Sustainable Chemistry and Pharmacy 11 (2019) 17–22

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Sustainable Chemistry and Pharmacy

journal homepage: www.elsevier.com/locate/scp

Re-using henna natural dyeing wastewater for coloration and T

multifunctional finishing of linen fabric
⁎
Ankit Sharma, Satish Kadam, Prasun Mathur, Shahid-ul-Islam, Javed Sheikh
Dept. of Textile Technology, Indian Institute of Technology, Delhi, India

A R T I C LE I N FO A B S T R A C T

Keywords: Owing to their renewability and environmental friendly nature, natural dyes have been widely investigated in
Reuse of dyebath the textile sector over the past few decades. Natural dyeing technology, however, generally require toxic metal
Linen salt mordants to improve fastness and other functional properties; a large amount of mordants are unfixed and
Dyeing are discarded into wastewaters which represent dramatic environmental problems. The present work represents
Functional finishing
a cleaner production strategy by reusing wastewater of henna dyebath for the development of functional and
coloured linen fabrics. The reuse of dyeing liquor was done in a systematic way and the dyed linen was char-
acterized by several spectroscopic techniques. The analysed colour measurements, UV protection, and anti-
oxidant property of dyed linen were very good. The obtained data in terms of chemical oxygen demand, TDS,
conductivity, redox potential and pH of the bath showed that almost zero percentage of mordant salt remains in
exhaust bath after three successive dyeing.

1. Introduction
Synthetic dyes are used widely all over the world for their use in
different application fields. However, recent research has suggested
that several synthetic dyes are non-degradable due to the fact that they
get converted to any of the banned aromatic amine structures. It is also
noteworthy to mention that dyeing of textiles uses several basic and
advanced chemicals and auxiliaries such as dispersing agents, wetting
agents, carriers, emulsifiers, pH regulators and surfactants. In view of
these facts, recently, search for eco-friendly and alternative methods for
dyes removal or remediation has received considerable research in-
terest. Among several methods, adsorption has been reported as one of
the most effective technique for the removal of toxic pollutants from
wastewaters. Lately, sustainable textile production through cleaner
production options has also gained momentum in recent years.
(Agnhage et al., 2017; Salama, 2017; Hassan and Bhagvandas, 2017).
Over the past decade, researchers have shifted their focus towards
exploring plant species as a new source of colorants for use in textile
colouration. This is due to the bans imposed by many countries on some
synthetic dyes which are carcinogenic and pose serious environmental
pollution (Baliarsingh et al., 2012). On the other hand functional
modification of textile fibres has recently gained increased importance.
Research into natural dyes sources and discovery of their several new
properties such antibacterial, UV protection, antioxidant and insect
repellent have greatly aided in widening the scope of natural dyes in
various application sectors. Natural dyes were widely studied for si-
multaneous dyeing and functional finishing of various textile materials
(Rattanaphol et al., 2011; Han and Yang, 2005; Koh and Hong, 2014;
Islam et al., 2018; Pisitsak et al., 2018). However, the dyebath con-
taining natural dyes were used once and no further investigations re-
garding the possibility of reuse of such dyebaths containing the un-
exhausted dye were reported. As already known most of the natural
dyes lack affinity towards textile fibres, especially cellulosic fibres, and
thus substantial quantity of dye remain unexhausted even after use of
pre-mordanting with metallic mordants. Such unexhausted dyebaths
will substantially increase the effluent load which might otherwise be
utilized for the further dyeing process. Textile wet processing industries
are generating huge quantity of effluents and there is an urgent need to
find sustainable solutions for the effluent. Therefore, attempts should be
made to reuse textile wastewaters for various dyeing and finishing
operations in order to reduce the demand for freshwater. Recycling and
reuse of spent dyebath would not only help to conserve water resources
but also will help to keep our environment clean.
Henna is widely used in the dyeing of textile fibres; however, it lacks
affinity towards textile fibres and generally applied in conjunction with
metallic mordants. Application of henna in dyeing of textile fibres is
reported (Badri and Burkinshaw, 1993; Jia, 2008; Li et al., 2011;
Rehman et al., 2012; Sheikh et al., 2016; Dev et al., 2009; Nazari, 2017;

⁎
Corresponding author.
E-mail address: jnsheikh@iitd.ac.in (J. Sheikh).

https://doi.org/10.1016/j.scp.2018.12.001
Received 7 August 2018; Received in revised form 30 November 2018; Accepted 1 December 2018
Available online 12 December 2018
2352-5541/ © 2018 Elsevier B.V. All rights reserved.
A. Sharma et al. Sustainable Chemistry and Pharmacy 11 (2019) 17–22

