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Restaino, O.F.; Giosafatto, C.V.L.; Mirpoor, S.F.; Cammarota, M.; Hejazi, S.; Mariniello, L.; Schiraldi, C.; Porta, R. Sustainable Exploitation of Posidonia oceanica Sea Balls (Egagropili). Encyclopedia. Available online: https://encyclopedia.pub/entry/43299 (accessed on 24 June 2024).
Restaino OF, Giosafatto CVL, Mirpoor SF, Cammarota M, Hejazi S, Mariniello L, et al. Sustainable Exploitation of Posidonia oceanica Sea Balls (Egagropili). Encyclopedia. Available at: https://encyclopedia.pub/entry/43299. Accessed June 24, 2024.
Restaino, Odile Francesca, Concetta Valeria L. Giosafatto, Seyedeh Fatemeh Mirpoor, Marcella Cammarota, Sondos Hejazi, Loredana Mariniello, Chiara Schiraldi, Raffaele Porta. "Sustainable Exploitation of Posidonia oceanica Sea Balls (Egagropili)" Encyclopedia, https://encyclopedia.pub/entry/43299 (accessed June 24, 2024).
Restaino, O.F., Giosafatto, C.V.L., Mirpoor, S.F., Cammarota, M., Hejazi, S., Mariniello, L., Schiraldi, C., & Porta, R. (2023, April 20). Sustainable Exploitation of Posidonia oceanica Sea Balls (Egagropili). In Encyclopedia. https://encyclopedia.pub/entry/43299
Restaino, Odile Francesca, et al. "Sustainable Exploitation of Posidonia oceanica Sea Balls (Egagropili)." Encyclopedia. Web. 20 April, 2023.
Sustainable Exploitation of Posidonia oceanica Sea Balls (Egagropili)
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Posidonia oceanica (L.) Delile is the main seagrass plant in the Mediterranean basin that forms huge underwater meadows. Its leaves, when decomposed, are transported to the coasts, where they create huge banquettes that protect the beaches from sea erosion. Its roots and rhizome fragments, instead, aggregate into fibrous sea balls, called egagropili, that are shaped and accumulated by the waves along the shoreline. Their presence on the beach is generally disliked by tourists, and, thus, local communities commonly treat them as waste to remove and discard. Posidonia oceanica egagropili might represent a vegetable lignocellulose biomass to be valorized as a renewable substrate to produce added value molecules in biotechnological processes, as bio-absorbents in environmental decontamination, to prepare new bioplastics and biocomposites, or as insulating and reinforcement materials for construction and building.

