Journal of Cleaner Production 226 (2019) 720e729

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Journal of Cleaner Production

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Leather tanning: Life cycle assessment of retanning, fatliquoring and

dyeing
Andrea Luca Tasca**, Monica Puccini*
Department of Civil and Industrial Engineering, University of Pisa, Pisa, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Tanneries boost the local economic development, but lead to severe environmental pollution; hence,
Received 30 October 2018 improving the environmental assessment of this sector is essential. In this paper, the Life Cycle
Received in revised form Assessment method was applied to estimate impacts on the environment and human health of retan-
25 March 2019
ning, fatliquoring and dyeing. The analysis was performed from a “gate to gate” perspective. Moreover,
Accepted 30 March 2019
sulpho chlorinated paraffin and epoxidized vegetable oil have been evaluated as alternative fatliquoring
Available online 4 April 2019
agents.
The production of electricity required for the rotation of drums gives the main contribute to most of
Keywords:
LCA
the impact categories, followed by the azo-dye production. Emissions of sulfur dioxide, nitrogen oxides,
Tannery manganese, vanadium and nickel associated to power plants are the main sources of terrestrial acidi-
Environmental impact assessment fication and particulate matter formation, as well as of human and marine toxicity (4.48$10 1 and
Water treatment 1.09$10 2 kg of 1,4-DBeq kg 1 crust leather, respectively). Nitrate loads from wastewater treatment and
Basic chromium sulphate oxidative treatments affect heavily marine eutrophication (6.9$10 1 g N eq kg 1 crust leather). The use of
epoxidized vegetable oil would affect human toxicity, ecosystem, metal and water resources depletion
more than the use of sulpho chlorinated paraffin, mainly due to pesticides distribution and other
cultivation practices. Phosphate and nitrate releases due to fertilization determine the high impact on the
categories freshwater and marine eutrophication.
Progress in increasing the conversion efficiency is demanded, but overall focus must be made on the
substitution of fossil fuels with cleaner alternatives. The transition towards a circular economy is
encouraged; increasing rates of reduction, reuse, recycle and recover of solid waste and tannery effluents
are recommended. Agricultural practices with a reduced consumption of phytosanitary products and
mineral fertilizers, alternative to conventional farming, would strongly contribute to increase the sus-
tainability of epoxidized vegetable oil as alternative fatliquoring agent.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction to reduce with the increasing development of production centers in

other regions of the world, as Mexico, Argentina, Brazil, South
There are approximately 10,000 tanneries in the world with an Korea, China, India, and Pakistan (Black et al., 2013). Italy, Spain and
estimated US$50 billion turnover, denoting the socio-economical France are the main EU producers; the industry of Southern Europe
relevance of hide production and of related environmental con- focus on the production of leather for the fashion sector, carried out
cerns (Giannetti et al., 2015). The EU became a net exporter of raw by small and medium-sized enterprises. Conversely, the tanning
bovine hides in 2004 and now it is the world's largest supplier of sector of Central and Northern Europe is mainly constituted by
leather (European Commission, 2012), with 1163.1 thousand tons large size companies, specialized in the upholstery destinations
exported in 2014. However, the EU's share of world markets tends (Brugnoli et al., 2013).
Italy represents the main tanning country in the European
Union, covering 65% of the EU turnover and 19% worldwide. In 2016
Italy imported about 800 thousand tons of raw or semi-finished
* Corresponding author. material, worth 2.3 billion euros, and exported tanned leather in
** Corresponding author. 110 countries for a value of 3.8 billion (Dell’Olio, 2018). Production
E-mail addresses: andrea.tasca@ing.unipi.it (A.L. Tasca), monica.puccini@unipi.it
(M. Puccini).
units in Italy are generally smaller than in the other countries, with

https://doi.org/10.1016/j.jclepro.2019.03.335
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729 721