Yusuf et al., 2012; Tutak et al., 2013). No studies in the area of reuse of Table 1
spent dyebath of henna are available. In the present work, the si- Dye absorbance of the spent dyebath.
multaneous coloration and functional finishing of linen fabric was at- Dyebath Absorbance at various Colour Decrease in
tempted using freshly prepared and exhausted dyebaths. The dyeing of Wavelengths values of K/S (%)
mordanted fabrics, one at a time, were carried multiple times using the dyed linen
same dyebath. The efficacy of coloration and functional properties, as 436 nm 525 nm 620 nm (K/S)$

well as the effluent characteristics of the subsequent dyebaths were
explored.
2. Materials and methods
2.1. Materials
The ready for dyeing linen fabric (EPI-45, PPI-41, GSM-241.5) was
provided by Jayshree Textiles (India). Henna powder was purchased
from local ayurvedic shop. The chemicals like copper sulphate, DPPH
were purchased from Sigma chemicals.
2.2. Methods
2.2.1. Mordanting and dyeing of linen using exhaust method
The mordanting of linen fabric with copper sulphate (1%, on weight
of fabric) was carried out in water bath (Julabo, Hongkong) at 90 °C for
60 mins. The mordanted fabric was squeezed and further subjected to
dyeing with henna extract (20% shade) at 90 °C for 60 mins. The dyed
fabric was further washed with cold water to remove superficial dye.
After dyeing, the spent dyebath was analysed for absorbance values on
UV–Visible spectrophotometer (Shimadzu, Japan) as per ISO7887
standard. The dyebath was further used for dyeing of another mor-
danted fabric. The procedure was repeated till four dyeing cycles.
2.2.2. Evaluation of colour strength and colour fastness
K/S values (representing the colour strength) of the dyed fabrics
were evaluated using Kubelka-Munk Equation as per the procedure
reported (Teli et al., 2013). The reflectance and colour coordinates were
measured on Gretag Macbeth Colour Eye 7000. Colour fastness to
washing and rubbing were evaluated using ISO II (Trotmann, 1984) and
ISO105-X12 (ISO technical manual, 2001) test methods respectively.
2.2.3. Estimation of Functional properties of dyed fabrics
UV-protection factor (UPF) was assessed according to the
Australian/ New Zealand Standard AS/NZS (4399): (1996) standard.
Radical scavenging activity of the dyed linen fabric was determined by
measuring the decrease in absorbance of 2,2-Diphenyl-1-picrylhydrazyl
radical (DPPH•) at 517 nm as per the method reported in the literature
(Sheikh and Bramhecha, 2018).
2.2.4. Ecological parameters
The chemical oxygen demand (COD) of the fresh and reused dye-
baths was determined using colorimetric method. The dye liquor was
digested initially using two reactants in NANOCOLOUR VARIO Mini
and then COD was measured in photometer (PF-3, MN Germany). The
total dissolved solids, pH and conductivity of the dye bath liquor was
analysed by using EUTECH PC 700 instrument.
2.2.5. Characterization of dyed fabrics
Scanning electron microscope (SEM) images of the untreated and
treated fabric samples were obtained with Zeiss EVO 50 & EVO 18
Special electron probe, equipped with energy disperse X-ray (EDX)
spectroscopy for the composition analysis. The thermal study was
performed by thermogravimetric analysis (TGA) using Perkin Elmer
TGA 4000. The rate of heating was 20 °C/min for temperature range
50–800 °C.
Dyeing Cycle 1 0.781 0.466 0.355 1.56 0
Dyeing cycle 2 0.727 0.438 0.279 1.43 8.33
Dyeing cycle 3 0.642 0.379 0.230 1.11 28.85
Dyeing cycle 4 0.491 0.289 0.188 0.92 41.03
$
average value of three determinations.
3. Results and discussion
3.1. Absorbance of the spent dyebath vs colour values of the dyed fabrics
The absorbance of the dyebaths was measured at various wave-
lengths and the results are summarized in Table 1. The photographs of
dyed linen fabrics and the spent dyebath are presented in Fig. 1. The
absorbance of the dyebath at all wavelengths showed an insignificant
reduction after the first dyeing cycle, thus indicating the possibility of
reuse of spent dyebath for further dyeing without loss of substantial
colour value of the dyed fabrics. The colour values of sample 2 also
displayed proportional decrease with respect to absorbance of the
dyebath. The colour values of both sample 1 and 2 were similar, in-
dicating similar depth of shade. It must be noted that the absorbance
values of the dyebath and the colour values of the dyed samples also
indicate the poor affinity of dye towards the mordanted linen fabric.
The absorbance of the dyebath showed further significant decrease
after dyeing cycle 2 and 3. The decrease, in turn, resulted in decrease in
colour values of sample 3 and 4. The sample 4 retains colour value of
59% as compared to that of sample. This technique of reuse of dyebath
can be utilized in the cases where shade of the fabric is less important as
compared to the functional properties of the dyed fabrics.
The colour coordinates also play important role in appearance of the
dyed fabrics as these decide the tonal variations among the samples. As
shown in Table 2, L* values showed progressive decrease from sample 1
to sample 4, indicating the decrease in depth of shade. These trends
were also confirmed from colour values as discussed earlier. In general,
the tones displayed by the dyed samples, as indicated by positive values
of a* and b* , were red-yellow and thus falling in same quadrant of the
a*-b* plot. These results clearly indicate the insignificant tonal varia-
tions among the samples even though the variations in colour values
were evident.
3.2. Colour fastness properties
Colour fastness of the dyed fabrics towards washing and rubbing
was evaluated and the results are summarized in Table 3. The reuse of
spent dyebath resulted in no detrimental effect on fastness of the dyed
fabrics. All samples (sample 1 to sample 4) displayed acceptable level of
washing fastness. The washing fastness is generally dependant on dye-
fibre interactions and the complex formed between dye and mordant
inside the fibre prevents the bleeding of colour during the subsequent
washings. Hence the fastness results. The rubbing fastness ratings were
in the scale of “very good” and displayed no effect of reuse of dyebath.
Hence it must be emphasized that the colour values were lowered from
sample 1 to sample 4 without substantial influence on tones and fast-
ness properties.
3.3. UPF property
UV-protection, expressed as UPF values, of the dyed linen fabrics is
presented in Table 4. It is shown that the fabric dyed in fresh dyebath
(Sample 1) has UPF 47.49 as a direct consequence of upgrading the