cellulose egagropili holocellulose lignin marine waste

1. Introduction

1.1. Biological Role of Posidonia oceanica and Derived Egagropili

Posidonia oceanica (L.) Delile (PO) is an aquatic plant that is a dominant and endemic sea grass of the Mediterranean basin belonging to the Posidoniaceas family [1], and therefore, it is not an alga, despite still being frequently and wrongly defined as such in numerous scientific papers [1]. PO is a slow-growing plant that might live for millennia, and it forms huge underwater meadows that are estimated to cover more than 2.0% of the Mediterranean seabed (for a total of more than 12,000 km2) and that could extend from the sea surface up to 40 m of depth [1][2]. PO mainly spreads itself by sexual reproduction, although asexual reproduction might also occur by stem extension. The sexual annual reproductive cycle starts in the fall with pollination, and after a period of six to nine months, its mature fruits release seeds that reach the seabed and can develop roots and produce a new plant [3]. In only one year, the meadows of PO produce a huge amount of debris as leaves (leaf blades and sheaths), rhizomes, and roots that could constitute a biological sediment on the seabed and, eventually, might be either degraded by macro-organisms, microorganisms, and abiotic factors, or being subjected to the hydrodynamic action of the sea and rolled on its floor or ripple marks, or transported by the waves on the coasts where they accumulate [3]. The leaves, in particular the portions called leaf blades, fall from the plant after 5–8 months of existence and, generally, at higher rates in the autumn, a lower amount of sunlight reaches the sea, and many strong storms occur. Conversely, the leaf sheaths usually remain attached to the rhizomes. The leaves, that reach the seashore transported by the waves and deposited on the beaches by the winds, usually form huge banquettes with thickness ranging from a few centimeters up to 2.5 m [3][4]. The annual total amount of PO leaves that reach the coast is in the range of 5 to 50 million tons, and nowadays the banquettes are estimated to cover about 50,000 km2 of sandy shores in the Mediterranean areas [1][2][3][5]. They are generally composed of wet and dried brown PO leaves, and they play an important ecological role in preserving the ecosystem and the biodiversity. In fact, they represent a favorable habitat for many species, promote sediment entrapment and stabilization, regulate the CO2 absorption of the sea and of the atmosphere, as well as water oxygenation, and protect the coasts from erosion by acting as a barrier [2][4][5][6]. PO roots and rhizome fragments, instead, might naturally be entangled by the constant rolling of the sea motions and aggregate as ball-shaped materials that are then delivered by the waves on the coasts, where they dried under the sun and the wind action [2][4]. These brown dried fibrous balls are generally known as PO egagropili (POEG), also spelled egagropilia, egagropoli, or aegagropiles, and reported as sea balls, sea rissoles, sea potatoes, beach balls, Neptune balls, or Kedron balls. The name “aegagropiles” derives from the ancient Greek words of αίγαγρoς (wild goat) and πῖλoς (fur), as the shape of these sea balls is reminiscent of the ones that are generally regurgitated by goats [4]. Figure 1 shows a representative image of some POEG samples collected by the scholars on the beach of Marzamemi, Sicily, Italy; 36°44′34″ N, 15°7′1″ E, and Figure 2 indicates the map of the sites in the Mediterranean Sea [2][5]. As with the leaves, every year millions of POEGs are delivered on the beaches by the winds, mainly in the period between October and March and especially after strong sea storms [3][5]. In some cases, POEG deposition could constitute a characteristic geomorphological feature of the landscape, such as along the southeastern Gulf of Sirte, in Libya, near the coastal town of Brega (30°26′06″ N, 19°40′01″ E) (Figure 2). Here the POEGs are deposited by the action of westerly winds, while the hot and arid wind of Ghibli, from the south, carries huge amounts of Sahara sand, thus forming peculiar POEG sandy sheets and dunes that are considered paleoenvironmentally interesting to study in Holocene era [5]. Indeed, POEGs have been frequently studied in integrated archaeological and geological investigations as a sign of the coastal barrier evolution in different Mediterranean areas as well as of the stratification and of the climate changes during the Holocene (e.g., the studies on the Mistras coastal barrier system in central Sardinia, Italy [7]).
Figure 1. Pictures of POEGs of both oval and elongated shapes of different sizes, with a ruler used as a reference. They were collected by the scholars on the beach of Marzamemi (Sicily, Italy; 36°44′34″ N, 15°7′1″ E).
Figure 2. Map of the sites in the Mediterranean Sea where the POEG samples.

1.2. POEG Structural Characteristics

POEGs have specific physical characteristics such as a texture of rough felt, oval shapes (ball-shape), spherical or subspherical, or sometimes also elongated ellipsoidal shapes (egg-shape) and have different sizes with diameter values from millimeters to centimeters up to 20 cm (Figure 1). They have a very light weight, so they easily float freely in the sea water [2][3][5]. Their shape and their geometrical and mechanical properties are conserved, although they are formed in the open sea and under not-constant environmental conditions. For these reasons, POEGs have been considered a natural archetype of fiber networks and studied as models to understand fundamental aspects of the clustering mechanisms and of the aggregation dynamic forces in the networking processes [4]. Indeed, the natural processes and forces, as well as the sequence of events that drives POEG formation, are not easy to decipher, and in the literature, there are only a few studies on their origin, properties, and structural composition. In a recent paper, the determination of the average mass, average size, in terms of length and radius, and of the volume was performed on 2000 POEG samples collected in two beaches in France, at Six Fours (43°63′06″ N, 5°49′20″ E) and at Porquerrolles Island (43°00′02″ N, 6°13′38″ E) (Figure 2) [4]. X-ray tomography analyses were used to determine the POEG average density and density profile, their internal structure, and their fiber orientation. The sea balls showed an average density of 128 kg·m−3 and an inhomogeneous fiber alignment, at least in the dense outward shell, in which the fibers had low orthoradial orientation [4].