characteristic concentrations of tanneries and municipalities inti- to clustered small and medium enterprises (Daddi et al., 2016).
mately connected, as Santa Croce sull’Arno (Tuscany), where is In this study, an overview of the environmental issues associ-
located the tanning district considered as primary source of data in ated to the tanning sector is presented in Section 2, then life cycle
this work. Santa Croce sull’Arno is a leading centre of bovine leather assessment of retanning, fatliquoring and dyeing, central steps of
making in Italy, with a production mainly directed to the shoe the process “from wet-blue to crust leather” of the leather tanning
industry. chain (Fig. 1), is carried out. Moreover, an alternative energy mix,
The tanning industry enhances the local economic develop- fatliquoring agent and input production and recovery ratios are
ment, but leads to severe environmental pollution (Hu et al., 2011); evaluated. Impacts on human health, ecosystem and resources are
therefore, improving the environmental assessment of this sector is presented and improvements are proposed and discussed.
essential (Shi et al., 2016). Giannetti et al. adopted a multicriteria,
multiscale approach to address cleaner production strategy costs 2. Environmental concerns
and benefits. The proposed recycling strategies, able to reduce by
one half the water demand used and to decrease chemicals con- Hides and skins are more and more often imported in a raw state
sumption up to 4% with respect to the business-as-usual process, or as partly processed products. Hence, certain steps of the leather-
have been associated to a 10% increase of the electricity demand making, as those carried out in the beamhouse and tanning are
(Giannetti et al., 2015). Life cycle Assessment (LCA) is a decision- transferred to other countries, particularly to third world countries,
making tool for the identification, quantification and evaluation leading to ‘pollution creep’. Moreover, chemicals prohibited within
of a product, process or activity, by estimating the associated the EU, might be used and could be found in the wastewater of
environmental impacts (Guine
e et al., 2001), regulated by the ISO finishing plants. The innovations in the tanning industry in terms of
14040 (International Organization for Standardization, 2006a) and environmental performance have been mostly focused on chem-
14044 (International Organization for Standardization, 2006b) icals rather than on machines (Black et al., 2013). Environmental
since 2006 (Shi et al., 2016). This methodology has been used to issues of the sector, and the best available techniques to address
identify the hot spots of leather manufacture in Italy and Spain; these issues have been identified by the Best Available Techniques
improvements in energy mix, industrial processes and solid waste Reference Document for the Tanning of Hides and Skins. This report
management have been identified, and further research dealing has been drawn up in the framework of the implementation of the
with inventories of recovery processes and landfill disposal have Industrial Emissions Directive (IED) 2010/75/EU Integrated Pollu-
been suggested (Notarnicola et al., 2011). The study of chrome- tion Prevention and Control, by the European Integrated Pollution
tanned bovine leather ‘from cradle to gate’ described landfilling Prevention and Control Bureau at the European Commission's Joint
of the tannery wastes and agriculture practices as the main pro- Research Centre (Black et al., 2013).
cesses affecting the environmental performance of the analyzed Environmental concerns in tanneries include emissions to wa-
the system (Mila~ i Canals et al., 2002). Greenhouse gas emissions of ter, terrestrial and atmospheric ecosystems (Song et al., 2004),
aniline leather have been examined in a cradle to gate scenario, which can be caused directly from accidental or illegal releases of
concluding that the thickness of finished bovine leather has rele- process chemicals and wastes. Air emissions of sulphides, thioles,
vant impact to the carbon footprint (Chen et al., 2014). More VOCs, ammonium and emissions of PCDD/F due to halogenated
recently, Daddi and co-workers investigated the technical issues organic compounds and PAHs from incineration processes of
related to the application of the LCA methodology in the tanning wastes for power supply are relevant. The emission of organic
industry, proposing and applying novel approaches with reference solvents is now regulated by Chapter V of the IED. Emissions of

Fig. 1. Leather tanning flow chart.