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A. Sharma et al. Sustainable Chemistry and Pharmacy 11 (2019) 17–22

Fig. 1. a) Photographs of spent dyebath at various dyeing cycles b) Photographs of dyed linen at various dyeing cycles.

Table 2 18 + which is considered as satisfactory level of protection. The results

Colour coordinates of the dyed fabrics. are encouraging as it represents the presence of active compounds even
Sample L* a* b*
after three subsequent dyeing cycles which could be utilized for func-
tionalization of linen fabrics.
Sample 1 72.28 3.30 15.90
Sample 2 72.3 3.29 15.17
3.4. Antioxidant properties of the dyed linen
Sample 3 75.49 2.06 13.05
Sample 4 76.32 1.99 12.27
As evident from Fig. 2, the radical scavenging action was displayed
by the sample 1, the extent of which got reduced subsequently in the
Table 3 cases of sample 2 to sample 4. The antioxidant activity of henna extract
Fastness properties of the dyed linen. is associated with the presence of lawsone and polyphenolic compounds
Sample Washing fastness Rubbing fastness (Dry)
which could scavenge the DPPH radicals. The DPPH radical shown
intense peak at around 517 nm. When DPPH accepts the electron do-
Change in shade Staining nated by an antioxidant compounds present in lawsone dye, the radical
is stabilized and thus decolorized.
Sample 1 4–5 4 4
Sample 2 4–5 4 4
Sample 3 4–5 4 4 3.5. Ecological parameters of the dyeing baths
Sample 4 4–5 4 4
The effluent characteristics are of utmost importance for sustainable
processing of textiles. The reuse of spent dyebath for further dyeing
Table 4
cycles can result in substantial decrease in effluent load both in terms of
Effect of reused bath on UPF values of the
volume and the toxicity. The ecological parameters of the dyebath were
dyed linen fabrics.
analysed and presented in Table 5.
Samples UPF$ The pH of the fresh dyebath was 6.76 which showed insignificant
Untreated 9.85
change after subsequent dyeing cycles. The TDS values of the fresh
Sample 1 47.49 dyebath was 259 ppm which showed reduction after subsequent dyeing
Sample 2 28.27 cycles. The TDS values of the dyebath were mainly due to soluble
Sample 3 20.91 electrolytes and dyes. It is a prime concern in effluent treatment during
Sample 4 18.70

$
average value of three determinations.

scattering/ absorption of copper sulphate as well as henna. UPF value of

unteated linen showed significant rise after dyeing. Henna extracts
contain lawsone along with various polyphenolic compounds which are
known to absorb UV-light. It can also be seen from Fig. 1 that the
wavelength of maximum absorption (λmax) of the henna extract lies in
the UV region. Hence the dyed fabric showed decrease in transmission
of UV light through it, mainly because of absorption by active com-
pounds, resulting in enhanced UV protection. The UPF value of 47.49
represents excellent UV protection offered by sample 1. The UPF values
of the samples dyed using spent dyebath decreased subsequently. This
is mainly attributed to loss of active compounds which was also re-
flected in decreased colour values. Sample 4 displayed UPF of Fig. 2. Radical scavenging action of the dyed linen.