2. Posidonia oceanica Egagropili as Lignocellulosic Biomass to Valorize

Every year, huge quantities of POEG fragments accumulate on Mediterranean coasts, resulting in a problem and a negative visual impact, creating the necessity for municipalities to remove this waste to keep beaches cleaned and ready for tourists and the summer season [6]. As disposal of this waste is performed every year and does not have negligible costs, it would be useful to find a way to valorize POEGs as readily available, low-cost, and renewable lignocellulose biomass and as a good source of cheap materials and fibers to produce added-value products from the perspective of an eco-friendly society [1][8][9]. The whole POEGs, themselves, have interesting properties that can be used for energy production [10], dye removal from the environment, building materials in the construction sector, as well as in the development of new packaging systems. They are also an optimal source of lignin and cellulose fractions that might be widely used in the paper-making industry, as well as a source of carboxymethyl cellulose in the production of fiber-reinforced composite materials and biopolymeric films. Lastly, they might be used as carbohydrate substrates to grow microorganisms in biotechnological processes. The lignin fraction, made of numerous 4-hydroxybenzoic acid groups, might instead be used for the synthesis of chemicals, such as parabens, and pharmaceutical molecules, such as paracetamol. All new applications of POEGs and their derived fractions are reported in the following paragraphs from the literature published in the last few years in the fields of biotechnology, environmental decontamination and bioremediation processes, bioplastic and biocomposite preparations, and construction materials (Figure 3).
Figure 3. Fields of applications of POEGs.

2.1. Posidonia oceanica Egagropili in Biotechnological Applications

The whole POEGs and/or their lignin and cellulose fractions have been employed in numerous biotechnological applications. For example, they have been recently used as substrates for microorganism growth. Recently, POEGs collected in Poetto (Figure 2) were added, after being washed and milled, as a raw source, in a glucose, yeast, and malt extract containing medium to boost the natural synthesis of melanin by Streptomyces roseochromogenes [11]. The researchers found that the addition of 2.5 g/L of POEG powder in shake flasks enhanced the biomass formation of 1.5–1.9 folds in a 120-hour run at 26 °C and 250 rpm and increased the melanin production of 7.4 times, up to about 3.9 g/L, compared to the control. In 2-liter batch experiments, the melanin production reached values of 9.2 g/L in only 96 h, with a further increase in both production and productivity of about 2.4 folds [11]. Melanin is a secondary metabolite that starts to be synthesized by streptomycetes in their late exponential and stationary phases of growth. The first two reactions in the melanin synthetic pathway are catalyzed by the action of a tyrosinase that converts the precursor L-tyrosine to L-3,4-dihydroxyphenylalanine (DOPA) in the presence of molecular oxygen. The scientists discovered that the addition of the POEG powder to the medium enhanced the tyrosinase activity of 1.5–1.7 folds compared to the control during the microorganism growth and drove to a higher and faster melanin production. Furthermore, studies have demonstrated that both the lignin and cellulose components of the POEGs are necessary to boost melanin production, but in different ways. The holocellulose chains were used by the bacteria as a substrate for their growth, whereas the isolated lignin carbohydrate complex was necessary to induce melanin synthesis, but only if the two components were supplied together higher biomass values and melanin concentrations were obtained [11]. In another paper, instead, only the cellulose component, isolated from the POEGs collected in Poetto again, was used to enhance the production of cellulases in the same strain, S. roseochromogenes [12]. This fraction, supplemented to the growth medium at a concentration of 2.5 g/L, was able to increase the enzyme production in shake flasks of 4.3 fold compared to the control, up to 268 U/L in 72 h with a productivity of 3.7 U/L/h and up to 347 U/L in 45 h in 2-liter batch experiments with a productivity of 7.7 U/L/h. The supplementation of cellulose induced the expression of a pool of three cellulases with molecular weights of about 115, 63, and 47 kDa. This pool had optimal activity at 60 °C and pH 5.0, and showed their ability to hydrolyze at the same time substrates such as carboxymethyl cellulose (CMCase activity) and filter paper (FPase activity), and it also showed a β-glucosidase action [12]. As POEGs contain salts in their fibers, they might also constitute an example of marine-origin lignocellulose biomass, a waste that needs to be studied to improve the knowledge of the bioconversion of sea raw materials into fermentable sugars to produce second-generation biofuels [13].

