Dyes and Pigments 173 (2020) 107953

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Dyes and Pigments

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Natural dye from Croton urucurana Baill. bark: Extraction, physicochemical

characterization, textile dyeing and color fastness properties
Patricia Muniz dos Santos Silva a, *, Ticiane Rossi Fiaschitello a, Rayana Santiago de Queiroz b,
Harold S. Freeman c, Silgia Aparecida da Costa a, Patricia Leo d, Anto ^nio Fernando Montemor d,
Sirlene Maria da Costa a
a
School of Arts, Sciences and Humanities, University of S~ ao Paulo, S~
ao Paulo, 03828-000, SP, Brazil
b
Laboratory of Technical Textiles and Protection Products, Institute for Technological Research of S~
ao Paulo State, S~
ao Paulo, 05508-901, SP, Brazil
c
College of Textiles, North Carolina State University, Raleigh, NC, USA
d
Laboratory of Industrial Biotechnology, Bionanomanufacturing Center, Institute for Technological Research of S~ao Paulo State, S~
ao Paulo, 05508-901, SP, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Natural dyes have become an alternative option of interest for textile dyeing. The selection of native species as a
Natural dyeing natural dye can make its use feasible and enhance local biodiversity. In the present study, the extract of Croton
Natural extract urucurana Baill. bark, which is native to Brazil, was investigated as a natural textile dye. The extract showed a
Cotton
reddish-brown color and the presence of tannins. The extract was characterized by physicochemical methods and
Wool
Full factorial design
optimization of the dyeing process was determined by factorial design 23. The dyed fabrics were evaluated for
Wastewater analysis color fastness to light, wash, rubbing and perspiration. They showed colors between beige and reddish-brown
and had good fastness properties. Antibacterial activity assessment was performed on the extract and fabrics
and UV protection was evaluated in the fabrics. The wastewater generated from the dyeing process was also
characterized. It exhibited high biochemical oxygen demand and chemical oxygen demand, in addition to a large
amount of dissolved iron and aluminum, when these metals were used as a mordant in the dyeing process. On
balance, the extract of C. urucurana has the potential to be employed as a textile dye.

1. Introduction extraction is important to enabling their use and value from native
species. In addition, this may be a differentiated competitive strategy for
Environmental concerns and awareness have favored the develop­ companies in the textile sector to meet niche markets in which con­
ment of sustainable products and processes that are less impacting to the sumers are concerned about environmental aspects in textiles and be
environment and human health [1]. In the context of the textile chain, willing to pay more for products that are less harmful to the environ­
many processes and products used have been questioned and reeval­ ment [2,6]. Thus, in recent years research on natural dyes has been
uated due to social and environmental damages associated with them, increasing, contributing to the recovery of traditional knowledge and
and new alternatives for production and consumption have been the dissemination of information on natural dyeing techniques, aligning
explored by designers and researchers [2]. Since natural dyes are traditional knowledge with scientific research. In addition, the number
generally less allergenic and toxic than synthetic dyes and generate of companies that use these dyes for textile dyeing has increased.
wastewater that can be treated by biodegradation, this family of color­ The search for new sources of natural dyes has included an exami­
ants has been increasingly contemplated as an environmentally less nation of the dyeing behaviour, antifungal activity, and ultraviolet
impactful alternative to certain synthetic dyes, especially certain azo protection properties of Pterocarya fraxinifolia extracts. P. fraxinifolia
dyes that release aromatic amines that are carcinogenic, presenting a was found to be suitable for dyeing wool, a source of antifungal com­
risk of cancer to users of articles dyed with these dyes, as well as causing pounds, and the juglone component exhibited protection activity against
allergy [3,4]. Thus, they have restricted use in some countries [5]. solar UV rays [7]. It has also been shown that extracts of eggplant skins
Knowing the potential of vegetable-based substrates for natural dye can be used to dye Iranian wool pre-mordanted with Fe2þ, Sn2þ, Cu2þ,

* Corresponding author.
E-mail address: [Link]@[Link] (P.M.S. Silva).

