Depollution of Polymeric Leather Waste by Applying the Most Current Methods of Chromium Extraction.

The leather industry is one of the most polluting industries in the world due to the large amounts of waste following raw hide processing but also due to the high content of chemical substances present in leather waste. The main problem with chromium-tanned leather solid waste is related to the storage, due to the ability of chromium to leach into soil or water, and also owing to the high ability of trivalent chromium to oxidize to its toxic form, hexavalent chromium. The purpose of this article is to present the most current methods of chromium extraction from solid tanned leather waste in order to obtain non-polluting leather, which can constitute secondary raw material in new industrial processes. The extraction methods identified in the present study are based on acid/basic/enzymatic hydrolysis and substitution with the help of organic chelators (organic acids and organic acid salts). In addition, this study includes a comparative analysis of the advantages and disadvantages of each identified extraction method. At the same time, this study also presents alternative chromium extraction methods based on the combination of conventional extraction methods and ultrasound-assisted extraction.

Adsorption of Metal Ions from Single and Binary Aqueous Systems on Bio-Nanocomposite, Alginate-Clay.

The aim of this work is to characterize and evaluate the retention of Cu2+ and Ni2+ from single and binary systems by alginate-Moroccan clay bio-composite with the utilization of calcium chloride as a cross-linking agent, using the ionotropic gelation method. The bio-nanocomposite was characterized by using a variety of techniques (SEM, EDX, XRD, and pHPZC). The efficiency of the adsorbent was investigated under different experimental conditions by varying parameters such as pH, initial concentration, and contact time. To demonstrate the adsorption kinetics, various kinetic models were tried and assessed, including pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models. The research results show that the adsorption process of Cu2+ and Ni2+ metal ions follows a pseudo-second-order kinetic model, and the corresponding rate constants were identified. To evaluate the parameters related to the adsorption process in both single and binary systems, different mathematical models of isotherms, such as Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, were investigated. The correlation coefficients obtained showed that the most suitable isotherm for describing this adsorption process is the Langmuir model. The process is considered to be physical and endothermic, as suggested by the positive values of ΔH° and ΔS°, indicating increased randomness at the solid/liquid interface during Cu2+ and Ni2+ adsorption. Furthermore, the spontaneity of the process is confirmed by the negative values of ∆G°. The bio-nanocomposite beads demonstrated a maximum adsorption capacity of 370.37 mg/g for Ni2+ and 454.54 mg/g for Cu2+ in the single system. In the binary system, the maximum adsorption capacities were observed to be 357.14 mg/g for Ni2+ and 370.37 mg/g for Cu2+. There is significant evidence for the use of alginate-Moroccan clay bio-nanocomposite as a cost-effective alternative adsorbent for the efficient removal of metal ions in single and binary systems.

Alginate-Moroccan Clay, New Bio-Nanocomposite for Removal of H2PO4-, HPO42-, and NO3- Ions from Aqueous Solutions.

