Progress and recent trends in biotechnological methods for leather processing

Global environmental regulations are changing the leather-processing industry. Pre-tanning and tanning processes contribute 80-90% of the total pollution in the industry and generate noxious gases, such as hydrogen sulfide, as well as solid wastes, such as lime and chrome sludge. The use of enzyme-based products is currently being explored for many areas of leather making. Furthermore, enzymes are gaining increasing importance in the de-hairing process, eliminating the need for sodium sulfide. This review discusses emerging novel biotechnological methods used in leather processing. One significant achievement is the development of a bioprocess-based de-hairing and fiber-opening methodology to reduce toxic waste.     

Simultaneous phytoremediation of tannery effluent and production of fatty acids rich biomass by Chlorella sorokiniana

Journal of Applied Phycology - Tanning is a technique of transforming hides to skins and the production of leather products involves a wide variety of processes that produce substantial amounts of...     

Use of Life Cycle assessment in the procedure for the establishment of environmental criteria in the catalan ECO-label of leather

Life Cycle Assessment (LCA) has been used to detect the environmental ‘hot spots’ in the chrome-tanned bovine leather industry. We have studied those stages in the life cycle of leather, which occur ‘from cradle to gate’. The production chain studied starts with the agricultural products (fertiliser and pesticide production is also included) needed for cattle raising, it is followed by the slaughterhouse, and ends at the tanning industry gate. Main chemicals and waste flows in and out of this chain have also been included in the analysis. One of the main conclusions is that the tannery is an important stage in most of the impact categories, mainly due to the landfilling of the tannery wastes. Agriculture and — to a lesser extent — cattle raising also play a very important role in most of the impact categories; the former, due to the related energy consumption and use of fertilisers, and the latter due to the emissions associated with animal care. The Autonomous Government of Catalonia is using the results of this study to establish the environmental criteria that a leather product must fulfil in order to attain the Catalan eco-label.     

A Life Cycle Assessment on the Dehairing of Rawhides: Chemical Treatment versus Enzymatic Recovery through Solid State Fermentation

The leather industry needs to switch from the traditional chemically based dehairing process to an environmentally friendly one so that the overall burdens to the environment are reduced. The primary goal of the work was thus to compare the chemical leather dehairing process to an enzymatically based one using the enzymes that are extracted after the application of solid state fermentation (SSF) on hair wastes generated after dehairing. The environmental burdens of the dehairing stage were determined using a life cycle assessment (LCA) approach by comparing the two aforementioned management scenarios. The first scenario was the commonly used technology in which hair is removed via a chemical process and then composted in open piles. This scenario included two subscenarios where hair waste is either incinerated or landfilled. In the second scenario, the proteolytic enzymes extracted during the SSF of the residual hair are used to dehair the new rawhides instead of chemicals. Industrial and laboratory data were combined with international databases using the SimaPro 8.0 LCA software to make comparisons. The environmental impacts associated with the enzymatic dehairing were significantly lower than the ones associated to the conventional chemical dehairing process. This difference is attributed to the impacts associated with the original production of the chemicals and to the electricity consumed in the conventional method. A sensitivity analysis revealed that the results are affected by the amounts of chemicals used during dehairing.     

Microorganisms resistant to heavy metals and toxic chemicals as indicators of environmental pollution and their use in bioremediation

Microorganisms present in water samples from various industrial effluents were analysed for their resistance to lead, chromium, and cadmium. The ability of these microorganisms to grow on or metabolize toxic hydrocarbons and pesticides was also checked. Microorganisms in samples from the steel and tanning industries were generally resistant to metal ions but were not capable of metabolizing toxic hydrocarbons. Conversely, microorganisms found in samples of pesticide and from the chemical industry were capable of metabolizing hydrocarbons and pesticides but were not much resistant to metal ions. Microorganisms from effluents of the paint industry and urban wastes were resistant to lead. A correlation between the population of microorganisms and the type of pollution was observed. Indigenous microorganism could be regarded as indicators of pollution and be used in various operations to resist, process, metabolize, and detoxify toxic industrial wastes.     