[Link]
Received 6 June 2019; Received in revised form 6 September 2019; Accepted 3 October 2019
Available online 5 October 2019
0143-7208/© 2019 Elsevier Ltd. All rights reserved.
P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Cr6þ and Al3þ mordants. Colorimetric properties were evaluated with a Table 1
reflectance spectrophotometer and wash and light fastness properties Geographical coordinates of the trees used in this research.
were measured using standard test methods [8]. Similarly, extracts of Conservation unit Trees Geographical coordinate
dried and powdered pistachio hulls were used to dye wool yarns
Latitude Longitude
pre-mordanted with Cu, Cr and Al salts. The Taguchi statistical method
involving an L18 orthogonal array (seven factors in three levels) was Juquery State Park 1 23� 20.1130 S 46� 41.4580 W
2 23� 20.1130 S 46� 41.4610 W
employed to evaluate the effects of different parameters on the dyeing Experimental Station of Itapetininga 1 23� 40.6560 S 48� 01.0460 W
process. The colorimetric properties of the dyed yarns were evaluated in 2 23� 40.6510 S 48� 01.0520 W
CIELAB system. A stepwise process for dyeing pre-mordanted wool yarns 3 23� 40.6520 S 48� 01.0520 W
for carpet fibers was reported [9]. In another study, Whitfieldia lateritia 4 23� 40.6490 S 48� 01.0540 W
5 23� 40.6430 S 48� 01.0550 W
leaves were extracted with 1% alkali and the extract used for dyeing
cotton fabric with an alum and tannic acid mixed mordant. Results from
spectroscopic and color fastness assessments suggested that Whitfieldia hydrolyzed [26]. The condensed tannins are oligomeric and polymeric
lateritia contained flavonoids, polyphenols and tannins, and dyed cotton proanthocyanidins, consisting of coupled flavan-3-ol units, such as
fabric in the presence or absence of a mordant. However, the mordant catechin and epicatechin [24,29].
afforded better color fastness on cotton [10]. Studies show that barks containing high tannin have potential for use
Studies involving dyeing fibers other than cotton have been under­ as natural dyes [30]. The tannins can form effective bonds with proteins
taken. In this regard, bentonite-type nano clay was used as an alternative because of their hydroxyl groups and play an important role in dyeing
to traditional mordants in the application of natural dye madder to wool. with cellulosic fibers, because it allows a better fixation of the dye [24,
Analysis of the resultant dyeings using methods such as FT-IR and 27]. This is because tannins, together with metal salts, form metal tan­
UV–Vis spectroscopy, DSC and TG analysis, and fastness testing indi­ nates, which in turn forms insoluble lakes with natural dyes, resulting in
cated chemical changes in the polypeptide functional groups in the wool better color fastness [27].
structure. Further, madder exhibited higher dye uptake on clay-pre­ Among the native trees of Brazil that are popularly used for natural
treated samples compared with untreated wool and the color strength of dyeing is the Croton urucurana Baill. (known as “sangra d’� agua” in
dyeing on wool improved with an increasing clay levels in the pre­ Brazil), of the Euphorbiaceae family [19,31]. The specie is distributed in
treatment baths [11]. Extracts of dried Delphinium Zalil flowers con­ all Brazilian states and are suitable for multiple uses [31,32]. The wood
taining quercetin were used for dyeing silk yarns. It was reported that can be used for hydraulic and external works, construction of canoes,
pre-mordanting increased dye uptake levels and that the resultant dye­ carpentry and joinery; the tree can be used in afforestation, in mixed
ings possessed good light fastness [12]. Regarding synthetic fibers, plantations in degraded riparian areas, and as a hedge; their flowers are
nylon 6 fabric pre-treated with Al3þ, tannic acid, and Sn2þ mordants has melliferous [31,33]. Its trunk exudes a red resin upon being wounded.
been dyed using extracted polyphenolic dyes from henna leaves, Other species that produce red resin, also known as Dragon’s blood,
pomegranate rind, and Pterocarya fraxinifolia leaves. FT-IR spectral have already been used as natural dye [34]. The C. urucurana resin has
