose to bond physically and chemically incinerator fly ashes (IFA) in a solid matrix, in order to reduce pollutant mobility. The chemical stability of geopolymers with Si/Al ratio of 1.8-1.9 and Na/Al ratio of 1.0, synthesized by alkali activation of metakaolin and the addition of 20wt% of two different kinds of IFA, is presented. The concentration of the alkaline solution, water to solid ratio and curing process have been optimized. The room temperature consolidation of IFA containing geopolymers has been tested for leachability in water for 1day, accordingly to EN 12457 regulation and extended to 7days to increase the water attack on solid granules. Leachable metals in the test solution, determined by ICP_AES, fall within limit values set by regulation for non-dangerous waste landfill disposal. Geopolymeric matrix evolution with leaching time has been also evaluated in terms of pH and electrical conductivity increase in solution.

Cathode ray tube glass recycling: an example of clean technology.

In this study the use of 'cleaned' end of life (EOL) cathode ray tube (CRT) glass as a raw material in ceramic glazes is described. At present, the recycling and industrial utilization of CRT, a glass material from TV and computer sets, is a subject of intense research with particular regard to the so-called open-loop recycling, namely cycles different from that of the origin. However, the use of CRT glass as a secondary raw material is strictly related to the demand of high-quality raw material. The good preliminary results reached by introducing clean TV and PC monitor panel and cone glass into ceramic glaze formulations pushed research toward the setting-up of a base glaze that is exploitable for the production of pigmented, silk-screened and flame-hardened glazes (products used industrially for coating floor tiles). The aesthetic and chemical characterization of the tiles glazed by this product showed an extremely similar behaviour to originals that did not contain CRT glass. The good technical results achieved have been supported by the life cycle assessment analysis, which has demonstrated a reduction of the environmental impact of the CRT glass-containing ceramic glaze with respect to the standard one.