The aim of this work is to synthesize and characterize alginate-Moroccan clay bio-composite in order to improve our understanding of the adsorption of inorganic pollutants found in textile effluents. Characterization of the bio-composite used was carried out using a variety of techniques (IR-TF, SEM, DRX, and pHZPC). The influence of the medium's physico-chemical parameters (temperature, pH, initial concentration, etc.) on the retention of inorganic pollutants was also studied. Studies of adsorption and inorganic pollutants such as orthophosphate (H2PO4- and HPO42-) and nitrate (NO3-) ions were carried out, using simple solutions from the laboratory, in a batch system. This study explored the impact of adsorbent dose, contact time, solution pH, and temperature on the adsorption process. Various kinetic models, including pseudo-first-order, pseudo-second-order, intra-particle diffusion, and Elovich models, were tested and evaluated, to illustrate the adsorption kinetics. This study's findings demonstrated that the adsorption process follows second-order kinetics, with associated rate constants successfully determined. The correlation coefficient for the pseudo-second-order kinetic model is nearly equal to 1 (>0.98), and the value of theoretical adsorption capacity (qe,the) is comparable to the experimental one (qe,the = 58.14 mg/g for H2PO4-, qe,the = 54.64 mg/g for HPO42-, and qe,the = 52.63 mg/g for NO3-). Additionally, the adsorption equilibrium was investigated through the application of various mathematical models, including the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, to assess the mechanistic parameters associated with the adsorption process. Among these models, the Langmuir isotherm emerged as the most suitable one for characterizing the adsorption of H2PO4-, HPO42-, and NO3- ions using bio-nanocomposite beads. The maximum adsorbed amounts of metal ions by the bio-nanocomposite used were 625 mg/g for H2PO4-, 909.09 mg/g for HPO42-, and 588.23 mg/g for NO3- from the batch system. The endothermic and physical nature of the adsorption is suggested by the positive values of ΔH°, which is consistent with experimental findings. The adsorption process is spontaneous, as evidenced by the negative ΔG° values. Positive ΔS° values indicate increased randomness at the solid/liquid interface during adsorption of ion-organic ions onto the engineered bio-nanocomposite. The obtained results demonstrated that, from a scientific perspective, alginate-Moroccan clay bio-nanocomposites exhibit a highly significant adsorption capability for the removal of oxyanions in aqueous environments.

The Behavior of Polymeric Pipes in Drinking Water Distribution System-Comparison with Other Pipe Materials.

The inner walls of the drinking water distribution system (DWDS) are expected to be clean to ensure a safe quality of drinking water. Complex physical, chemical, and biological processes take place when water comes into contact with the pipe surface. This paper describes the impact of leaching different compounds from the water supply pipes into drinking water and subsequent risks. Among these compounds, there are heavy metals. It is necessary to prevent these metals from getting into the DWDS. Those compounds are susceptible to impacting the quality of the water delivered to the population either by leaching dangerous chemicals into water or by enhancing the development of microorganism growth on the pipe surface. The corrosion process of different pipe materials, scale formation mechanisms, and the impact of bacteria formed in corrosion layers are discussed. Water treatment processes and the pipe materials also affect the water composition. Pipe materials act differently in the flowing and stagnation conditions. Moreover, they age differently (e.g., metal-based pipes are subjected to corrosion while polymer-based pipes have a decreased mechanical resistance) and are susceptible to enhanced bacterial film formation. Water distribution pipes are a dynamic environment, therefore, the models that are used must consider the changes that occur over time. Mathematical modeling of the leaching process is complex and includes the description of corrosion development over time, correlated with a model for the biofilm formation and the disinfectants-corrosion products and disinfectants-biofilm interactions. The models used for these processes range from simple longitudinal dispersion models to Monte Carlo simulations and 3D modeling. This review helps to clarify what are the possible sources of compounds responsible for drinking water quality degradation. Additionally, it gives guidance on the measures that are needed to maintain stable and safe drinking water quality.

Innovative Collagen Based Biopolymers Tested as Fertilizers for Poor Soils Amendment.

Improving soil quality is of growing interest and, among optimal solutions, the reuse and recycling of biopolymers of pelt waste from the tannery industry have been proposed, one of them being for collagen hydrolysate with micronutrients and polymers incorporated, to be used as fertilizers for poor soils rehabilitation. As functionalization agents, polyacrylamide, starch and dolomite were included into biopolymer matrixes in order to enhance their specific efficiency. These fertilizers were adequately characterized for their physical-chemical properties, including nutrient content, and tested on three poor soils, while a fourth sample of normal soil was chosen for comparative purposes. These soils were also characterized for their texture and physical-chemical properties in order to establish the fertility state of the soils as a function of nutrient content. In this respect, a series of agrochemical tests were developed at laboratory scale, simulating real agriculture environments in a vegetation room, where a significant plant growth in height was observed for all the agro-hydrogels with nutrients encapsulated, and multiplication of the nodosities number was observed in the case of the soybean culture. The most significant effect was obtained in the case of the fertilizer functionalized with starch. Finally, the application dose of the organic fertilizers for specific culture plants was estimated, such as field cultures (cereals, corn), field vegetables, vineyards or fruit-growing plantations. These agro-collagen fertilizers are particularly recommended for amendment of field cereals and vegetables. The novelty of this study mainly consists of the recovery and recycling of the pelt waste as efficient fertilizers after their adequate functionalization with synthetic or natural biopolymers.