analysis was used to characterize the interaction between the mordants different components with antibacterial and analgesic properties [34].
and the dyes. As expected, the mordants increased color strength and The extract of its bark also has antibacterial properties [35,36].
improved the fastness properties on nylon and it was suggested that the The objective of the present work was to evaluate the Croton uru­
metal mordants can be effectively replaced with tannic acid [13]. curana Baill. bark extract as natural textile dye. The aqueous extract
Brazil has great potential for use of native plant species, since it has obtained was characterized by physicochemical methods and optimi­
the most diverse flora in the world [14]. To consolidate the use of native zation of dyeing conditions was investigated using a full factorial design
plant species, it is important to combine: i) availability of raw material; methodology with the independent variables: temperature, time and
ii) knowledge of traditional communities; iii) development of research concentration of extract. Color fastness to light, wash, rubbing and
and technology; iv) interactions with government and society to pro­ perspiration of the dyed fabrics from optimized dyeing conditions with
mote the sustainable use of these raw materials; v) the marketplace [15, and without mordants were analyzed. The wastewaters of dyeing were
16]. Of the products of the local flora, the bark of trees possesses great characterized by physicochemical methods.
social and cultural importance and economic value and are used for In view of previous reports indicating that C. urucurana has different
different purposes [17]. Barks also have potential for the extraction of components exhibiting antibacterial and analgesic properties [34–36],
natural dyes for textile dyeing. The use of this type raw material the extract of C. urucurana Baill bark was also examined antibacterial
(extract) as a dye in Brazil is reported by Garcia [18], Maureau, Fonseca properties in the present study.
and Altafin [19] and Ferreira [20]. In addition, studies with the barks of
certain species have already been carried out by researchers such as 2. Material and methods
Bechtold, Mahmud-Ali and Mussak [21], Pisitsak et al. [22] and Pun­
rattanasin et al. [23]. 2.1. Bark – gathering and processing
Tree bark consists of all tissues surrounding and external to its
vascular exchange and consists generally of polysaccharides (cellulose Bark samples were collected from C. urucurana specimens in con­
and hemicellulose), pectic substances, lignin, tannin, polyesters of cross- servation units of the State of Sa
~o Paulo, Brazil: Juquery State Park
linking, low molecular mass phenolic compounds, fatty acids and resins (Franco da Rocha) – Identification of the species carried out by MSc.
[24]. The composition will vary with the species, the part of the tree, the Osny Tadeu de Aguiar; Experimental Station of Itapetininga (Itapeti­
geographic location, the climate and the soil conditions [24]. The main ninga) – Identification of the species carried out by Dra. Cristina de
classes of extracted chromophores in the bark are phenolic compounds, Marco Santiago.
such as flavonoids, stilbenes and tannins [25]. Tannins are the group The barks were collected from the trunk by the bark board removal
most widely used as a natural dye, being traditionally extracted with method [17]. The geographical coordinates of the specimens were
water [24,25]. They consist of water soluble and high molar mass determined with the application GPS Status 8.0.170 – PRO for Android
polyphenols containing an aromatic ring structure with hydroxyl sub­ (Table 1).
stituents [26,27]. There are two main types of tannins: hydrolysable The barks were washed under running water with the aid of a brush
tannins (yellowish colors) and condensed tannins (reddish colors) [26, and dried in an oven at 40 � C until constant mass. Subsequently, the
28]. The hydrolyzable tannins can be grouped into galotannins and barks were milled with 10 mesh granulometry.
ellagitannins and form gallic acid and ellagic acid, respectively, when