Biochemical and Molecular Characterization of a Serine Keratinase from Brevibacillus brevis US575 with Promising Keratin-Biodegradation and Hide-Dehairing Activities

Dehairing is one of the highly polluting operations in the leather industry. The conventional lime-sulfide process used for dehairing produces large amounts of sulfide, which poses serious toxicity and disposal problems. This operation also involves hair destruction, a process that leads to increased chemical oxygen demand (COD), biological oxygen demand (BOD), and total suspended solid (TSS) loads in the effluent. With these concerns in mind, enzyme-assisted dehairing has often been proposed as an alternative method. The main enzyme preparations so far used involved keratinases. The present paper reports on the purification of an extracellular keratinase (KERUS) newly isolated from Brevibacillus brevis strain US575. Matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF/MS) analysis revealed that the purified enzyme was a monomer with a molecular mass of 29121.11 Da. The sequence of the 27 N-terminal residues of KERUS showed high homology with those of Bacillus keratinases. Optimal activity was achieved at pH 8 and 40°C. Its thermoactivity and thermostability were upgraded in the presence of 5 mM Ca²⁺. The enzyme was completely inhibited by phenylmethanesulfonyl fluoride (PMSF) and diiodopropyl fluorophosphates (DFP), which suggests that it belongs to the serine protease family. KERUS displayed higher levels of hydrolysis, substrate specificity, and catalytic efficiency than NUE 12 MG and KOROPON® MK EG keratinases. The enzyme also exhibited powerful keratinolytic activity that made it able to accomplish the entire feather-biodegradation process on its own. The kerUS gene encoding KERUS was cloned, sequenced, and expressed in Escherichia coli. The biochemical properties of the extracellular purified recombinant enzyme (rKERUS) were similar to those of native KERUS. Overall, the findings provide strong support for the potential candidacy of this enzyme as an effective and eco-friendly alternative to the conventional chemicals used for the dehairing of rabbit, goat, sheep and bovine hides in the leather processing industry.     

Alkaline protease from Thermoactinomyces sp. RS1 mitigates industrial pollution

Proteases have found a wide application in the several industrial processes, such as laundry detergents, protein recovery or solubilization, prion degradation, meat tenderizations, and in bating of hides and skins in leather industries. But the main hurdle in industrial application of proteases is their economical production on a large scale. The present investigation aimed to exploit the locally available inexpensive agricultural and household wastes for alkaline protease production using Thermoactinomyces sp. RS1 via solid-state fermentation (SSF) technique. The alkaline enzyme is potentially useful as an additive in commercial detergents to mitigate pollution load due to extensive use of caustic soda-based detergents. Thermoactinomyces sp. RS1 showed good protease production under SSF conditions of 55 °C, pH 9, and 50 % moisture content with potato peels as solid substrate. The presented findings revealed that crude alkaline protease produced by Thermoactinomyces sp. RS1 via SSF is of potential application in silver recovery from used X-ray films.     

A novel process for biodegradation and effective utilization of chrome shavings,a solid waste generated in tanneries,using chromium resistant Bacillus subtilis P13

Present work deals with the development of an efficient and value-added process for the management of chrome shavings, a protein-rich, chromium-containing solid waste, produced in large quantities during the post-tanning operations in the leather industry, using Bacillus subtilis P13, a hot spring isolate. This bacterium was able to effectively degrade and grow using chrome shavings as the protein source and produce in the spent medium high levels of a keratinolytic serine protease that can be proficiently applied for the pre-tanning processing step of hide dehairing. The bacterium was moderately chromium resistant tolerating up to 35 ppm and 350 ppm of Cr(VI) and Cr(III) salts, respectively and showed bioaccumulation and bio-sorption of Cr(III) and Cr(VI). Growth profile and enzyme production were comparable in basal and production media containing chrome shavings. An efficient waste management process is described using solid substratum column reactor, leading to the liquefaction of the proteinaceous waste and the recovery of dehairing protease as concentrated product as well as Cr recovery for reuse in tanning. A continuous reactor scheme is proposed, where the biomass can be reused as the seed for chrome shaving hydrolysis for in-house waste management and by-product recovery in the tannery industry.     

Leather tanning workers: chromosomal aberrations in peripheral lymphocytes and micronuclei in exfoliated cells in urine

A cytogenetic study was performed on workers of a leather tanning industry. Two different approaches for the biological monitoring of the individuals were used: chromosomal aberration analysis in peripheral lymphocytes and the frequency of micronucleated cells exfoliated in urine samples. 26 men working in the sections considered to present a greater risk were included in the study. Controls were 20 men that were not exposed to chemicals. The percentage of abnormal cells was higher in workers than in controls. Smokers showed higher values of chromosome breaks than non-smokers in both groups. These differences were not statistically significant. The percentage of cells with chromatid and chromosome gaps in workers and controls was different (p less than 0.01). A slight but not significant increase in the mean percentage of micronuclei was observed in the exposed group. We conclude that exposure to chemicals during leather tanning did not produce genotoxic effects measured by chromosomal aberrations in peripheral lymphocytes and micronuclei in urine in this group of workers.     

