Tuning a green carboxymethyl cellulose-based pre-tanning agent via peroxide oxidation for high chrome exhaustion in leather industry.

The low chrome uptake by collagen in the conventional tanning process leads to the pollution of the wastewater. Due to environmental concerns, leather scientists are already searching for innovative ways to produce pre-tanning agents as a high exhaustion chrome tanning auxiliary. Herein, a novel kind of pre-tanning agent is engineered by converting carboxymethyl cellulose (CMC) to oxidized carboxymethyl cellulose (OCMC) via the hydrogen peroxide process. FT-IR and carboxyl content analysis demonstrated the increase in carboxyl content after oxidation. After that, the obtained OCMC was utilized as a pre-tanning agent, resulting in a high exhaustion of chrome (92.76 %) which is 27.76 % more than conventional chrome tanning (65 %), and the amount of chrome in wastewater reduced to 7.24 %. The hydrothermal stability of wet-blue increased by increasing the uptake of chrome (Ts = 118 °C). The obtained crust leather represented excellent mechanical properties (Tensile strength: 305.68 kg/cm2; tear strength: 50 kg/cm) and desirable organoleptic properties. The environmental analysis signifies a significant step towards a cleaner and sustainable tanning process (COD = 1600, BOD5 = 560 mg/L) compared to the conventional chrome tanning process. Consequently, the obtained results offer a green pre-tanning agent to meet the requirements of the sustainable development of the leather industry.

New materials-based on gelatin coordinated with zirconium or aluminum for ecological retanning.

Ecological retanning agent is an effective way to solve the pollution source of leather manufacturing industry. In this study, the gelatin from chrome-containing leather shavings in the leather industry was used to realize sustainable leather post-tanning. The gelatin hydrolysate (GH) coordinated with Zr4+ or Al3+ to prepare eco-friendly retanning agents GH-Zr and GH-Al. The successful coordination between GH and metal ions was characterized by FTIR and XPS. The retanning agents were characterized by FTIR curve-fitting and circular dichroism spectroscopy. The results showed that the conformation of the secondary structure of the polypeptide became ordered and stable after coordinating with the metal ions. The particle size and weight average molecular weight of the retanning agents were ~1700 nm and ~2100, respectively, measured by nanoparticle size analyzer and gel permeation chromatography (GPC). The retanning agents were applied to retanning of chrome tanned leather and glutaraldehyde tanned leather. The abundant free amino from retanning agents can consume the free formaldehyde. Meanwhile, retanning agents can effectively improve the multiple binding sites, resulting in favorable thickening rate (>110 %) and excellent dye and fatliquor absorption rate with ~99.91 % and ~93.18 %. Thus, this strategy can provide a viable choice for solid leather waste and sustainable development of the leather industry.

May 1,3,5-Triazine derivatives be the future of leather tanning? A critical review.

Leather is produced by a multi-step process among which the tanning phase is the most relevant, transforming animal skin collagen into a stable, non-putrescible material used to produce a variety of different goods, for the footwear, automotive, garments, and sports industry. Most of the leather produced today is tanned with chromium (III) salts or alternatively with aldehydes or synthetic tannins, generating high environmental concern. Over the years, high exhaustion tanning systems have been developed to reduce the environmental impact of chromium salts, which nevertheless do not avoid the use of metals. Chrome-free alternatives such as aldehydes and phenol based synthetic tannins, are suffering from Reach restrictions due to their toxicity. Thus, the need for environmentally benign and economically sustainable tanning agents is increasingly urgent. In this review, the synthesis, use and tanning mechanism of a new class of tanning agents, 1,3,5-triazines derivatives, have been reported together with organoleptic, physical mechanical characteristics of tanned leather produced. Additionally environmental performance and economic data available for 1,3,5-triazines have been compared with those of a standard basic chromium sulphate tanning process, evidencing the high potentiality for sustainable, metal, aldehyde, and phenol free leather manufacturing.

NaH2PO4 synergizes with organic matter to stabilize chromium in tannery sludge.