Comparative Study of Useful Compounds Extracted from Lophanthus anisatus by Green Extraction.

Essential oils were obtained from different parts of Agastache foeniculum (Lophanthus anisatus) plants by means of extraction: green extraction using hydro-distillation (HD) and bio-solvent distillation, BiAD, discontinuous distillation, and supercritical fluid extraction, in two stages: (1) with CO2, and (2) with CO2 and ethanol co-solvent. The extraction yields were determined. The yield values varied for different parts of the plant, as well as the method of extraction. Thus, they had the values of 0.62 ± 0.020 and 0.92 ± 0.015 g/100 g for the samples from the whole aerial plant, 0.75 ± 0.008 and 1.06 ± 0.005 g/100 g for the samples of leaves, and 1.22 ± 0.011 and 1.60 ± 0.049 g/100 g for the samples of flowers for HD and BiAD, respectively. The yield values for supercritical fluid extraction were of 0.94 ± 0.010 and 0.32 ± 0.007 g/100 g for the samples of whole aerial plant, 0.9 ± 0.010 and 1.14 ± 0.008 g/100 g for the samples of leaves, and 1.94 ± 0.030 and 0.57 ± 0.003 g/100 g for the samples of flowers, in the first and second stages, respectively. The main components of Lophanthus anisatus were identified as: estragon, limonene, eugenol, chavicol, benzaldehyde, and pentanol. The essential oil from Agatache foeniculum has antimicrobial effects against Staphylococcus aureus, the Escherichia coli and Pseudomonas aeruginosa. Acclimatization of Lophantus anisatus in Romania gives it special qualities by concentrating components such as: estragole over 93%, limonene over 8%, especially in flowers; and chavicol over 14%, estragole over 30%, eugenol and derivatives (methoxy eugenol, methyl eugenol, etc.) over 30% and phenyl ether alcohol over 20% in leaves. As a result of the research carried out, it was proven that Lophanthus anisatus can be used as a medicinal plant for many diseases, it can be used as a spice and preservative for various foods, etc.

Methods for Natural and Synthetic Polymers Recovery from Textile Waste.

Trends in the textile industry show a continuous increase in the production and sale of textile materials, which in turn generates a huge amount of discarded clothing every year. This has a negative impact on the environment, on one side, by consuming resources-some of them non-renewables (to produce synthetic polymers)-and on the other side, by polluting the environment through the emission of GHGs (greenhouse gases), the generation of microplastics, and the release of toxic chemicals in the environment (dyes, chemical reagents, etc.). When natural polymers (e.g., cellulose, protein fibers) are used for the manufacturing of clothes, the negative impact is transferred to soil pollution (e.g., by using pesticides, fertilizers). In addition, for the manufacture of clothes from natural fibers, large amounts of water are consumed for irrigation. According to the European Environment Agency (EEA), the consumption of clothing is expected to increase by 63%, from 62 million tonnes in 2019 to 102 million tonnes in 2030. The current article aims to review the latest technologies that are suitable for better disposal of large quantities of textile waste.

Advanced Collagen-Based Composites as Fertilizers Obtained by Recycling Lime Pelts Waste Resulted during Leather Manufacture.

Recent trends in ecological agriculture practices are focused on finding optimal solutions for reuse and recycling of pelt waste from tannery industry. In this context, new collagen-based hydrogels with NPK nutrients encapsulated have been functionalized with synthetic and natural additives, including starch and dolomite, to be used as composite fertilizers. Possible interaction mechanisms are presented in case of each synthetic or natural additive, ranging from strong linkages as a result of esterification reactions until hydrogen bonds and ionic valences. Such interactions are responsible for nutrient release towards soil and plants. These fertilizers have been adequately characterized for their physical chemical and biochemical properties, including nutrient content, and tested on three Greek poor soils and one Romanian normal soil samples. A series of agrochemical tests have been developed by evaluation of uptake and leaching of nutrients on mixtures of sand and soils. It was observed that the clay soil exhibits a higher adsorption capacity than the loam soil for most of nutrients leached from the composite fertilizers tested, with this being correlated with a slower control release towards cultivated plants, thus assuring efficiency of these collagen-based composite fertilizers. The most significant effect was obtained in the case of collagen-based fertilizer functionalized with starch.