Measuring the Environmental Footprint of Leather Processing Technologies

The selection of materials and manufacturing processes often determines most of the environmental impact that a product will have during its life cycle. In directing consumption toward products with the least impact on the environment, measuring and comparing material alternatives with site‐specific data is a fundamental prerequisite. Within the apparel and footwear industry, some famous brands have recently been basing their advertising on the claim that vegetable‐tanned leather is more environmentally friendly than chromium‐tanned leather. However, there is a lack of scientific research assessing and comparing vegetable‐ and chromium‐tanned leather in a wider context than the toxicity of chromium. To fill this gap, this study measured and compared the carbon, water, and energy footprint of vegetable and chromium leather processing technology and intermediate processing stages in 12 selected tanneries in seven different countries worldwide. Each tannery proved to be very individual, and therefore attempting to perform this type of analysis without simply producing meaningless generalities is a challenge for companies, researchers, and regulators. The variability in results demonstrates that secondary data for the tanning phase should be utilized with caution in a decision‐making context. The use of primary data would be advisable for life cycle assessment studies of leather goods. No significant differences were found in the footprint of vegetable and chromium leather processes, but these are only indicative findings and need confirmation in further studies. An important area needing investigation is then how a fair comparison can be made between renewable natural materials and nonrenewable materials used in both leather‐processing technologies.     

Determination of total chromium in tanned leather samples used in car industry

Despite the high competition of synthetic fibers leather is nowadays still widely used for many applications. In order to ensure a sufficient stability of the skin matrix against many factors, such as microbial degradation, heat and sweat, a tanning process is indispensable. Using chromium (III) for this purpose offers a multitude of advantages, thus this way of tanning is widely applied. During the use of chromium tanned leather as clothing material as well as for decoration/covering purposes, chromium is extracted from the leather and may then cause nocuous effects to human skin, e.g. allergic reactions. Thus the knowledge of the total chromium content of leather samples expected to come into prolonged touch with human skin is very important. In car industry leather is used as cover for seats, steering wheel and gearshift lever The chromium contents often chromium tanned leather samples used in car industry were determined. First all samples were dried at 65 degrees C overnight and then cut in small pieces using a ceramic knife, weighed and analyzed by inductively coupled plasma--optical emission spectrometry (ICP-OES) after acidic microwave assisted digestion. The total chromium amounts found were in the range from 19 mg/g up to 32 mg/g. The extraction yield of chromium from leather samples in sweat is approximately 2-7%. Thus especially during long journeys in summer chromium can be extracted in amounts which may cause nocuous effects for example on the palm of the hands or on the back.     

Use of immobilised biocatalysts in the processing of cheese whey

Food processing industry operations need to comply with increasingly more stringent environmental regulations related to the disposal or utilisation of by-products and wastes. These include growing restrictions on land spraying with agro-industrial wastes, and on disposal within landfill operations, and the requirements to produce end products that are stabilised and hygienic. Much of the material generated as wastes by the dairy processing industries contains components that could be utilised as substrates and nutrients in a variety of microbial/enzymatic processes, to give rise to added-value products. A good example of a waste that has received considerable attention as a source of added-value products is cheese whey. The carbohydrate reservoir of lactose (4–5%) in whey and the presence of other essential nutrients make it a good natural medium for the growth of microorganisms and a potential substrate for bioprocessing through microbial fermentation. Immobilised cell and enzyme technology has also been applied to whey bioconversion processes to improve the economics of such processes. This review focuses upon the elaboration of a range of immobilisation techniques that have been applied to produce valuable whey-based products. A comprehensive literature survey is also provided to illustrate numerous immobilisation procedures with particular emphasis upon lactose hydrolysis, and ethanol and lactic acid production using immobilised biocatalysts.     

Chitosan/Collagen Hydrolysate Based Films Obtained from Hide Trimming Wastes Reinforced with Chitosan Nanoparticles

One of the long-standing problems of the leather manufacturing industry is that tons of solid leather waste generated during production meet environmental standards. Among all these solid wastes, untanned trimming wastes are of primary interest because of their relative collagen content, and therefore, in this research, hide trimming wastes from tanneries were used to prepare biodegradable films. The SDS-PAGE results suggested that obtained collagen hydrolysate (CH) was in its natural molecular form. Chitosan nanoparticles (CSNPs) were synthesized by ionotropic gelation technique with chitosan (CS) and tripolyphosphate anions and used in the preparation of CS/CH/CSNPs films containing different concentrations of CSNPs. The incorporation of CSNPs in CS/CH films has positively improved the films' remarkable physical properties. The DSC result showed that CS/CH films incorporated with CSNPs had higher glass transition and melting temperature. As a result, it was determined that CS/CH/CSNPs nanocomposite films have a high potential in biodegradable film systems.