Heavy metal stabilization is an effective method to treat chromium in tannery sludge. Here we show that mainly investigated NaH2PO4 (MSP) and organic matter (OM) to stabilize chromium in tannery sludge. The experimental investigation revealed that the addition of montmorillonite (MMT) and MSP samples showed a significant increase in the percentage of reducible and oxidizable Cr in the former compared to the samples with the addition of MMT. This is attributed to the formation of Cr-O bond, which allows the MSP to undergo an inner-sphere complexation reaction with the metal oxide of Cr via ligand exchange. Significantly, the MSP moiety adsorbs on the surface of OM through monodentate, which increases the adsorption sites of OM for Cr6+ and promotes the reduction of Cr6+ to Cr3+. Moreover, PO43- reacts with Cr3+ to produce CrPO4 precipitation, thus reducing the free Cr3+ content. Finally, DFT calculations confirmed that a ternary system is formed between PO43-, OM, and Cr, and the binding energy is negative, which indicated that PO43- could co-stabilize Cr with OM.

Synthesis and crosslinking of collagen using 4-3,4,5-tris(oxiran-2-ylmethoxy)benzamido)benzenesulfonic acid for the development of robust metal-free leather.

The leather manufacturing sector is actively pursuing organic alternatives to replace the utilization of inorganic tanning chemicals such as chromium, zirconium, and aluminum due to concerns over their environmental impact. Although glutaraldehyde has been considered a feasible alternative, it still falls short in providing the leather with greater tensile properties and is also considered to be toxic. In this study, we report the synthesis of a sulfonated gallic acid-based epoxide (GSE) and evaluate its performance as a metal-free tanning compound. The synthesized compound was subjected to comprehensive characterization using FTIR (functional group), ESI-MS (molecular weight), and NMR (chemical environment) spectroscopy. Furthermore, the leather treated with GSE demonstrated organoleptic and physical properties that were comparable to those achieved with glutaraldehyde tanning systems. SEM analysis of the GSE-tanned leather exhibited a homogeneous distribution pattern, confirming the stability of the collagen. In addition, the hydrothermal stability temperature of leather crosslinked with epoxide was found to be 83 ± 2 °C. The wastewater generated from the GSE tanning process exhibited a BOD to COD ratio of 0.35 ± 0.04, indicating its high treatability. The results showed that the GSE tanning system provided better tanning efficiency and improved crosslinking and thermal stability without the use of metal salts. Furthermore, the use of GSE as a tanning agent offers several advantages, such as easy availability, biodegradability, and low toxicity, making it a sustainable and environment-friendly option for the leather industry.

A continuous process in mixers-settlers for the removal/recovery of chromium in effluents from the tanning industry.

One of the main environmental issues caused by the tanning industry is given by the high concentration of chromium contained on its effluents. The removal of this pollutant has become a technological challenge. To solve this issue, this work proposes a continuous process based on mixers-settlers for the removal of the chromium present in effluents from the tanning industry. The process involves the use of liquid-liquid extraction systems. The study includes the development of isotherms for the removal and stripping, which are further represented through a mathematical model to determine the number of theoretical extraction stages and other operational variables. The results show that a better extraction is achieved in a system with two theoretical stages using Cyanex 272 as extractant, reaching more than 94% of removal of chromium with an extractant concentration of 0.32 mol/L. For stripping, sulfuric acid is used, obtaining a maximum recovery of 94%.

Potential of biofuel production from leather solid wastes: Indian scenario.

India is one among the major leather-producing countries in the world which shares close to one-fourth of the world's leather solid wastes and most of these wastes are not effectively utilized. These wastes are rich in protein and lipids that could be a potential feedstock for biofuel production, i.e., biogas, biodiesel, etc. Among the 150,000 tons of daily leather solid wastes in India, approximately 87,150 tons are shared by pre-tanning operations (i.e., raw trimmings, fleshing, and hair wastes) while the rest of the 62,850 tons are shared by tanning, post-tanning, and finishing operations (i.e., wet blue trimmings, chrome splits, shavings, buffing dust, crust trimming wastes). This review article shows that there is considerable bioenergy potential for the use of leather solid wastes as a green fuel. The biogas potential of leather solid wastes is estimated to be 40,532.9 m3/day whereas the biodiesel potential is estimated as 15,452.6 L/day. The bio-oil and bio-char potential of leather solid wastes is estimated to be 80,513.0 L/day and 45.8 tons/day, respectively. Several factors influence the biofuel process efficacy, which needs to be taken into consideration while setting up a biofuel recovery plant. The overall biofuel potential of leather solid wastes shows that this feedstock is an untapped resource for energy recovery to add commercial benefits to India's energy supply. Furthermore, in addition to the economic benefits for investors, the use of leather solid wastes for biofuel production will yield a positive environmental impact.