2.2. Posidonia oceanica Egagropili in Environmental Decontamination Processes

PO is a natural biomonitor of pollution in the sea as it catches heavy metal ions such as arsenic (As), cadmium (Cd), lead (Pb), and zinc (Zn) present in the water to store them in its organs at concentrations of up to several mg/kg [14]. Additionally, the dried fibrous balls of POEGs have promising features, such as being green adsorbents for cationic pollutants since they are already found in nature as cation-imprinted lignocellulose networks that contain a high presence of salts [14]. The high biosorption properties of POEGs could constitute a new potential way for their valorization and reusing in cleaning systems of blackish water decontamination processes from dyes, phenol compounds, and heavy metals [8][14]. According to some scholars, the POEGs’ ability to uptake metals might be due to the porosity of their cell walls, which allow the entrance of small ions, and due to their lignocellulose composition [15]. In the literature, many studies have focused on POEGs’ absorption abilities and their possible applications in diverse decontamination processes. In these investigations, some key parameters of the process have been taken into account, such as the pH of the contaminant solution, the temperature at which the process is performed, the contact time between the solution and the POEGs, the initial concentration of the contaminant, the amount and size of the POEGs, and the enthalpy and entropy of the process. In a recent paper, some POEGs collected in Marsa Matrouh, Egypt (31°21′15″ N, 27°14′14″ E) (Figure 2) were “activated” by soaking them after pulverization in 1 M acetic acid overnight and then used as an eco-adsorbent for the removal (in 30 min of shaken run) of methylene blue and lead ions (Pb2+) present in aqueous solutions in concentration ranges from 0.6 to about 2.6 g/L [14]. The initial acetic acid activation method resulted in greatly reducing the presence of some ions, such as barium (B), cadmium (Cd), chromium (Cr), copper (Cu), magnesium (Mg), and zinc (Zn), in the fibers that are naturally present in the collected samples without altering the lignocellulose composition. On the basis of these analyses of the adsorption isotherms and thermodynamic studies, the scholars proposed that the POEG adsorption mechanism of methylene blue, present in water as monomers, dimers, or trimers, might be due to combined electrostatic and physical multi-layer adsorption processes, whereas the lead was chemically adsorbed. The activated fibers were then applied to decontamination of waste blackish waters to remove the methylene blue from Manzala Lake, Egypt, with an efficiency of 91.5–99.9% [14]. The use of POEGs as new bio-sorbents for heavy metals (M) with an oxidation state of II was investigated in another paper using samples collected in Tipaza, Algeria (36°37′4″ N, 2°23′28″ E) (Figure 2).

