This document provides an introduction to European standards for chemical testing in leather. It discusses the collaboration of an Italian company, ALPA, with Shafi Reso Chem to provide leather chemicals and technical services. The purpose is to educate about using hazardous chemicals in leather processing from an ecological perspective, as the EU and US have banned many toxic products. Key toxic chemicals discussed include chromium VI, azo dyes, formaldehyde, nonyl phenols and pentachlorophenol. The roles of organizations like REACH in regulating these chemicals are also summarized.

1. Introduction to European
Standards for Chemical
Testing in Leather
Shafi Reso Chem

2. Introduction
SHAFI RESO CHEM
- Sister concern of Shafi Group
- Established in 1994
- Chemicals and Auxiliaries for Leather
and Textile Industries.

3. Collaboration with foreign
company ALPA
 Shafi Reso chem. has recently collaborated
with an Italian company ALPA for the
manufacturing of leather chemicals and to
provide technical services to their customers
from this platform so that we can upgrade
our customers according to new fashion
trends in international markets and to provide
them ALPA chemicals at suitable costs.

4. Purpose of the presentation
 To provide know how about the using of
hazardous chemicals in leather processing
with respect to ecological point of view.
 From the last two decades European
countries and united states are working on
these matter very seriously and already
banned the usage of foregoing discussing
products with respect to production and
import point of view.

5. International Organizations
involved in this project
 REACH (Registration, Evaluation and
Authorization of chemicals) – project on the
environment and human health.
 APERC (Alkyl phenols and Ethoxylates and
Research Council) – project on NP/NPE
 UNIDO(united nations industrial development
organization)- project on Chrome VI
 ETAD (Ecological, Toxicological Association of
dyes)

6. Role of REACH
 To provide necessary information on the safe
use of substances which are transmitted
along the industrial supply chain leading to
reduced risks for workers, for consumers, and
for the environment.
 The project was started in 2003 initially based
on collection of information of toxic products
and their alternatives. In 2006, they already
started their working on the implementation
of such legislations which will stop or
discourage the use of these products on
industrial level.

7. Implementation Time
 In 2008, REACH have the instructions
from EU countries for the
implementation of these regulatory for
these hazardous and toxic products in
all over the world.

8. Need of Time
 So on the basis of above information.
We feel, It is our responsibility to
educate our people as much as
possible about the toxicity of these
products and to educate them about
the substitutes of these products.

9. Toxic chemicals related to
leather
 1- chrome (VI)
 2- Azo Dyes
 3- Formaldehyde
 4- Nonyl phenols
 5- Pentachlorophenol

10. Relationship between chrome
III and chrome VI
 Chromium tanning is preferred because the
process is quick, simple, reproducible and is
very cost effective. Chrome III is not toxic to
water, ground, ground life, micro-organisms,
vegetables and animals.
 But when it is converted in to chrome VI by
oxidation, then it becomes harmful for the
water and animal.

11. 1- Chrome (VI)
Trivalent chromium salts are the most widely
used as tanning agent in the world for the
transformation of hides and skins into leather.
The presence of chromium (VI) in the leather is
a subject of considerable interest in the
tannery sector due to atmospheric hazards.
Chromium (VI) is one of the criteria of the
European Standard EN 420, table 1 lists the
specifications for chromium (VI) content in
the leather.

12. Maximum limits for chrome VI
Table 1 according to journal of the society
of leather technologies and chemists.
Vol.83.p.300.
Standard/ Label Application Limit
EN 420: 1994
standard
protective
gloves
2mg/kg
European eco-label footwear 10mg/kg
Ecolabels: SG,
OKO-tex, LGr
Leather 5mg/kg)

13. Conditions for formation of
chrome VI
 The formation of hexavalent chromium in
leather may be due to three main reasons
 1- Oxidation by air favored by high
neutralization or dying pH.
2- Photo-ageing oxidation by air subjected to
light.
 3- Thermal ageing, oxidation by air subjected
to heat.

14. 1-Oxidation by air favored by
high neutralization or dying
pH.
- Chrom VI only stables at high pH. It is
almost a reversible process and may be
adjusted just by using formic acid.
- The alkaline chromates are not fixed to
the skin and are very soluble with the
result that they can eliminate from float
just washing.