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Table 2 Table 3
Independent variables and their actual values used in factorial design. Physicochemical properties of the C. urucurana bark extract.
Independent variable Symbol Unit Level pH Total (%) solids content Color

1 0 1 L* a* b*

Temperature A �
C 40 69 98 5.39 1.63 30,23 8,31 6,76
Time B min 20 40 60
Concentration of extract C % 10 55 100
were prepared from the extract (1.63% solids) without dilution (100%)
and at dilutions of 2 mL extract to 20 mL bath (10%) and 11 mL extract
2.2. Aqueous extraction to 20 mL bath (55%). The pH of all baths was adjusted to 5 using solu­
tions of acetic acid (HOAc) and sodium hydroxide (NaOH), both at 1 M
The barks were immersed in distilled water for 24 h (weight ratio of concentration. The pH of all dyebaths was adjusted to 5, because the pH
1:10) in a 500 mL flat-bottomed flask. The extraction was carried out on of the extract is near to this value (Table 3). The exhaust dyeing process
a hot plate, with the flask connected to a reflux condenser. The extrac­ was performed on the Mathis HT ALT-I equipment. For each combina­
tion was carried out at boiling temperature of the water for 1 h. The tion of temperature (40, 69 and 98 � C) and time (20, 40 and 60 min) the
extract was filtered through polyester voile fabric. equipment was programmed to generate a dyeing curve. After dyeing,
the samples were washed in running water and dried at 80 � C.
2.3. Characterization of the extract The dyed samples were evaluated by a HunterLab UltraScan PRO
spectrophotometer, by total reflectance, in the CIELAB space, with
The pH of the extract was measured in triplicate with a pH meter. illuminant D65 at 10� observer angle and 400–700 nm scan. Data was
The total solids content was measured in triplicate with a Mettler Toledo analyzed using EasyMatch QC software. The coordinates of color (L*, a*
HB43-S moisture analyzer. The color in the CIELAB space was read by and b*) and the color strength values (K/S) were determined at 400 nm.
total reflectance using a spectrophotometer with illuminant D65 at 10�
observer angle and 400–700 nm scan. A quartz transmission cell was 2.4.1. Optimization of dyeing conditions
used. Data was read by EasyMatch QC software. L* is the lightness and A 23-statistical experimental design (three independent variables at
varies from white (100) to black (0); a* is the red-green variation, when two levels) including replication with central point was used to deter­
it is positive the color varies for red, when negative, for green; b* is the mine the optimized conditions for the textile dyeing with natural dye
yellow-blue variation, when positive the color varies from yellow, when extract of C. urucurana to obtain a higher color strength (K/S). The in­
negative, to blue. dependent variables viz., temperature (A), time (B) and concentration of
extract (C), were coded at two levels as 1 and 1 and are given in
2.3.1. UV–Vis spectroscopy Table 2. The experimental design was generated by the statistical soft­
UV–visible spectral analysis of the extract was carried out using an ware Dell Statistica 13.2. Three replications were performed at the
Ultrospec 1100 pro spectrophotometer (Amersham Biosciences). The central point. A total of 11 experiments were performed in triplicate.
UV–visible spectrum was obtained in 245–455 nm wavelength range Data analyses was performed using results obtained (response vari­
with a 1 cm quartz cuvette. The dilution used was 1 ml of extract to ables) for color strength (K/S) from the reflectance values determined on
100 ml of water. Deionized water as the reference was used. dyed fabrics at 400 nm. Data were treated by analysis of variance
(ANOVA) and multiple regression analyses, for the development of
2.3.2. Lyophilization procedures mathematical models that represented the individual and interaction
C. urucurana aqueous extract (50 mL) was placed in a 50 mL volume effects of the independent variables on the color strength. The prediction
high density polyethylene bottle. The sample frozen at 80 � C was of the models was performed with 95% significance.
placed to a freeze dryer Thermo Modulyo D at 47 � C for 71 h.
2.4.2. Mordanting
2.3.3. Fourier transform infrared spectroscopy (FT-IR) To establish the influence of the mordant on the color fastness
Pressed pellets were prepared with the freeze-dried extract and KBr. properties a meta-mordanting procedure was used. Dyeing was per­
The FT-IR spectra were recorded with a Thermo Fisher Scientific Nicolet formed under the optimized dyeing conditions, using the extract and
iS10 spectrophotometer, with 32 scans in spectral range of mordant aluminum potassium sulfate (KAl(SO4)2⋅12H2O, alum) and
4000–400 cm 1 at a resolution of 4 cm 1. ferrous sulfate (FeSO4⋅7H2O) (6% owf).