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A. Sharma et al. Sustainable Chemistry and Pharmacy 11 (2019) 17–22

Table 5 elemental analysis confirms the presence of copper in case of dyed

Effect of reused bath on dye liquor and ecological parameters. samples (sample 1-4) while it was absent in undyed linen. The objective
Sample pH Conductivity (µScm−1) TDS$ (ppm) COD$ (ppm) of analysis was to confirm the presence of dye-mordant complex inside
the fibres and thus to correlate the functional properties obtained as
Initial Bath 6.76 519 259 15000 discussed earlier. As the dyed samples were washed after dyeing, the
First bath 6.77 426 208 13600
probability of presence of free copper, which is not in complex form
Second bath 6.76 394 177 4100
Third bath 6.75 351 156 1900
with henna extract, is negligible. Hence the EDX analysis confirms the
Fourth bath 6.76 333 142 1200 presence of copper in the complex form with henna extracts.

$
average value of three determinations.
3.6.2. Thermogravimetric analysis of the linen fabrics
Thermogravimetric analysis was used to study the effect of dyeing
reverse osmosis process as high TDS during the process can affect ef-
using henna extract in presence of copper sulphate as mordant on
ficiency and life of RO membrane. Even though the decrease in TDS was
thermal properties and the effect of subsequent dyeing in spent dyebtah
evident, the extent was not very much substantial as compared to that
on the same. Thermogravimetric analysis (TGA) provides quantitative
of COD. This may be because of exchange of some mordant solution in
information on weight change during heating process and gives a broad
dyebath during dyeing. COD values of the fresh dyebath were reduced
idea about the thermal stability of the linen. The temperatures corre-
drastically after subsequent dyeing cycles reaching the COD reduction
sponding to weight loss of 25%, 50%, and 75% was noted from the
of 92% for the fourth cycle. This is mainly attributed to the exhaustion
spectra and presented in Table 6. The dyeing with henna extract re-
of dye extract from the dyebath. The organic components from the
sulted in interesting changes in thermal behaviour of linen; the initial
dyebath exhausted to the fibre, as a result of complex formation be-
weight loss values were lower while the samples were rapidly degraded
tween extract and mordant, which resulted in lowering of oxygen de-
later on. The temperatures corresponding to 25% and 50% weight loss
mand for oxidation. This is quite encouraging as COD reduction is
were higher for dyed samples while that for 75% was higher for undyed
highly desirable before the discharge of effluent to water resources. The
fabric. This might be attributed to the presence of copper inside the
reuse of spent dyebath not only resulted in dyeing cum functionaliza-
fabric which might provide initial stability while at higher tempera-
tion of linen fabric but also the reduction of effluent load. The systems
tures, it might facilitate the degradation of linen. The sample 1, 2 and 3
where the functional characteristics are of greater importance than the
having difference in depth of shade as well as copper content showed
depth of shade of the final fabric, the spent dyebath can be used for
insignificant difference in their temperatures corresponding to 25%,
repeated dyeing of linen. The subsequent standing bath technique can
50% and 75% weight loss values. However, it must be noted that the
also be established in order to reproduce the exact shade on the fabric
sample 1 showed higher values of degradation temperatures and the
dyed using spent dyebath.
final residue among all dyed samples.

3.6. Characterization of the dyed fabrics 4. Conclusion

3.6.1. SEM and EDX
The SEM photographs of undyed and dyed linen are presented in
Fig. 3 which indicate insignificant difference in the morphology of
samples. The surface deposition, however, was visible in case of dyed
samples which may be attributed to the action of henna in complexa-
tion with copper ion as well as the reducing the copper ions to copper
micro-particles.
The EDX spectra of the linen samples are presented in Fig. 4. The
The spent dyebath of henna dyeing was successfully utilized for
simultaneous dyeing and functionalization of linen fabric. The study
revealed the possibility of reuse of spent dyebath to achieve satisfactory
results of coloration as well as functional properties. The best advantage
can be gained in reduction in requirement of fresh water in dyeing as
well as the effluent load. The sustainable way of natural dyeing of linen
with henna extract was reported in a new direction in terms of reuse of
spent dyebath.

Fig. 3. SEM photographs of linen fabrics a) Undyed b) Sample 1c) Sample 2 d) Sample 3 e) Sample 4.

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A. Sharma et al. Sustainable Chemistry and Pharmacy 11 (2019) 17–22

Fig. 4. EDX spectra of linen fabrics.

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