A cleaner leather chemical from feather waste for reducing ammonia-nitrogen pollution and improving biological treatment efficiency of tannery wastewater.

Feather waste is produced in millions of tons globally every year, resulting in a waste of biomass resources and even environmental pollution. A sustainable strategy for utilizing feather waste was proposed by preparing a clean deliming agent for ammonia-nitrogen (NH3-N) reduction in leather manufacture and biological treatment efficiency improvement of tannery wastewater. Briefly, chicken feather wastes were deeply hydrolyzed with sulfuric acid, and the optimized keratin hydrolysate (KHopt) that contained 53.6% crude protein and 41.2% amino acids, such as glutamic acid, serine, proline, leucine, phenylalanine, glycine, valine, and arginine, was obtained and used to delime limed cattle hides. The appropriate ratio of amino acids in KHopt gave KHopt a great pH-buffering capacity and maintained a stable float pH of approximately 9 throughout the deliming process. The isoelectric points of KHopt (3.8) and the limed hide (6.3) were both lower than the float pH, thereby bringing about an electrostatic repulsion between the KHopt and the hide surface, which is helpful for KHopt to penetrate and deswell the limed hide rapidly. Moreover, the KHopt deliming effectively removed calcium from the limed hide and achieved leather comparable to conventional leather for commercial applications. KHopt reduced the NH3-N concentrations of deliming effluent and tannery wastewater by 91.1% and 80.6%, respectively, compared with the conventional deliming agent (ammonium sulfate), and dramatically increased the biological treatment efficiency of tannery wastewater. The results showed that efficient and high-value use of feather waste was made by preparing KHopt for sustainable leather manufacturing.

Unexpected associations of long-term and excessive exposure to trivalent chromium with hypertension and glycosuria in male tannery workers.

Serious health hazards including renal, skin and hearing disorders have been reported in Bangladeshi tannery workers (TWs) who were chronically exposed to a large amount of trivalent chromium [Cr(III)]. However, the effects of Cr(III) exposure on the prevalence of hypertension and the prevalence of glycosuria in TWs remain unknown. Since the Cr level in toenails is an established marker reflecting long-term exposure to Cr(III) in humans, the associations of Cr levels in toenails with the prevalence of hypertension and the prevalence of glycosuria in male tannery and non-tannery office workers (non-TWs) in Bangladesh were investigated in this study. The mean toenail Cr level in non-TWs (0.5 µg/g, n = 49) was comparable to that in the general population reported previously. Mean Cr levels in TWs with a low toenail Cr level (5.7 µg/g, n = 39) and those with a high toenail Cr level (298.8 µg/g, n = 61) were >10-fold and >500-fold higher, respectively, than that in non-TWs. Our univariate and multivariate analyses indicated that the prevalence of hypertension and the prevalence of glycosuria in TWs with a high toenail Cr level, but not in TWs with a low toenail Cr level, were significantly lower than those in non-TWs. This study showed for the first time that long-term and excessive exposure to Cr(III) that is more than >500-fold but not >10-fold higher than the usual exposure level could decrease the prevalence of hypertension and the prevalence of glycosuria in TWs. Thus, this study revealed unexpected effects of exposure to Cr(III) on health.

Degradation of tannery hide raw trimming hairs using keratinolytic bacteria isolated from tannery effluent-contaminated soil.