2.3. Posidonia oceanica Egagropili in Bioplastic and Biocomposite Preparations

POEG fibers have been widely used to strengthen the matrix of plastics, both of bio-based and oil-based origins. Mirpoor et al. [2] have exploited both the lignin-carbohydrate (LCC) and the nanocrystalline cellulose (NC) fractions, after extraction from egagropili collected in Poetto (Figure 2), as reinforcing agents for hydroplastic materials. The two fractions were able to improve the physicochemical properties of biodegradable films obtained from hemp (Cannabis sativa) oil seedcake protein concentrates. In fact, such materials exhibited a high tensile strength and Young’s modulus; the Young’s modulus increased from around 20 to 45 and to 80 MPa, while the elongation at break was reduced from 300% to 250% and to 120% in the presence of LCC and NC, respectively. They possessed barrier properties towards water vapor, O2, and CO2. In addition, both fractions decreased film hydrophilicity, infact, moisture content, solubility, and swelling ratio were lower for the films prepared in the presence of additives. In 2021, the same scholars [16] investigated deeply the LCC fraction obtained from the same POEG samples from a chemical point of view using FT-IR and NMR analyses (see also Section 1.2). The LCC fraction was water soluble as it contained monosaccharides and exhibited a brownish-to-black color due to certain functional groups, such as phenylpropane-based polymers. Furthermore, it exhibited a remarkable and stable antioxidant activity that was easily released over 6 months when it was used as an additive in hemp protein-based films. On the other hand, in another paper, lignin-containing cellulose micro/nanofibrils (LCM/NF) were also obtained by combining the steam explosion process or twin-screw extrusion (as energy-efficient pretreatments) with a conventional grinding step [17]. The chemical composition of the fibers, collected in Monastir (Figure 2), before and after pulping, was analyzed. The obtained LCM/NF suspensions were characterized by several techniques, such as morphological and mechanical analysis. It has been shown that if the sulfonation method was coupled with steam explosion or twin-screw extrusion, then it was possible to obtain LCM/NF gels with relatively low viscosity and nano papers with a Young’s modulus of around 5 GPa. Sulfonation was revealed to be an effective pretreatment to lower the energy during grinding, and therefore it can be considered a valid technique to be applied in the field of packaging [17]. POEG fibers, collected in Campello Beach in Alicante, Spain (38°21′00.01″ N, 0°29′00″ W) (Figure 2), were exploited in the reinforcement phase and in oil-based polymeric matrices, such as the high-density polyethylene (HDPE) [18] samples), and more recently even in polyesters [18][19].

2.4. Posidonia oceanica Egagropili in Construction Materials and as Decoration

POEGs have been widely studied in recent years as environmentally friendly materials to be employed in buildings having fire, sound, and water-resistant properties. For example, POEGs have been used in the construction sector as insulating material to reduce the risk of energy source shortages and better manage energy consumption in buildings [20]. In this context, the use of insulating materials is a key factor, as they might provide better thermal comfort, sound insulation, and fire protection [21]. It is worth noting that so far, many of the insulation materials used in the building sector were petroleum derivatives, and they must be replaced with materials derived from renewable natural resources from the perspective of a sustainable bioeconomy [22]. Benjeddou et al. [23] studied the effect of adding POEGs to cement composites and found that the mechanical strength, sound, and thermal diffusivity were all improved. The POEG fibers were able to reduce sound transmission by increasing the fiber volume and, consequently, the air voids in the cement paste. Another study carried out by Jedidi and Abroug [22] reported that the addition of POEG fibers (collected in Monastir, Tunisia; Figure 2), up to 10%, to the plasters significantly improved their mechanical properties. Thermal conductivity also decreased from 0.35 W/m/K in the absence of fibers to 0.11 W/m/K in the presence of 20% of them.

3. Conclusions

In recent years, POEGs have caught more and more attention as interesting marine-origin raw materials. Due to their structural and physical properties, they have demonstrated that they could be employed in a variety of applications and fields. The whole POEG fiber network constitutes an interesting nutrient that can be supplemented to a medium for both plant and microorganism growth, while their cellulose components have already been used in biotechnological processes to obtain added valuable molecules, such as enzymes and biofuels. Due to their physical and mechanical properties, these fibers could easily constitute the base of newly developed bioplastics and biocomposites, as well as insulating materials for buildings. Moreover, their isolated lignin fractions might be easily used as reinforcement in newly designed biomaterials. The ability of their fibers to adsorb metals and water contaminants also makes POEGs the ideal ecological tools for environmental decontamination.