722 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729

sulphides, ammonia, organic solvents, leather dust and powdered 3. Methodology

dye stuffs require rigorous ventilation of the workplace (UNEP,
1991). The LCA is a method used for the quantification of the envi-
About 20e25% of raw bovine hide weight is transformed into ronmental impacts associated to a product or a service throughout
leather, with a further 65% transformed to sole leather. The its lifecycle. LCA was here applied according to the four-stages
remaining organic material is only partially recovered as by- structure well recognized at the international level, embodied
products. Most of the leather manufacture operations are per- into the technical standards issued by ISO (International
formed in water. Normally when 1 ton of raw hides is transformed Organization for Standardization, 2006a, 2006b) and as defined
into ~250 kg leather, 15e50 m3 of wastewater and 450e730 kg of by ILCD Handbook guidelines (European Commission - Joint
solid waste are generated; furthermore, up to 500 kg of sludge are Research Centre - Institute for Environment and Sustainability,
generated in wastewater treatment plants (Hu et al., 2011). Overall, 2010). The four stages include goal and scope definition, in-
European bovine tanneries generate approximately 4$105 tons per ventory analysis, impact assessment and interpretation of the re-
year of sludge and approximately the same amount of other solid sults (Tasca et al., 2017). The analysis was carried out with the
residues (Black et al., 2013). support of the software SimaPro 8.3.0; impacts on the environment
The wastewater produced from 1 ton of raw hides includes and human health have been estimated according to the method:
about 240 kg of COD, 100 kg of BOD, 150 kg of suspended solids, Recipe Midpoint (H) v.1.13.
170 kg of sodium chloride, 80 kg of sulphate, 10 kg of sulfide and
5 kg of chromate (Duan, 2000). Most of the salt pollution comes
3.1. Goal, system boundaries and functional unit
from the raw hides, as the preservation of 1 ton of fresh hides re-
quires 300e400 kg of salt. Moreover, high amounts of sulfide and
The analysis was performed from a “gate to gate” perspective.
lime are not absorbed by the pelts in the liming process. COD and
The main objective considered was the creation of a framework for
BOD are increased by broken hair, epidermis, non structural protein
quantifying the impacts of retanning, fatliquoring and dyeing steps
from soaking and liming stages, while amines produced from
of the chrome-tanning process; to this end LCAs on the productions
liming, deliming, bating and retanning could lead to the develop-
of chromium sulphate, sulpho chlorinated paraffin, epoxidized
ment of anaerobic systems which are toxic for the bacteria oper-
vegetable oil and dye production have been carried out, as no in-
ating in wastewater treatment facilities.
formation was available on the ecoinvent v.3.1 database (Wernet
Other pollutants of concern of the tanning effluents are azo-
et al., 2016). Energy consumption, water demand and chemicals
dyes, Cobalt, Copper, Antimony, Barium, Lead, Selenium, Mercury,
have been computed, while infrastructure are not included within
Zinc, Arsenic, Cadmium compounds, Polychlorinated Biphyenils
the system boundaries (Fig. 2). Water and electricity inputs have
(PCB), Nickel, formaldehyde resins and pesticides residues.
been considered as sourced from Italian production. Furthermore, a
(Mwinyihija, 2010). Alkyl phenol ethoxylates (APEs), surfactants
sensitivity analysis was also performed to investigate an alternative
used as emulsifiers, dispersing agents and fatliquoring agents, are
energy mix, fatliquoring agent and basic chromium sulphate pro-
widely known due to their toxicity, poor biodegradability, and
duction and recovery ratios.
bioaccumulation potential. The chemical of major concern is
According to the ISO standards (International Organization for
chromium (VI), oxidized from chromium (III) in tanning as well as
Standardization, 2006a, 2006b), a functional unit should repre-
in nature. Its carcinogenic, mutagenic and allergenic potential has
sent qualitative and quantitative aspects of the function that a
been recognized, and the current legislation sets the limit of
product proposes to fulfill and it must be measurable. The assess-
3 mg kg 1 based on the leather weight (Hu et al., 2011). Notwith-
ment was carried out by considering 1 kg of tanned leather as
standing the increasing emphasis on wet-white (chrome free)
output from the dyeing step, named ‘crust leather’. This unit was
manufacture, 80e90% of all world tanneries still produce wet blue
used as a reference to compile the inventories of the environmental
leather (i.e.: moist chrome-tanned leather), due to lack of alterna-
burdens of the examined chain and to estimate the related impacts.
tive able to provide leathers with the same qualities. Chromium (III)
removal is mostly attained by precipitation with alkaline agents, as
Na2CO3, Ca(OH)2 and NaOH. Alternative methods comprise: liquid- 3.2. The analyzed system
liquid extraction with partially ammoniated di(2- ethylhexyl)
phosphoric acid (D2EHPA) and di(2,4,4trimethylpentyl) phosphinic The tanning district considered as primary source of data in this
acid, four-stage extraction/re-extraction with (D2EHPA) or mono(2- work is located in Santa Croce sull’Arno (Tuscany, Italy); data are
ethylhexyl) phosphoric acid (M2EHPA), ion exchange, partial presented in Table 1. The system comprises all the steps from the
freezing, application of high temperature and pressure, membrane retanning of wet blue to the dyeing of the leather. All the treat-
technologies, absorption on kaolinite, flotation process using active ments are carried out in 6 kW drums with intermediate washing
charcoal and oleic acid surfactant (Black et al., 2013; Wionczyk stages. Hides are loaded in drums with water (35  C), acetic acid
et al., 2006). and an ethoxylate surfactant. After 45 min, washing is carried out
European tanneries usually discharge their effluents to large and water, basic chromium sulphate (BCS) and sodium formiate are
wastewater treatment plants. Most tanneries discharging to sewer introduced. This bath is maintained overnight, then sodium bicar-
systems have an on-site effluent treatment installed. The settled bonate and sodium formiate are introduced and maintained for
sludge resulting from the primary treatment of tannery effluent 45 min. After washing, water (30  C) and a synthetic tannin is
amounts from 5 to 10% of the total volume of effluent treated, added, further washing is carried out 60 min later and sulpho
increasing up to 20% when biological treatment is employed, and it chlorinated paraffine is introduced. The use of epoxidized vegetable
has a solid content of 3e5%, raised to 25e40% by dewatering. oil as alternative fatliquoring agent is also evaluated. The procedure
Sludge disposal options are strongly dependent on the local of dyeing requires two consecutive addition of formic acid, before
acceptability of applying sludge to agricultural land. EU Member with an azo-dye and cold water, and then with water at 55  C. The
States are required to establish a national strategy for the reduction first bath is maintained for 30 min, the latter lasts 45 min. The
or elimination of biodegradable waste going to landfills, by means leather is finally washed and being piled onto a ‘horse’ to ‘age’, i.e.
of recycling, composting, biogas production, materials and energy to letting the fat migrate into the interior of the material (Black
recovery (Black et al., 2013). et al., 2013).
 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729 723