2.3.4. Thermal analyses 2.5. Color fastness assessment

The thermal analyses were carried out in freeze-dried extract as well
as in cotton and wool fabrics before and after dyeing with C. urucurana Color fastness of dyed fabrics were evaluated for their light, wash,
extract in optimized dyeing condition, according to item 2.4. Ther­ rubbing and perspiration fastness properties, according to standard test
mogravimetric (TG) analyses were carried out on a Mettler Toledo TGA/ methods ISO 105-B02:1994 (method 1, exposure cycle A1), ISO 105-
DSC 1 STARe System apparatus under nitrogen atmosphere C06:2010 (method A1S), ISO 105-X12:2016 and ISO 105-E04:2013,
(50 mL min 1), at a heating rate of 10 � C min 1 and a temperature range respectively.
between 25 and 600 � C. Differential scanning calorimeter (DSC) mea­
surements were performed on a Mettler Toledo DSC822e apparatus 2.6. UV protection properties
under nitrogen atmosphere (50 mL min 1), at a heating rate of 10 � C
min 1 and a temperature range between 25 and 350 � C. The TG and DSC UV protection of the cotton and wool fabrics before and after dyeing
curves were analyzed in the STARe SW 12.10 thermal analysis software. with C. urucurana extract was evaluated according to standard test
method AATCC TM 183:2014. The UPF value for label and the UV-
2.4. Dyeing procedure protection category was determined according to standard test method
ASTM D 6630:2019.
Samples of 100% cotton woven fabric (203 g m 2) and 100% wool
woven fabric (215 g m 2) were prepared with 1 g each. The bath ratio
used in the dyeing process was 20:1. Aqueous dye baths (20 mL each)

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Fig. 2. Absorption spectrum of C. urucurana bark extract following a 1 to

Fig. 1. Images of the C. urucurana (a) bark and (b) aqueous extract. 100 dilution.

2.7. Antibacterial activity assessment

Cotton fabrics dyed under optimal conditions with and without

aluminum potassium sulfate and ferrous sulfate mordants, along with
the aqueous extract and freeze-dried extract of C. urucurana, were
evaluated for antibacterial activity. The untreated fabric samples and
fabric samples which went through the same dyeing conditions, but only
with the use of water (mock dyeing) and with the application of both
mordants only were evaluated too. In this assay, freeze-dried extract
(0.1 g) was suspended in 1.0 mL of deionized water and a non-toxic filter
paper disc was soaked in this suspension. The assessment was conducted
according to standard test method AATCC TM 90:2016. The antimi­
crobial potential of the fabrics and the extract was evaluated by the halo
test against Staphylococcus aureus ATCC 6538 and Klebsiella pneumoniae
ATCC 4352.

2.8. Wastewater analyses

Fig. 3. FT-IR spectra of C. urucurana extract.