     

Hair,serum, and urine chromium concentrations in former employees of the leather tanning industry

In this study, we measured concentrations of Cr in hair, serum, and urine of men who were previously employed in the leather tanning industry. Concentrations of Cr in hair and serum were significantly lower than corresponding values obtained during their employment and were comparable to levels obtained for controls in a previous study. These results suggest that Cr III accumulated from employment in the leather tanning industry does not result in longterm elevation of Cr concentrations in the body     

Assessment of pelt quality in leather making using a novel non-invasive sensing approach

Excessive removal of structural material from skin during leather processing results in unattractive crease formation in leather. It is difficult to detect this in pelts at an early processing stage as it only becomes really apparent once the skin is made into leather. There would be great advantages in detecting the problem at the pickled pelt stage (skins treated with sodium sulphide and lime, bated with enzymes, and then preserved in NaCl and sulphuric acid) so that adjustments to the processing could be made to mitigate the effect. A novel bio-sensor for inspection of pickled lamb pelts has been fabricated and developed. The sensor has the planar Interdigital structure. The experimental results show that the sensor has a great potential to predict the quality of leather in a non-invasive and non-destructive way.     

Losses cause by ixodid and demodectic ticks and mites in the tanning industry

Damage done to skin of cattle and defects of raw leather, which are caused by ixodid and demodecid ticks, parasitic on animals, are described. Losses of tanning industry amount to 1.6 to 3.7 thousand roubles per each thousand of finished box-calf leathers.     

Bacterial succession on raw buffalo hide and their degradative activities during ambient storage

Inception of microbiology in leather industry was with reference to tanning processes where major concern was finished product bacteriology. Present investigation aims to study the bacteriology of unprocessed raw material, buffalo hide in particular using culture based and culture independent approach. Denaturing gradient gel electrophoresis (DGGE) analysis of the stored hide at different time intervals was done to study temporal successional shifts in the bacterial community. Considering the protein and fat content of hide, proteolytic and lipolytic bacteria were isolated and identified as major degradative flora. The degradative nature of individual isolate was confirmed through in vitro and in vivo investigations as collagenase production and ability to deteriorate raw hide to release amino acids and free fatty acids, respectively. Furthermore, the histological analysis of bacterially spiked raw hides was done as aid to the conclusions drawn. It was found that the temporal bacterial successional shifts occurring on ambient stored raw buffalo hide could be better understood using DGGE. Isolated and characterized degradative flora could be used as test organisms to discover new preservatives and to assess the process of preservation. Even though the process of degradation is very complex, the culture based and culture independent analysis of degradative microflora is comprehensive.     

Ultrasonically assisted liquefaction of lignocellulosic materials

In our research, we have utilized high energy ultrasound for the liquefaction of different lignocellulosic materials, wood wastes in particular. We developed a highly efficient way of transforming this biomass waste into valuable chemicals. It was found, that the reaction yield in all experiments was high and that the reaction times were shortened up to nine times when using the ultrasound process with smaller residual particles and with no influence on the hydroxyl number of the final products. The use of the ultrasound process inhibits the formation of the large molecular structures during the liquefaction from the degradation products, by keeping the reactive segments apart and due to such a short reaction time being used. The short reaction time and subsequent low energy consumption for the liquefaction reaction leads to the creation of the new method for the transformation of the wood waste materials into valuable chemicals.     

Biodegradability of tannin-containing wastewater from leather industry

Tannins occur commonly in the wastewaters from forestry, plant medicine, paper and leather industries. The treatment of this kind of wastewaters, including settling and biodegradation, is usually difficult because tannins are highly soluble in water and would inhibit the growth of microorganisms in activated sludge. The objective of this study is to investigate biodegradability of tannin-containing wastewaters, so as to characterize the pollution properties of such wastewaters and provide a reference for their biological treatment in wastewater treatment plants. The research was typified by using the wastewater collected from vegetable tanning process in leather industry. A model was developed to describe the activated sludge process, and the biodegradation kinetics of vegetable tanning wastewater (VET wastewater) was studied. It was found that the biodegradability of tannin-containing wastewater varies heavily with the content of tannins in wastewater. The biodegradation of VET wastewater with tannin content around 4,900 mg/l occurred inefficiently due to the inhibition of tannins to the activated sludge process, and only 34.7% of biodegradation extent was reached in 14 days of incubation. The optimal biodegradability of VET wastewater was observed when its tannin content was diluted to 490 mg/l, where the COD and tannin removals reached 51.3% and 45.1% respectively in 6 days. Hence, it is suggested that a proper control of tannin content is necessary to achieve an effective biodegradation of tannin-containing wastewaters in wastewater treatment plants.