Fig. 2. System boundaries.

Table 1 dewatering, thermal drying to 25% ss, conditioning and incinera-

Retanning, fatliquoring and dyeing: inputs and outputs, referred to 1 kg of crust tion of sewage sludge. The outflow goes directly to natural surface
leather. water.
Process Amount Unit

Retanning Input 3.3.1. Basic chromium sulphate

Ethoxylated Surfactant 0.003 kg A considerable fraction of basic chromium sulphate applied in
Acetic Acid 0.003 retanning is commonly recovered from dewatered tannery sludge,
Sodium Formiate 0.005
by consecutive washing and filtration steps (Fig. 3). First, a chromate
Basic Chromium Sulphate 0.040
Water (35  C) 3 solution is separated by two alkaline washings, with hydrogen
Electric Energy 1.750 kWh peroxide, required to oxidize Cr(III) to Cr(VI), while other metals
Heat 0.051 kWh remain in the sludge. The last washing step is carried out under
Output
acidic conditions and Cr(VI) is reduced and recovered in the form of
Wastewater 1.500 kg
Cr(III) solution. The pH of the chromate solution resulting from
Fatliquoring Input alkaline washing is lowered by using H2SO4, then Fe2SO4 and so-
Sodium bicarbonate 0.012 kg dium bisulfite are added. Hydrogen peroxide and Fe(II) act as
Sodium Formate 0.008 reducing agents for Cr(VI). Precipitation of Cr(OH)3 is obtained by
Syntan (tannin) 0.050 NaOH addition to the reduced chromate solution and BCS is ob-
Sulpho chlorinated paraffin/Epoxidized 0.100
Vegetable Oil
tained by filtration. Wastewater and sludge residues are sent to
Water (30  C) 0.700 another Wastewater Treatment Plant (WWTP) for further treatment,
Water (50  C) 1 which is not included in the system boundaries as their impacts are
Electric Energy 0.550 kWh attributed to the tanning step (Kiliç et al., 2011a). Notarnicola et al.
Heat 0.042 kWh
found out that 86.7% of the BCS utilized in a tannery located in Santa
Output
Wastewater 2.7 kg Croce, as the tannery here analyzed, is recovered by wastewater
treatment (Notarnicola et al., 2011). Hence, eighty-five per cent of
Dyeing Formic Acid 0.033 kg BCS used in the retanning process is here considered as coming from
Azo Dye 0.030 BCS recovery. Data related to the BCS production and recovery have
Cold Water 0.300
been taken from the recent work of Kiliç et al. (2011a).
Water (55  C) 2
Electric Energy 0.350 kWh
Heat 0.080 kWh 3.3.2. Sulpho chlorinated paraffin
Output Sulpho chlorinated paraffin production data have been provided
Wastewater 2.8 kg
from a production plant located in Vapi, India (Project Pre-
Feasibility Report (PFR), 2017). The process is represented in
Fig. 4. Heavy normal paraffin is charged in a lead-lined chlorinator,
3.3. Sub-systems modelling together with Cl2 and SO2. Hydrochloric acid and Cl2 released
during the chlorination are scrubbed in water to obtain HCl
Life cycles of basic chromium sulphate, sulpho chlorinated 27e30%, while excess gas is passed through an alkali scrubbed.
paraffin, epoxidated vegetable oil and dye production have been Inputs and emissions of the process (Table 2) have been allocated
modeled on the basis of data from literature, as no primary data between sulpho chlorinated paraffin and HCl applying the eco-
were available and related modules are still not implemented on nomic allocation criterion method, assuming as reference values
the ecoinvent v.3.1 database (Wernet et al., 2016). All relevant in- 1400 $/ton and 215 $/ton, respectively. Treatment of the effluent
puts and outputs from the treatment of incoming waste water from has not been accounted.
industrial processes have been considered, according to the
ecoinvent data set considered. It contains mechanical, biological 3.3.3. Epoxidized vegetable oil
and chemical steps for wastewater treatment and thickening, This process includes the production of crude sunflower oil from
724 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729