The wastewaters from dyeing under optimized conditions before and

after mordant treatments were evaluated. A multiparameter Aquaread 3.1.1. UV–Vis spectroscopy
AP 800 Aquameter probe was used to measure the pH, turbidity, and Determination of the absorption properties of the extract afforded
total dissolved solids. Biochemical oxygen demand (BOD) and chemical the results shown in Fig. 2, where it can be seen that the principal ab­
oxygen demand (COD) were determined according to Standard Methods sorption lies in the UV region, specifically at 275 nm. The observed
for the Examination of Water and Wastewater [37] by method n� 5210 B absorption properties provided a basis for examining the UV-protection
and method n� 5220 D, respectively. The analysis of dissolved aluminum properties of textiles dyed with the extract.
and iron levels was carried out in an CCD simultaneous ICP-OES Varian The phenolic compounds exhibit intense absorption in the UV region
Vista MPX spectrophotometer and performed in triplicate. Initially, the of the spectrum [38]. Phenols and phenolic acids show absorption bands
samples were calcined and dissolved in aqua regia 1:1 (7.5 mL of HCl, between 250 and 290 nm while flavones and flavonols exhibit two ab­
3.5 mL of HNO3 and 10 mL of ultrapure water). The samples were then sorption bands of approximately at about 250 and 350 nm [38]. The
filtered through filter paper 40 and the filtrate diluted to 50 mL with principal absorption of the present extract may be associated with the
ultrapure water. The spectrophotometer was calibrated, and the samples presence of phenolic systems.
were read.
3.1.2. Fourier transformed infrared spectroscopy (FT-IR)
3. Results and discussion An FT-IR spectrum derived from the freeze-dried bark extract con­
tains characteristic bands at 1616 and 3386 cm 1 (Fig. 3). The intense
3.1. Physicochemical evaluations and relatively broad band centered at 3386 cm 1 is probably due to –OH
groups from polyphenols, such as flavonoids and tannins [39–41] and
Fig. 1 shows images of the C. urucurana bark and aqueous extract from associated (H-bonded) water molecules [42]. Similarly, the
used in this study. From the results presented in Table 3 it is possible to intense, sharp band at 1616 cm 1 is consistent with the presence of a
observe that the bark extract has acidic pH. Visually the extract was substituted benzene system. Representative structures for the
reddish-brown in color. Based on CIELAB values the extracts have red hydroxyl-rich flavonoids and tannin moieties are given in Fig. 4.
(cf. a*) and yellow (cf. b*) character. Since the coordinate a* and b* are Strong peaks in the 1620 to 1610 cm 1 suggest the presence of
closer to the achromatic point (0), the red and yellow colors are less condensed tannins [41]. The high intensity of this peak is consistent
saturated, that is, it has grayer. The value of L* is low, which indicates with a high degree of polymerization [41]. According with Foo [43],
that the extract is dark. bands in the region between 1540 and 1520 cm 1 are commonly
attributed to the stretching of an aromatic ring. In this case,

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Fig. 4. Flavonoid (left) and tannin (right) type compounds in C. urucurana bark extract.

Fig. 5. TG curves from C. urucurana extract and cotton and wool fabrics.

gallocatechin and catechin can be differentiated, since gallocatechin has

Table 4
three hydroxyl groups on aromatic ring B and gives twin peaks around
Results from TG analysis of the C. urucurana bark extract.
1535 and 1520 cm 1, while catechin has two hydroxyl groups and gives
a single peak near 1520 cm 1 [43]. In addition, the hydroxylation of ring Mass loss events Tinitial (� C) Tfinal (� C) Loss of mass (%)