The disposal of keratinous wastes produced by several leather industries is evolving into a global problem. Around 1 billion tonnes of keratin waste are released into the environment each year. In the breakdown of tannery waste, certain enzymes, such as keratinases produced from microorganisms, might be a better substitute for synthetic enzymes. Keratinase enzymes are able to hydrolyze gelatin, casein, bovine serum albumin and insoluble protein present in wool, feather. Therefore, in this study, bacterial strains from tannery effluent-contaminated soil and bovine tannery hide were isolated and assessed for their ability to produce the keratinolytic enzyme. Among the six isolates, the strain NS1P showed the highest keratinase activity (298 U/ml) and was identified as Comamonas testosterone through biochemical and molecular characterization. Several bioprocess parameters such as pH, temperature, inoculum size, carbon sources, and nitrogen sources were optimized in order to maximize crude enzyme production. The optimized media were used for inoculum preparation and subsequent biodegradation of hide hairs. The degradation efficacy of the keratinase enzyme produced by Comamonas testosterone was examined by degrading bovine tannery hide hairs, and it was found to be 73.6% after 30 days. The morphology of the deteriorated hair was examined using a field emission scanning electron microscope (FE-SEM), which revealed significant degradation. Thus, our research work has led to the conclusion that Comamonas testosterone may be a promising keratinolytic strain for the biodegradation of tannery bovine hide hair waste and the industrial production of keratinases.

Analysis of heavy metals and toxicity level in the tannery effluent and the environs.

Heavy metals have found a large number of applications in the recent times. These heavy metals are being continuously added to our environment through various natural and anthropogenic activities. Industries employ heavy metals to process raw materials into final products. Effluents from these industries carry heavy metals. Atomic absorption spectrophotometer and ICP-MS (inductively coupled plasma-mass spectrometer) are of great help in detecting various elements in the effluent. They have been extensively applied to solve problems related to environmental monitoring and assessment. Heavy metals like Cu, Cd, Ni, Pb, and Cr can be easily detected using both the techniques. Some of these heavy metals are toxic to both humans and animals. They can have significant related health effects. Presence of heavy metals in the industrial effluent has gained varied attention in the recent times and it has become one of the major causes of water and soil pollution. Significant contributions can be linked with the leather tanning industry. As the effluent from the tanning industry has been found to contain a large number of heavy metals in many studies. Continuous monitoring and treatment of the effluent is necessary to keep a check on the concentration of heavy metals in these effluents. This study focuses on the analysis of the various studies available on tannery effluents, methods used for heavy metal analysis, toxicity of these heavy metals, and the related major health effects. Data for heavy metals in the tannery effluent from different studies in last two decades has been collected and analysed. The data from various studies indicates that Cr, Cd, Pb, Zn, Cu, Fe, and Ni are the most commonly found heavy metals released from the tanning industry. Proper management of the tannery effluent is thus very essential for saving the environment.

Preparation and application of tremella polysaccharide based chrome free tanning agent for sheepskin processing.

The abuse of chrome tanning agent in leather processing has caused great harm to human health and the natural environment. We use tremella polysaccharides (TP), lentinan (LNT) and konjac gum (KG) as raw materials, and sodium periodate as oxidant to prepare the corresponding polysaccharide tanning agent. Tremella polysaccharide was selected as the best tanning agent according to the shrinkage temperature, and the subsequent experiments were carried out. Tremella polysaccharide (TP) as raw material and sodium periodate as an oxidant, dialdehyde tremella polysaccharide (DTP) was prepared and applied in leather tanning. The effects of different oxidation conditions (sodium periodate dosage, temperature, pH, and reaction time) on the shrinkage temperature of DTP tanned leather were studied. The change of shrinkage temperature showed that the dosage of sodium periodate had the greatest influence on the shrinkage temperature. Therefore, the effects of different dosage of sodium periodate on the aldehyde content and molecular weight of DTP were investigated, including the analysis of physical properties and microstructure of tanned leather. In general, the increase of sodium periodate dosage was found to increase the aldehyde content and reduce the molecular weight, which was more conducive to leather tanning.

Management of tannery waste effluents towards the reclamation of clean water using an integrated membrane system: A state-of-the-art review.