Fig. 3. Basic chromium sulphate recovery. Adapted from Kiliç and co-workers. Related energetic inputs are: 74.01 kJ/kg BCS recovered (Kiliç et al., 2011b).

Fig. 4. Sulpho chlorinated paraffin production. Energetic inputs and air emission are detailed in Table 2.

a sunflower seed crushing process, and the epoxidation of the oil,

Table 2 carried out by the in-situ generation of the peracid from hydrogen
Sulpho chlorinated paraffin production: inputs and outputs (Project Pre-Feasibility peroxide and an organic acid. Inputs of the cultivation (Durlinger
Report (PFR), 2017).
et al., 2017), as well as transport, electricity, water, heat from nat-
Sulpho chlorinated paraffin, production Amount Unit ural gas, auxiliary materials, waste and wastewater treatment
Inputs associated to crude oil production (Zeist et al., 2012) and epoxi-
Paraffin 650 kg dation (Milchert and Smagowicz, 2008; Zolkarnain et al., 2015)
Chlorine gas 650 kg have been taken from literature. Data are presented in Table 3.
Sulfur dioxide gas 100 kg
Hydrated lime 4 kg
Water for HCl scrubber 900 kg 3.3.4. Dye
Electric energy 2.43 kWh
Coal for boiler 7.60 kg
There are many different classes of dyes and about half of those
Fuel 0.12 kg used in industry are azo dyes. These compounds have the basic
Water for cooling 113.60 kg structure, Ar1 N]N Ar2, where Arn is an aromatic group. The
Cooling tower 26.73 kWh nature of the aromatic substituents controls the colors and the
Outputs
solubility of the dyes, as well as how they bind to a particular fabric
Sulpho Chlorinated Paraffin 1000 kg
Industrial wastewater 0.72 m3 (Synthesis of an Azo Dye, 2014). Dye manufacturing includes:
Domestic wastewater 0.12 m3 diazotization, coupling, isolation-filtration, drying, grinding, and
Sludge 0,00086 m3 standardization. A diazonium salt is produced, then nitrosation of
primary aromatic amines is followed by the reaction of the diazo-
nium salt with an electron-rich coupling component, like a phenol
or an aniline (Bernard, 2017). Data related to the dye used in the
 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729 725