B also produces peaks around 780 and 730 cm 1, where the out-of-plane 1� 29.15 129.37 4.19
deformations of the hydrogen atoms of the aromatic rings are absorbed, 2� 129.37 227.35 10.23
3� 226.92 438.34 28.37
being more accentuated between 780 and 770 cm 1 for procyanidins
4� 438.34 605.25 9.10
(catechins) and in 730 cm 1 for the prodelfinidines (gallocatechins)
[42]. In the spectrum it is possible to observe a peak near 1520 cm 1
(1521 cm 1) and a peak at 778 cm 1, which suggests the presence of loss in the first event (4.19%) may be associated with desorption of
catechin type condensed tannin in this extract. water and evaporation of other volatile components. The total mass loss
A peak was observed around 1452 and 1446 cm 1 (1448 cm 1) was 51.9%. According to Wesołowski and Konieczyn � ski [45], when
which corresponds to the vibration of elongation of aromatic rings [41]. samples of plants are evaluated by thermal analyzes, the observed
Peaks around 1509 cm 1, indicate the existence of aromatic rings and decomposition is a physicochemical phenomenon involving various
C–H in the samples, which may be associated with the presence of lignin organic and inorganic compounds, and it is therefore not feasible to
[44]. associate the loss of mass with the decomposition of a specific compo­
Peaks in 1300 to 800 cm 1 are related to C–O stretching and may nent present in the sample. Although the author refers to the analysis of
indicate the presence of cellulose and hemicellulose [40,41]. The most plants and not natural extracts, tree bark extracts also have different
informative bands for the presence of aromatic compounds are in the components, due to the presence of multiple components that are easily
900 and 675 cm 1 region and are related to deformation outside the extracted with water [24,25,27]. Thus, it is possible to infer that the
plane of the C–H connections [40]. Peaks in this region can also be freeze-dried extract of C. urucurana has a complex composition and that
attributed to the presence of tannin in the evaluated extract [41]. the observed mass loss is associated with loss of mass from different
components.
3.1.3. Thermal analysis The TG curves of the cotton and wool fabrics without and with
The thermogravimetric profile of the extract (Fig. 5) shows the dyeing showed mass loss events between 25 to 150 � C and 150–600 � C,
presence of four mass loss events, which is summarized in Table 4. Mass which are summarized in Table 5.

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Table 5 fiber [49]. In Fig. 5, a large loss of mass of the wool samples in the range
Results from TG analysis of cotton and wool fabrics before and after dyeing. of 200–350 � C. This event may be related to thermal degradation of
Substrate Mass loss (%) keratin, which occurs around 230 � C [50]. Regarding the behaviour of
the dyed fabrics, it is possible to infer that the dyeing did not generate a
25–150 � C 150–600 � C Total
significant change in the thermal degradation properties of the sub­
Cotton 3.78 80.84 84.62 strates, because the mass loss curves of the dyed substrates presented a
Dyed cotton 4.14 85.89 90.03
Wool 8.42 66.16 74.58
very similar profile to the non-dyed substrates. This indicates that the
Dyed wool 8.02 64.95 72.97 loss mass, in these cases, is mainly occurring due to the composition of
the substrates.
As regards to the analysis using DSC (Fig. 6), in Table 6 the
The first mass loss presented in Table 5, between 25 and 150 � C, may
indicate water desorption of the fabrics, since both wool and cotton are
hydrophilic [46]. It is possible to observe in Fig. 5 that in the range 320 Table 6
and 370 � C there is a large loss of mass in the cotton samples, which may Results from DSC analysis of C. urucurana extract and wool fabrics.
be related to the thermal degradation of the cellulose, which occurs Event Sample Peak temperature (� C) ΔH (J.g 1
)
around 350 � C [47,48]. At temperatures below 300 � C, cellulosic dam­ Endothermic Extract 54.8 151.0
age occurs in its amorphous region, however, between 300 and 380 � C Exothermic Extract 299.9 704.8
there is a significant mass loss, this being the main stage of pyrolysis of Endothermic Wool 80.7 197.5
Dyed wool 66.7 307.9
the cellulosic fibers, occurring generally in the crystalline region of the

Fig. 6. DSC curves from C. urucurana extract and cotton and wool fabrics.

Table 7
Composition of the runs of the factorial design and experimental responses.
Substrate Run Independent variables Responses – Color strength (K/S)