15. 2- Photo-ageing oxidation by
air subjected to light.
 - unsaturated lipids can produce free radicals
when exposed to UV light. In the presence of
oxygen, these radicals evolve continuously
developing very reactive derivatives such as
peroxides, and radicals such as HO`
(hydroxyl) LO` (fatty oxide) AND LOO` (fatty
peroxide), Which possess a strong oxidant
potential,which is probably the reason for
chromium VI formation in leather exposed to
light

16. 3- Thermal ageing
 oxidation by air subjected to heat
 During ironing at high temperature,
chrome VI is produced in the leather
due to air oxidation.

17. Harmful Effects of chrome VI
 1- skin allergy
 2- cancer
 3- liver and kidney necrosis

18. How to Control Chrome VI
Formation
 Use of antioxidants
 Use of aldehyde as tanning materials
 Use of tannin extracts
 Use of pigment finishes.

19. Use of antioxidants
 Magnesium chloride should use as an
antioxidant in waste water to chromium
VI below permissible limit 0.05mg/L.
 BHT (Butyl hydroxy toluene), BHA
(butyl hydroxy aniline) and tocopherol
(Vitamin E) are also used as antioxidant
in leather processing.

20. Use of aldehyde as tanning
materials
 Use of Organic tanning materials like
Aldehyde is also preferable in the
dyeing formulations because they are
considered antioxidants (having
reducing ability).

21. Role of tannin extracts
 Use of tannin extracts in retanning processes
also forcedly preferred because they are
transparent in UV region have ability of
reduction chrome VI
 Most tannins extracts are antioxidant since
they inhabit the propagation of free radicals.
 These tannin act as radical scavengers,
capturing most radicals and transferring them
into suitable substances
these tannins are Mimosa, Chestnut, and
Qubracho,

22. USE OF MINEREL TANNINGS
Mineral tanning
a)Zirconium tanning
b)Aluminum based tanning
c)Phosphonium based tanning

23. Role of pigment finish
 Chromium VI formation will be lower in
leather with pigment finish.UV effect
remain only 50% with only this
application.

24. USE OF DYES
 To impart to materials of which it
becomes an internal part.
 An aromatic ring structure coupled with
side chain required for resonance to
impart color in the visible spectrum of
light.

25. Parts of dye
 It contains three groups
a) Chromogen
b) Chromophore
c) Auxochrome

26. a) Chromogen
It is an aromatic structure containing
benzene and naphthalene.

27. b) Chromophore
It is a color giver group and is used for chemical
classification of dyes when coupled with
chromogen.
Azo (– N=N-);
Carbonyl (=C=O);
Carbon carbon (=C=C=);
Carbon Nitrogen (>C=NH or –CH=N-);
Nitroso (-NO or N-OH);
Nitro (-NO2 or =NO-OH) and
Sulfur (>C=S) and
other sulfur groups

28. c) Auxochrome
 It is bonding affinity group and consist
on amine, hydroxyl, carboxyl and
sulphonic radicals or their derivatives
and is used to increase the color value
of the dye.
 These are important in the use for
classification of dyes.

29. Properties of auxochrome
 The chromogen-chromophore structure
is often not sufficient to impart
solubility and cause adherence of dye to
fiber. So
 In order to get better results,
chromogen and chromophore are linked
with auxochrome during synthesis

30. Chemical Processes Involved In
Dye Manufecturing
 Dyes are synthesized in a reactor,filtered, dried and
blended with other additives to produce the final
product. The synthesis step involves reactions such
as
 -Sulfonation
 -Halogenation
 -Amination
 -Diazotization and Coupling
followed by separation processes that may include
distillation, precipitation and crystallization, and
finishing operations including drying, grinding, and

31. Waste Characteristics-
In Air
 The principle Air pollutants from dye
manufacturing are
 Volatile organic compounds ( VOCs)
 Nitrogen oxides( NOx)
 Hydrogen chlorides (HCL) and
 sulfur oxides (SOx)

32. Waste Characteristics-
In Water
 Liquid effluent resulting from equipment
cleaning after batch operation can contain
toxic organic residues.
 Waste water generation rates for dyes except
Vat dyes 700 liters / kg and for
Vat dye 8000 liters / kg.
- Bio oxygen demand (BOD) and Chemical
oxygen demand (COD) level for reactive and
azo dye 25kg / kg of product and 80kg / kg
of the product respectively