Table 3 Terrestrial Ecotoxicity; FT: Freshwater Ecotoxicity; MT: Marine

Epoxidized vegetable oil, production: inputs and outputs (Milchert and Smagowicz, Ecotoxicity; IR: Ionising Radiation; WD: Water Depletion; MD:
2008; Zolkarnain et al., 2015).
Metal Depletion; FD: Fossil Depletion.
Epoxidized vegetable oil, production Amount Unit The production of electricity required for the rotation of drums
Input is the main contribute to most of the impact categories, followed by
Oil 1000 kg the azo-dye production. The primary sources of ozone depletion
Hydrogen peroxide 423.19 kg (0.26 mg CFC-11) are bromochlorodifluoro and bromotrifluoro-
Formic acid 69.57 kg
methane, emitted by electricity generation, and the production of
Electrical energy, coal 1143.1 MJ
Electric energy, natural gas 3280.2 MJ the azo-dye and naphthalene. Sulfur dioxide and nitrogen oxides
Electric energy, hydro 546.7 MJ mostly emitted from power plants are the main sources of terres-
Output trial acidification and particulate matter formation. Disposal of
Epoxidized vegetable oil 1056.90 kg
spoils from lignite (used as combustible in power plants) mining
generates significant phosphate emission, with consequent eutro-
phication of freshwaters. The major contributes to human toxicity
Table 4 (0.45 kg of 1,4-DBeq), terrestrial (8.98$10 5 kg of 1,4-DBeq), fresh-
Azo dye, production: inputs and outputs (Synthesis of an Azo Dye, 2014).
water and marine water ecotoxicity (1.14$10 2 and 1.09$10 2 kg of
Azo dye, production Amount Unit 1,4-DBeq) are given by manganese, vanadium and nickel, respec-
Input tively, both emitted by the combustion of fossil fuels. Combustion
Water 8 g of natural gas is the main source of ionizing radiation, through the
Hydrochloric acid 0.0045 mg emission of Radon-222. Nitrate loads from wastewater treatment
Nitroaniline 0.70 g
and chemical oxidation carried out in WWTPs affect heavily marine
Sodium nitrite 0.38 g
1-naphthol 0.74 g eutrophication (6.91$10 1 g Neq kg 1). Wastewater treatment also
Sodium hydroxide 1 g generates N2O emission, which gives the main contribute to the
Sodium chloride 1 g formation of photochemical oxidants. Direct greenhouse gas (GHG)
Output emissions of WWTPs include emissions of CH4 and N2O biologically
Azo dye 1.51 g
produced and emitted in sewers and at plant during the treatment
of wastewater and sewage sludge. Indirect emissions of CO2 and
other GHGs at WWTPs are mainly due to the consumption of
process under consideration are presented in Table 4. electricity, combustion of fossil fuels for transportation, sludge
disposal and chemicals required for phosphate precipitation and
4. Results and discussion sludge dewatering. GHG emissions from municipal WWTPs corre-
spond to ~0.45% of the yearly average pro capita CO2eq emission in
4.1. Impact assessment Europe; however, the optimization of plant operations can be
relevant at local scale and help improving the carbon footprint of
Results of the impact assessment are represented in Fig. 5 and urban areas (Parravicini et al., 2016). Forty g of basic chromium
detailed in Table 5, referred to 1 kg of crust leather. Impact cate- sulphate are required to produce 1 kg of crust leather; notwith-
gories considered are: CC: Climate Change; OD: Ozone Depletion; standing the high fraction of BCS recovered and recycled, its pro-
TA: Terrestrial Acidification; FE: Freshwater Eutrophication; ME: duction is the main responsible of metal depletion (5.6$10 2 kg Fe
Marine Eutrophication; HT: Human Toxicity; PO: Photochemical eq kg 1 crust leather), while the depletion of fossil resources is
Oxidant Formation; PM: Particulate Matter Formation; TE: mainly due to the oil required for electricity production.

Fig. 5. Impact assessment. Estimated impacts of retanning, fatliquoring (ftl) and dyeing and main processes involved.
726 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729

Table 5
Impact assessment of retanning, fatliquoring (ftl) and dyeing.

Impact category Unit Retanning Ftl Dyeing Substances

Climate change kg CO2 eq 1.19 0.74 0.71 CO2, CH4, N2O

Ozone depletion kg CFC-11 eq$10 8 9.72 7.67 8.33 CBrClF2, CF3Br, CCl4
Terrestrial acidification kg SO2 eq$10 3 4.90 3.15 2.72 SO2, NOx, NO2
Freshwater eutrophication kg P eq$10 4 2.57 1.15 1.48 PO3-
4
Marine eutrophication kg N eq$10 4 2.21 1.68 3.01 NO3 , NOx
Human toxicity kg 1,4-DB eq$10 1 1.95 1.09 1.43 Mn, As, Se
Photochemical ox. formation kg NMVOC$10 3 3.05 2.03 1.92 NOx, NO2, NMVOC
Particulate matter formation kg PM10 eq$10 3 1.43 0.96 0.92 SO2, NOx
Terrestrial ecotoxicity kg 1,4-DB eq$10 5 3.70 2.41 2.87 V, Cu, Ni
Freshwater ecotoxicity kg 1,4-DB eq$10 3 4.54 2.56 4.34 Ni, Cu, Mn
Marine ecotoxicity kg 1,4-DB eq$10 3 4.76 2.62 3.54 Ni, Cu, Mn
Ionising radiation kBq U235 eq$10 1 1.91 0.92 0.76 222
Rn, 14C
Water depletion m3$10 2 3.95 1.57 1.71 H2O
Metal depletion kg Fe eq$10 2 2.61 1.33 1.63 Cr, Fe, Cu
Fossil depletion kg oil eq$10 1 3.32 2.74 1.92 Gas, Oil, Coal