Tanning and other leather processing methods utilize a large amount of freshwater, dyes, chemicals, and salts and produce toxic waste, raising questions regarding their environmental sensitivity and eco-friendly nature. Total suspended solids, total dissolved solids, chemical oxygen demand, and ions such as chromium, sulfate, and chloride turn tannery wastewater exceedingly toxic for any living species. Therefore, it is imperative to treat tannery effluent, and existing plants must be examined and upgraded to keep up with recent technological developments. Different conventional techniques to treat tannery wastewater have been reported based on their pollutant removal efficiencies, advantages, and disadvantages. Research on photo-assisted catalyst-enhanced deterioration has inferred that both homogeneous and heterogeneous catalysis can be established as green initiatives, the latter being more efficient at degrading organic pollutants. However, the scientific community experiences significant problems developing a feasible treatment technique owing to the long degradation times and low removal efficiency. Hence, there is a chance for an improved solution to the problem of treating tannery wastewater through the development of a hybrid technology that uses flocculation as the primary treatment, a unique integrated photo-catalyst in a precision-designed reactor as the secondary method, and finally, membrane-based tertiary treatment to recover the spent catalyst and reclaimable water. This review gives an understanding of the progressive advancement of a cutting-edge membrane-based system for the management of tanning industrial waste effluents towards the reclamation of clean water. Adaptable routes toward sludge disposal and the reviews on techno-economic assessments have been shown in detail, strengthening the scale-up confidence for implementing such innovative hybrid systems.

Facile degradation of chitosan-sodium alginate-chromium (III) gel in relation to leather re-tanning and filling.

Natural polysaccharide hydrogel, exemplified by chitosan­sodium alginate (CS-SA), has been prevailing in adsorption of chromium (III) (Cr(III)) containing contaminant. However, the traditional desorption of CS-SA-Cr(III) to recycle the adsorbent faces the problems including chemical desorbents secondary pollution, resource waste of the terminal CS-SA adsorbents, and tedious work of reusing the desorbed Cr(III). Herein, the adsorption product, CS-SA-Cr(III) gel, was degraded to CS/SA/Cr(III) sol and applied in leather re-tanning and filling processes directly. To achieve this goal, three degradation methods were used to transform the gel to sol. Due to the excellent overall performance of the CS/SA/Cr(III)-HMD4 sol (obtained by the hydrothermal-mechanical degradation method for 4 h (HMD4)), including wide size and distribution range, moderate viscosity (54 ± 3.1 mPa·s), high electronegativity (-38.6 ± 5.8 mV), and good stability, the resultant leather after re-tanning and filling by the sol achieved fascinating properties such as good thermal stability (Ts, 116.8 ± 1.8 °C; Td, 94.2 ± 1.7 °C), mechanical performance (tensile strength, 6.9 ± 0.52 MPa; elongation at break, 95 ± 3.0 %), and superduper thickening rate (31.8 %). Moreover, the mechanism of good re-tanning and filling effects was deciphered. Therefore, this work intends to overcome the limitation of traditional desorption technology and further realizes the high-valued application of the exhausted CS-SA-Cr(III) in leather re-tanning and filling processes.

An efficient dehairing system supported by oxidative-enzymatic auxiliary towards sustainability.

A method of dehairing of goat skins using oxidative chemicals and protease enzymes has been attempted. The dehairing process is one of the important and essential steps in leather making, where hair is removed by lime and sodium sulphide in the conventional process. This conventional dehairing system generates a higher amount of pollution problem as compared to the other unit operations and unit processes. In this work, dehairing of the goat skins through oxidative agents namely magnesium peroxide and protease enzyme has been attempted. For this, protease has been produced from Bacillus sp. at the laboratory level and the activity was found. The dehairing of goat skins takes place for the duration of 14-16 h. The leather produced with the experimental sample showed comparable organoleptic and strength properties with the conventional sample. This method paved the way for the reduction of pollution loads especially BOD, COD, and TDS to the level of 59, 27, and 77%, respectively, in comparison with the control sample. The reaction kinetics for the formation of the ligand-macromolecular complex is found in the isothermal titration calorimetry (ITC) experiment and a mathematical model has been formulated. The dyed crust leather showed comparable colour properties. In addition to that, there is a reduction in processing time for leather making through skipping reliming and deliming processes which are said to be another advantage of this method. The physical strength properties of the experimental leather were also comparable with conventionally produced leather.