Review of Soil Quality Improvement Using Biopolymers from Leather Waste.

This paper reviews the advantages and disadvantages of the use of fertilizers obtained from leather waste, to ameliorate the agricultural soil quality. The use of leather waste (hides and skins) as raw materials to obtain biopolymer-based fertilizers is an excellent example of a circular economy. This allows the recovery of a large quantity of the tanning agent in the case of tanned wastes, as well as the valorization of significant quantities of waste that would be otherwise disposed of by landfilling. The composition of organic biopolymers obtained from leather waste is a rich source of macronutrients (nitrogen, calcium, magnesium, sodium, potassium), and micronutrients (boron, chloride, copper, iron, manganese, molybdenum, nickel and zinc), necessary to improve the composition of agricultural soils, and to remediate the degraded soils. This enhances plant growth ensuring better crops. The nutrient release tests have demonstrated that, by using the biofertilizers with collagen or with collagen cross-linked with synthetic polymers, the nutrient release can be controlled and slowed. In this case, the loss of nutrients by leaching into the inferior layers of the soil and ground water is minimized, avoiding groundwater contamination, especially with nitrate.

Composite Polymers from Leather Waste to Produce Smart Fertilizers.

The leather industry is facing important environmental issues related to waste disposal. The waste generated during the tanning process is an important resource of protein (mainly collagen) which can be extracted and reused in different applications (e.g., medical, agricultural, leather industry). On the other side, the utilization of chemical fertilizers must be decreased because of the negative effects associated to an extensive use of conventional chemical fertilizers. This review presents current research trends, challenges and future perspectives with respect to the use of hide waste to produce composite polymers that are further transformed in smart fertilizers. Hide waste contains mostly protein (collagen that is a natural polymer), that is extracted to be used in the cross-linking with water soluble copolymers to obtain the hydrogels which are further valorised as smart fertilizers. Smart fertilizers are a new class of fertilizers which allow the controlled release of the nutrients in synchronization with the plant's demands. Characteristics of hide and leather wastes are pointed out. The fabrication methods of smart fertilizers and the mechanisms for the nutrients release are extensively discussed. This novel method is in agreement with the circular economy concepts and solves, on one side, the problem of hide waste disposal, and on the other side produces smart fertilizers that can successfully replace conventional chemical fertilizers.

Collagen-Based Hydrogels Composites from Hide Waste to Produce Smart Fertilizers.

The study aims at reusing and recycling the protein hide waste from the leather industry in ecological conditions by elaborating an innovative procedure in order to obtain a collagen matrix functionalized with nitrogen, phosphorus, and potassium (NPK) nutrients to be used for preparing smart fertilizers. This is an interdisciplinary approach, as it starts from hide waste raw material as a critical industrial waste, which is then subjected to several technological steps by selection of optimal processing parameters, followed by product fabrication at the laboratory, and next scales to the industrial pilot plant to obtain novel agro-hydrogels. In this context, the technology scheme for collagen hydrolysate with encapsulated nutrients was proposed and the process parameters were optimized by functionalization of agro-hydrogels with various natural and synthetic polymers, such as polyacrylamide, poly(sodium 4-styrenesulfonate-co-glycidyl methacrylate) copolymer, starch or dolomite. Based on the laboratory experiments, a pilot plant was constructed and tested. Taking as reference the collagen hydrolysate with encapsulated nutrients, the new fertilizers were adequately characterized by chemical analysis, determination of biodegradability and the degree of release of oxidable compounds in water. Based on the biodegradation mechanism and kinetic analysis of oxidable compounds release, adequate arguments are evidenced to demonstrate that these fertilizers can be applied for amendment of poor agricultural soils.