References

  1. Trache, D.; Tarchoun, A.F.; De Vita, D.; Kennedy, J.F. Posidonia oceanica (L.) Delile: A Mediterranean seagrass with potential applications but regularly and erroneously referred to as an algal species. Int. J. Biol. Macromol. 2022, 230, 122624.
  2. Mirpoor, S.F.; Giosafatto, C.V.L.; Di Pierro, P.; Di Girolamo, R.; Regalado-González, C.; Porta, R. Valorisation of Posidonia oceanica sea balls (egagropili) as a potential source of reinforcement agents in protein-based biocomposites. Polymers 2020, 12, 2788.
  3. Lefebvre, L.; Compère, P.; Léonard, A.; Plougonven, E.; Vandewalle, N.; Gobert, S. Mediterranean aegagropiles from Posidonia oceanica (L.) Delile (1813): A first complete description from macroscopic to microscopic structure. Mar. Biol. 2021, 168, 37.
  4. Verhille, G.; Moulinet, S.; Vandenberghe, N.; Adda-Bedia, M.; Le Gal, P. Structure and mechanics of aegagropilae fiber network. Proc. Natl. Acad. Sci. USA 2017, 114, 4607–4612.
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  12. Restaino, O.F.; Cuomo, S.; D’Ambrosio, S.; Vassallo, V.; Mirpoor, S.F.; Giosafatto, C.V.L.; Porta, R.; Schiraldi, C. Cellulose from Posidonia oceanica sea balls (egagropili) as substrate to enhance Streptomyces roseochromogenes cellulase biosynthesis. Fermentation 2023, 9, 98.
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  15. Boulaiche, W.; Belhamdi, B.; Hamdi, B.; Trari, M. Kinetic and equilibrium studies of biosorption of M(II) (M = Cu, Pb, Ni, Zn and Cd) onto seaweed Posidonia oceanica fibers. Appl. Water Sci. 2019, 9, 173.
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  17. Khadraoui, M.; Nader, S.; Khiari, R.; Brosse, N.; Bergaoui, L.; Mauret, E. Effectiveness of sulfonation to produce lignin-containing cellulose micro/nanofibrils (LCM/NF) by grinding. Cellulose 2023, 30, 815–832.
  18. Puglia, D.; Petrucci, R.; Fortunati, E.; Luzi, F.; Kenny, J.M.; Torre, L. Revalorisation of Posidonia oceanica as reinforcement in polyethylene/maleic anhydride grafted polyethylene composites. J. Renew. Mater. 2014, 2, 66–76.
  19. Haddar, M.; Elloumi, A.; Koubaa, A.; Bradai, C.; Migneault, S.; Elhalouani, F. Synergetic effect of Posidonia oceanica fibres and deinking paper sludge on the thermo-mechanical properties of high-density polyethylene composites. Ind. Crops Prod. 2018, 121, 26–35.
  20. Hamdaoui, O.; Ibos, L.; Mazioud, A.; Safi, M.; Limam, O. Thermophysical characterization of Posidonia Oceanica marine fibers intended to be used as an insulation material in Mediterranean buildings. Constr. Build. Mater. 2018, 180, 68–76.
  21. Varun Teja, K.; Meena, T. Performance of ternary blended concrete and binary concrete made with perlite powder at elevated temperatures. Jordan J. Civ. Eng. 2020, 14, 198–209.
  22. Jedidi, M.; Abroug, A. Valorization of Posidonia oceanica balls for the manufacture of an insulating and ecological material. Jordan J. Civ. Eng. 2020, 14, 417–430.
  23. Benjeddou, O.; Jedidi, M.; Khadimallah, M.A.; Ravindran, G.; Sridhar, J. Effect of Posidonia oceanica fibers addition on the thermal and acoustic properties of cement paste. Buildings 2022, 12, 909.
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