Tanning effluents are characterized by a high chemical and of solid waste and tannery effluents are recommended. (Hu et al.,
biochemical oxygen demand, salts and chemicals content. The 2011).
benefits of high pollutant abatements have to be weighed against
the additional production of sludge (Black et al., 2013). The 4.1.1. Sensitivity analysis
reduction of wastewater in tannery process can be realized acting Electric energy required for the rotation of drums is the main
on the technological conditions. Hence, water consumption can be source of impact of the tanning steps analyzed in the present work,
reduced by proper mechanical action which relates to the load, the due to the proportion of fossil fuels required for its generation if the
drum speed and float ratio. Moreover, tanning effluent can be italian energy mix is considered. A different energy mix has been
heated up and recycled at the retanning stage, resulting in an investigated and the comparison between Italy and France is shown
improvement of chrome fixation (i.e.: reduced demand of chrome), in Fig. 6; the differences are mainly ascribed to the use of nuclear
due to the enhancement of pH and temperature of the tanning float power, which is absent in Italy, while it is the main electric energy
(Hu et al., 2011). The decrease of the required chrome powder can source in France. These differences would be further highlighted if
be achieved by controlling the float ratio, fixing time, temperature, not only the energy demand of rotating drums, but also the energy
pH, high exhaustion chrome and masking agent. Furthermore, required for the production of other inputs and for the treatment of
chromium is recovered from the tanning effluent and recycled. wastewater would be produced with a different energy mix.
Kanagaraj and co-workers recovered chromium from the spent tan The analysis is based on energetic mix data provided by Simapro
liquor using the neutralized wattle extract, using the wattle extract 8.3.0, which relies on the International Energy Agency (IEA) sta-
left in the tanning bath as a retanning agent (Kanagaraj et al., 2008). tistics of 2011. Italy, as many other countries, has increased the
The use of salt-based preservation methods is commonly prac- quote of geothermic, wind power and photovoltaic sources in the
ticed, while excessive sulfide is still applied in traditional process, last years, but the use of fossil fuels has been only slightly reduced.
to guarantee the complete removal of hair and epidermis. Hu and The same consideration applies for most of the countries around
co-workers have recently demonstrated that applying a circular the world: according to the IEA statistics 2017, which refer to 2015,
economy model very clean pelts can be obtained with a reduced most of the world energy demand is covered by fossil fuels (81.4%),
dosage of sulfide (Hu et al., 2011). Considering the amounts 28.1% still by coal (Central Statistics Office, 2017). Progress in
generated, reuse of the solid waste is fundamental; common increasing the conversion efficiency is demanded, but overall focus
practices include the reuse of fleshing to obtain grease and feed- must be made on the substitution of fossil fuels with cleaner
stuff, and the employ of hair for the production of brushes or as soil alternatives.
regulator. Moreover, natural fats obtained in fleshing can be reused As stated in Section 2, the environmental performance of the
as leather fatliquoring agent (Santos and Gutterres, 2007), or for the tanning industry is mostly focused on chemicals rather than on
production of biodiesel (Çolak et al., 2005). The shavings from machines; hence, different substances can be alternatively used as
chromium-tanned leather constitute an attractive raw material for dyes or fatliquoring agents. However, different impacts should be
the ceramic tile sector (Basegio and Bernardes, 2005), while expected and addressed. The comparison between different fatli-
retanning agents can be synthetized from blue shavings and quoring agents is shown in Fig. 7. The use of epoxidized vegetable
trimmings. Finishing agents and pet chews can be obtained from oil would impact human toxicity, ecosystem, metal and water re-
waste liming pelt scraps (Eleanor et al., 1996); (Stockman, 1996) and sources depletion more than the use of sulpho chlorinated paraffin.
finishing agents (Mu et al., 2003). Chromium-containing solid The production of hydrogen peroxide and electricity required for
waste has been tested to produce fertilizer (Nogueira et al., 2010), the oil epoxidation, and the production of naphtalene sulphonic
as well as low cost materials for dyes adsorption (Oliveira et al., acid are the main sources of manganese in water, which gives the
2007). Chrome-free tanning towards Eco-leather manufacture has primary contribution to human toxicity. Phosphate and nitrate re-
been increasingly encouraged, as the novel nano-SiO2 process (Liu leases due to cultivation stages determine the high impact on the
et al., 2010), and titanium based tannage (Crudu et al., 2014). The categories freshwater and marine eutrophication. The major
use of vegetable tannin and nano-silicate are considered as a contribution to terrestrial acidification is given by the cultivation
promising alternative to conventional chrome-based processes (Shi practices and the synthesis of naphthalene sulphonic acid utilized
et al., 2016). in the epoxidation process, through the emission of sulfur dioxide
The transition towards a circular economy is encouraged as a and ammonium.
new way of raw materials, water and energy consumption reduc- The heavy difference in terms of impact on freshwater and
tion in the tanning industry. Reduction, reuse, recycle and recover terrestrial ecotoxicity is due to the use of the organophosphate
 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729 727