Strategical development of chrome-free tanning agent by integrating layered double hydroxide with starch derivatives.

The development of sustainable and eco-friendly leather industry requires green tanning agents because of unbounded chromium (easily converted into hazardous Cr-VI) in chrome tanned leather. In this study, a chrome-free tanning agent (OS-LDHs) was established by integrating layered double hydroxide (magnesium aluminum zirconium hydrotalcite, LDHs) with starch derivatives. A series of oxidized starch (OS) were prepared as masking agents for LDHs tanning process. Among them, the weight-average molecular weight (Mw) of 1685 g/mol could be reached, which will promise the well-distribution of OS. The SEM and EDS analysis confirmed the uniform penetration of OS-LDHs, avoiding accumulation on the surface of crust leather. Notably, leather tanned by OS-LDHs achieved shrinkage temperature of 66.7 °C, porosity of 75.51 % and tear strength of 66.7 N/mm. Not only the hydrogen bond but also the coordination between NH2, COOH in collagen and OS-2-LDHs improved the thermal stability of leather without destroying the collagen triple helix.

Electrochemical conversion of chromium from tannery effluents for potential reuse in industrial applications.

Electrochemical oxidation of trivalent chromium from leather tanning mud waste leachates (containing ca 6 g.L-1 Cr(III)) to its hexavalent form was carried out using a PbOx/Pb anode electrode in a prototype small (0.4 L) cylindrical batch electrochemical reactor. The PbOx/Pb anode was prepared by electrochemical anodization at constant current (75 mA cm-2 for 30 min) in a sulfuric acid solution and characterized by the cyclic voltammetry technique to investigate the effect of pH on the process. It was found that at pH = 3, Cr(III) oxidation prevails over the competing water oxidation-oxygen evolution reaction (OER), hence increasing the efficiency of the process. A detailed study of pH (0-3), current density (12-24 mA cm-2), and cell type (divided-undivided) effects on bulk electrolysis of Cr(III) leachates in the batch prototype reactor resulted in process optimization. At pH = 3, 12 mA cm-2 and a cathode inserted in a porous diaphragm envelope, nearly 70% conversion was achieved at a nearly 60% current efficiency, among the highest in the previously reported literature. The method (further optimized with an ion-selective membrane separator) could offer an attractive route for tannery Cr(III) conversion to Cr(VI) for reuse as an etchant or electroplating agent.

Tannery waste as a renewable source of nitrogen for production of multicomponent fertilizers with biostimulating properties.

The studies presented in this work show that solid tannery waste-like shavings can be used as high-protein materials for fertilizer production following the concept of the circular economy. To select appropriate process parameters (mass ratio of shavings meal to the hydrolyzing agent (S:L), hydrolysis medium concentration, temperature) and to ensure the highest possible hydrolysis efficiency, it is useful to apply the well-known response surface methodology (RSM). The analyses revealed that chromium shavings (SCr) were most preferably treated with 10% KOH in a ratio of S:L 1:1 with the process being carried out at 160 °C (6.59% N). The optimal hydrolysis conditions for non-chromium (S) shavings were: S:L ratio 1:2, 10% H2SO4, and temperature 160 °C (4.08% N). Chromium concentrations in hydrolysates from S and SCr shavings obtained under optimal conditions were 15.2 mg/kg and 9483 mg/kg, respectively. Hydrolysate samples were analyzed by reversed-phase high-pressure liquid chromatography (RP-HPLC) that revealed that the type of hydrolysis (acidic/alkaline) affects the amino acid profile. Approximately 4.5 times more amino acids were extracted in the KOH environment than during acidic treatment. The hydrolysates contained mainly glycine, alanine, and proline, which are primarily responsible for stimulating plant growth by supporting chlorophyll synthesis, chelating micronutrients, improving pollen fertility, or resistance to low temperatures. The conversion of tannery waste into fertilizer requires the control of contaminant levels, especially chromium, which can oxidize to the carcinogenic form Cr(VI) that is hazardous to humans and the environment.