33. Waste Characteristics-
In Solids
 It includes,
- filtration sludges,
- process and effluent treatment
sludges and
- container residues

34. Types of dyes
 Acetate rayon dyes
 Acid dyes
 Azoic dyes
 Basic dyes
 Direct dyes
 Mordant or chrome dyes
 Pigment dyes
 Sulfur or Sulfide dyes
 Vat dyes

35. 2- Azo Dyes
 Invented in Germany in late 19th century.
 Azo-dyes a collective term used to describe a
group of synthetic dyes made from amines,
about 70%of all organic dyes based on this
group.
 Azo is a group (-N=N-) which is used to
increase conjugation in the molecule to give
color, which is produced by the diazotization
of primary amines.

36. Harmful Effects of Azo Dyes
 Azo dyes are carcinogenic and cause allergic if
they exceed the permissible limit (30ppm)
 Basically the harmful effect of azo dyes is due to
free amine component which is produced on
reduction of the azo group.
 The detectable concentrations of any amine
should not exceed 30ppm in the finished article.
 All the amines are not harmful for life, a list of 22
aromatic amines which are harmful are given
below

37.  4-aminodiphenyl
 Benzidine
 4- chloro-O-toluidine
 2- naphthylamine
 4-amino-2,3-diamethyl azobenzene
 2-amino-4-nitro toluene
 4-chloroaniline
 2,4-diaminoanisole
Aromatic Amines according to the
EU directive 2002/61/EC

38. 22 Aromatic Amines
 4,4’-diaminodiphenylmethane
 3.3’-dichlorobenzidine
 3,3’-dimethoxybenzidine
 3,3’dimethylbenzidine
 3,3’-dimethyl-4,4’-diaminodiphenylmethane
 4 -cresidine
 4,4’-methylene-bis-(2-chloroaniline)
 4,4’-oxydianiline
 4,4’-thiodianiline

39. 22 aromatic amines
 2-aminotoluene
 2,4-diaminotoluene
 2,4,5-trimethylaniline
 2-methoxyaniline
 4-aminoazobenzene
 P-amino azo benzene
 2- methoxy aniline(o-anisidine)

40. Countries banned on Azo-dyes
 Since 1990s, OECD Countries banned on
manufacturing, import,export and sale of
textiles and other products that could come
in contact with human skin for prolonged
periods,that are made with Azo–dyes that
have capacity to release, by reductive
cleavage, hazardous aryl amines.
 Germany was the first who ban, and then
followed by Netherlands, Austria and Norway

41. Why Germans take this step
 In 1992,a paper presented to an
international conference held in Wurzburg,
Germany in October, it was reported that in
one plant all 15 workers involved in distilling
2-naphthylamin had developed bladder
cancer.
 Aryl amines are also found in Tobacco smoke

42. ETAD Role
 In 1992, ETAD- Ecological, Toxicological Association
of dyes and organic pigments manufacturing's,
decided to request that all ETAD European and
North American companies voluntarily cease of
benzidine dyes and salts.
 According to them Azo -dyes are manufactured in
mostly Asian countries and Argentina

43. 3- Formaldehyde
 Formaldehyde belongs to the class Aldehyde
and is widely used in the leather for fixation
of casein finishes, textile processing, building
materials and household products.
 According to the environmental Defense
Scorboard it is ranked as one of the most
hazardous compounds to ecosystems and
human health.

44. Acute effects of Formaldehyde
 Low exposure levels (0.1-5ppm) causes
burning, tearing of eyes and skin irritation.
 Moderate exposure levels (10-20ppm) causes
burning of eyes, nose and trachea, severe
coughing, severe difficulty in breathing and
intense tearing of the eyes.
 High exposure levels (50-100ppm) causes
tightening in the chest, irregular heartbeat,
severe headache, pulmonary edema(fluids in
the lungs),

45. Acute effects of Formaldehyde
Inflammation of the lungs and possibly
even death.

46. Possible sources in home
 Adhesives
 Air fresheners
 Carpet backings
 Cigarette smoking
 Cosmetics
 Drapery fabric
 Dyes

47. Possible sources in home
 Fiberboard
 Floor polishes
 Fuel burning appliances-wood, kerosene or
natural gas
 Glues
 Household liquid scouring cleaners
 Markers
 paints

48. Possible sources in home
 Paper products
 Particle board- furniture, fixtures,
cabinets
 Permanent press clothing
 Plywood paneling resins
 Toilet bowl cleaners
 Wall coverings

49. Alternatives of Formaldehyde
in leather processing
 Phenols and glutaraldehyde can be
used as safer alternatives for
formaldehyde.
 Formalin used in finishing process,
aldehyde resins used in tanning and
retanning processes.