Fig. 6. Retanning, fatliquoring and dyeing: impact assessment if French (green bars) or Italian (purple bars) energy mix is assumed for the rotation of drums. (For interpretation of
the references to color in this figure legend, the reader is referred to the Web version of this article.)

Fig. 7. Fatliquoring: comparison between the use of epoxidized vegetable oil (blue) and sulpho chloro paraffin. (For interpretation of the references to color in this figure legend, the
reader is referred to the Web version of this article.)

pesticide Chlorpyrifos. It has been recognized as part of endocrine strongly contribute to increase the sustainability of epoxidized
disruptor substances (Ventura et al., 2016); the current lack of vegetable oil as alternative fatliquoring agent.
knowledge regarding exposure scenarios of this class of chemicals Impacts of the use of vegetable oil or sulpho chloro paraffin as
still hinders the assessment of human health risk and impact (Tasca alternative fatliquoring agents have been compared and discussed
and Fletcher, 2017). Chlorpyrifos, O,O-diethyl O-(3,5,6-trichloro-2- in relation to their production stages. Hidden impacts are those
pyridyl), is a broad spectrum insecticide used world-wide (Wang related to their treatment as part of the contaminants of the
et al., 2007), lipophilic in nature with a log P value of 4.96 wastewater discharged from the drums. Hence, the analysis here
(Sharma et al., 2010). It exerts its toxicity affecting central and pe- conducted of the post tanning steps includes the treatment of in-
ripheral cholinergic nervous systems, mainly by inhibiting acetyl- dustrial wastewater, but no difference has been considered to
cholinesterase (AChE) activity (Mileson et al., 1998). The use of specifically evaluate the presence of the different fatliquoring
agricultural practices alternative to conventional farming, which agents. The feasibility of quantification of the increase of the
avoids or at least reduces the use of phytosanitary products, would treatment intensity required when sulpho chloro paraffin is used is
728 A.L. Tasca, M. Puccini / Journal of Cleaner Production 226 (2019) 720e729

questionable, due to the extreme width of the range of pollutants control of the operating conditions, to reduce the demand of this
content of the effluent. However, an analysis of the removal chemical. The use of epoxidized vegetable oil would impact human
mechanisms of the pollutants along the treatment steps of the toxicity, ecosystem, metal and water resources depletion more than
WWTPs highlights the heavier intensity required to remove sulpho the use of sulpho chlorinated paraffin. Agricultural practices with a
chloro paraffin, when compared to the separation of the vegetable reduced use of pesticides, alternative to conventional farming,
oil. Indeed, more than 80% of the vegetable oil is separated by would enhance the sustainability of epoxidized vegetable oil as
coagulation and flocculation with FeCl3 or Al2(SO4)3 (Basibuyuk and alternative fatliquoring agent.
Kalat, 2004), while chlorinated paraffins removal requires the
entire sequence of primary, secondary and tertiary treatments. Acknowledgements
Zeng and co-authors demonstrated that a removal efficiency of 82%
can be attained in a municipal plant through an aerated grit The authors kindly thank Beatrice Zamponi for the support
chamber, aerobic, anaerobic and anoxic bioreactors, secondary provided in the processing of data.
sedimentation, hyperfiltration and ozonation.
The decrease of basic chromium sulphate demand can be ach- Appendix A. Supplementary data
ieved by controlling operating conditions, as discussed in section
4.1. Moreover, chromium can be recovered from the tanning Supplementary data to this article can be found online at
effluent by chemical coagulation, precipitation with alkaline and https://doi.org/10.1016/j.jclepro.2019.03.335.
then dissolution with sulfuric acid (Mu et al., 2003; Song et al.,
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