A novel synergistic covalence and complexation bridging strategy based on multi-functional biomass-derived aldehydes and Al(III) for engineering high-quality eco-leather.

To get rid of the chrome pollution faced by the leather industry, we explored a novel engineering high-quality eco-leather technology based on the synergistic interactions between biomass-based aldehydes and Al(III). Firstly, dialdehyde xanthan gum (DXG) was prepared to covalently crosslink with the collagen fibers (CFs) via Schiff-base linkages under alkaline conditions, endowing the leather with a shrinkage temperature (Ts) of 80 °C and opening channels for the subsequent penetration of Al species (AL). Secondly, and for this latter purpose, the DXG-tanned leather was acidified to release part of the DXG from the leather according to the dynamic nature of the Schiff-base. Containing suitable oxygen-containing groups (OGs) with excellent complexation capabilities, the released DXG served as masking agents for AL, facilitating the penetration of AL into the inner CFs network for further complexation crosslinking. Consequently, a denser crosslinking network was constructed in the leather, and the crust leather exhibited higher Ts (82.2 °C), improved mechanical (tensile strength: 13.4 N/mm2, tear strength: 53.3 N/mm) and organoleptic properties than those of the DXG crust or AL crust leathers. This demonstrates that this synergistic covalence and complexation bridging strategy is a sustainable option to substitute highly restricted chrome tanning agent for eco-leather production.

Biological Solubilisation of Leather Industry Waste in Anaerobic Conditions: Effect of Chromium (III) Presence, Pre-Treatments and Temperature Strategies.

Collagen-based polymers and their blends have attracted considerable interest for new materials development due to their unique combination of biocompatibility, physical and mechanical properties and durability. Leather, a modified natural biopolymer made from animal rawhide and the first synthetic collagen-based polymer known since the dawn of civilization, combines all these features. Rawhide is transformed into leather by tanning, a process in which the collagen is cross-linked with different agents to make it stronger and more durable and to prevent its decay. Research on the development of environmentally friendly procedures and sustainable materials with higher efficiency and lower costs is a rapidly growing field, and leather industry is not an exemption. Chrome-tanned and vegetable-tanned (chromium-free) shavings from the leather industry present a high content of organic matter, yet they are considered recalcitrant waste to be degraded by microbiological processes like anaerobic digestion (AD), a solid technology to treat organic waste in a circular economy framework. In this technology however, the solubilisation of organic solid substrates is a significant challenge to improving the efficiency of the process. In this context, we have investigated the process of microbial decomposition of leather wastes from the tannery industry to search for the conditions that produce optimal solubilisation of organic matter. Chrome-tanned and chromium-free leather shavings were pre-treated and anaerobically digested under different temperature ranges (thermophilic-55 °C-, intermediate-42 °C- and mesophilic-35 °C) to evaluate the effect on the solubilisation of the organic matter of the wastes. The results showed that the presence of chromium significantly inhibited the solubilization (up to 60%) in the mesophilic and intermediate ranges; this is the fastest and most efficient solubilization reached under thermophilic conditions using the chromium-free leather shaving as substrates. The most suitable temperature for the solubilization was the thermophilic regime (55 °C) for both chromium-free and chrome-tanned shavings. No significant differences were observed in the thermophilic anaerobic digestion of chromium-free shavings when a pre-treatment was applied, since the solubilisation was already high without pre-treatment. However, the pre-treatments significantly improved the solubilisation in the mesophilic and intermediate configurations; the former pre-treatment was better suited in terms of performance and cost-effectiveness compared to the thermophilic range. Thus, the solubilisation of chromium-free tannery solid wastes can be significantly improved by applying appropriate pre-treatments at lower temperature ranges; this is of utter importance when optimizing anaerobic processes of recalcitrant organic wastes, with the added benefit of substantial energy savings in the scaling up of the process in an optimised circular economy scenario.