50. Steps to reduce exposure
 The united states Environmental protection agency
(EPA) recommends taking the following steps to
reduce household exposure to formaldehyde:
 Use “Exterior grade” pressed wood products (low
emitting because they contain phenol resins, not urea
resins).
 Use of air conditioning and dehumidifier to maintain
moderate temperature and reduce humidity levels.
 Increase ventilation, particularly after bringing new
sources for formaldehyde into the home.

51. 4- Nonylphenols
 Nonylphenol Ethoxylates (NPEs) are primarily
used as cleaning agent or detergents since
last 50 years in number of industries
including leather processing because of their
high performance to extract fat, removing
dung and improving wet ability from the hide
matrix.

52. Environmental and Regulatory issue
surrounding (NEPs)
 The International Union Of Pure and Applied
Chemistry (IUPAC) has checked many
references regarding the toxic effects of NPEs
on a variety of aquatic organisms (water
animals). There are some toxic effects
observed in fishes are as below

53. Toxic Effects Of NPEs
- NPEs effect sexual health.
- NPEs cause breast cancer.NPEs damage
respiratory system & destroy lungs.
- NPEs produces estrogenic response
(Hormonal Disorder)
- NPEs effects reproductivity of fish due to lack
of laying egg.

54. Ban on use of NPEs
- Since, fish or sea life stock are a main source
of human food and their reproduction in
most preferable in all respects therefore
NPEs use in leather processing and other
industries has been decided to be banned

55. Alternative To NPEs
 Recently research has proved that the Fatty Alcohols
ethoxylates (oleo chemicals) are alternative of NPEs
due to their excellent performance in leather industry
and enviournament friendly nature.
 These oleo chemicals show excellent wetting,
detergency and grease removing characteristics its
hydrophilic- lipophylic balance also better than NPEs.
These fatty alcohols recommended only for lower
level of emulsification.

56. 5- Pentachlorphenol(PCP)
 PCP is a chlorinated hydrocarbon which is
used as
 Fungicide; bactericide; algaecide; herbicide;
manufacturing of sodium
pentachlorophenate; preservation of wood,
starches, glues; wood preservative for
agricultural products.

57. Toxic Effects of PCP
 TLV 0.5 mg/m3 (skin).
 Inject able Path are sub cut routes.
 skin irritant; may be fatal if swallowed or
absorbed through skin
 acute poisoning causes weakness, respiration /
blood pressure, urinary output changes,
dermatitis, chronic exposure can injure liver,
kidneys; metabolic stimulant; reproductive
effectors.

58. Substitute of PCP
 copper naphthenate (CuNap) is used as
alternative in place of PCP.
 It is prepared by reacting copper and
copper salts with naphthenic acid(by
product of petroleum refining and
contains a mixture of monocarboxylic
acids) or with sodium copper
naphthanate.

59. Uses of copper Naphthenate
 It has been used as wood preservative
since 1889. It was first used in
Germany since 1911.
 It was recognized in American Wood
Preservers Association standards in
1949
 Its use begin for cross arms, bridges, utility
poles, fence posts and lumber.

60. Uses of copper Naphthnate
 Also in 80s, regulatory activities stimulated interest
in copper naphthenate because of its general use
classification.
 Copper naphthenate is also used in non pressure
applications, including field applied preservatives
and coatings.
 Its uses includes also wood shingles,
millwork,pallets,beehives and non wood
applications such as tents, fishnets and other
fabrics.

61. Sources for testing toxic
materials
 HEJ ( Haji Ibrahim Jamal) laboratory in
Karachi University.
 Microtex lab in Karachi.
 PCSIR in Karachi and Lahore.
 BLC in UK
 TNO in Netherlands
 LGR in Germany

62. THANKS
FOR YOUR PATIENCE