Repetition Average Standard deviation

A B C I II III

Cotton 1 1 1 1 0.18 0.19 0.19 0.186667 0.005774

2 1 1 1 0.83 0.77 0.79 0.796667 0.030551
3 1 1 1 0.20 0.20 0.18 0.193333 0.011547
4 1 1 1 0.82 0.88 0.83 0.843333 0.032146
5 1 1 1 0.39 0.40 0.38 0.390000 0.010000
6 1 1 1 1.56 1.56 1.50 1.540000 0.034641
7 1 1 1 0.48 0.47 0.46 0.470000 0.010000
8 1 1 1 1.84 1.79 1.90 1.843333 0.055076
9 0 0 0 0.70 0.70 0.76 0.723333 0.023979
10 0 0 0 0.72 0.71 0.71
11 0 0 0 0.76 0.71 0.74
Wool 1 1 1 1 0.72 0.70 0.66 0.693333 0.030551
2 1 1 1 0.91 0.88 0.94 0.910000 0.030000
3 1 1 1 0.60 0.61 0.62 0.610000 0.010000
4 1 1 1 0.98 0.97 0.96 0.970000 0.010000
5 1 1 1 1.35 1.36 1.40 1.370000 0.026458
6 1 1 1 3.55 3.54 3.56 3.550000 0.010000
7 1 1 1 2.00 1.81 1.86 1.890000 0.098489
8 1 1 1 5.24 5.26 5.47 5.323333 0.127410
9 0 0 0 1.25 1.17 1.22 1.222222 0.026822
10 0 0 0 1.25 1.21 1.20
11 0 0 0 1.22 1.25 1.23

Note – The mean and standard deviation values for the center point include the nine results obtained from the three runs: 9, 10 and 11.

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Table 8 the heat flow around 300 � C, which may be related to the onset of for­
Variance analysis of dyeing of cotton and wool with C. urucurana bark extract. mation of an exothermic peak of heat. Peaks around 350 and 370 � C are
Substrate Term SS df MS F-value p-value associated with the degradation of hemicellulose, cellulose and lignin
[52,53]. This result corroborates what was observed in the TG analyzes.
Cotton A 1.853704 1 1.853704 1131.112 0.000000
B 0.071504 1 0.071504 43.631 0.000001 If DSC analyzes comprised a higher temperature range, exothermic
C 5.367604 1 5.367604 3275.259 0.000000 peaks could have been observed in cotton fabric analyzes.
AB 0.040837 1 0.040837 24.919 0.000038 Two endothermic peaks were observed in the wool fabrics evaluated
AC 0.598504 1 0.598504 365.201 0.000000 (Fig. 6). The first endothermic peak corresponds to the first mass loss
BC 0.026004 1 0.026004 15.867 0.000517
ABC 0.012604 1 0.012604 7.691 0.010337
evident in the TG curves. Xu et al. [54] observed an endothermic peak
Error 0.040971 25 0.001639 around 80 � C when evaluating wool fibers by DSC. This peak is close to
Total 8.011733 32 that obtained in the analysis of the undyed wool fabric, therefore
Wool A 30.03844 1 30.03844 234.6061 0.000000 referring to the evaporation of water [54]. The undyed wool fabric had a
B 1.93234 1 1.93234 15.0919 0.000666
slightly displaced peak compared to dyed wool fabric, occurring in
C 14.36854 1 14.36854 112.2211 0.000000
AB 2.01260 1 2.01260 15.7188 0.000542 66.7 � C. A second event occurred around 230 � C, where a significant
AC 9.51300 1 9.51300 74.2984 0.000000 mass loss was observed in the TG curves. Xu et al. [54] related the peaks
BC 0.73150 1 0.73150 5.7132 0.024693 at 230 � C to the cleavage of cystine, ionic and hydrogen bonds and
ABC 0.46204 1 0.46204 3.6086 0.069077 changes in the matrix and microfibrillar regions of wool fiber. In the DSC
Error 3.20094 25 0.12804
Total 62.25941 32
curves of the wool fabrics, it is possible to observe an overlap of endo­
thermic and exothermic events, since immediately after the endothermic
peak around 230 � C, an exothermic peak begins, and its end is probable
temperature peaks and the enthalpy of the extract and of the wool to occur after 350 � C. This overlap of events makes it difficult to deter­
fabrics are given. For the extract, a peak was observed at 54.8 � C, which mine the integration limits for the enthalpy calculation. Thus, it was not
may be related to the evaporation of water and volatile components of calculated for the second peak observed in the DSC curves of the wool
the sample. In TG analysis it was observed that the first loss of mass in fabrics.
both extracts occurred approximately between 30 and 120 � C and may
therefore encompass this endothermic peak. The extract showed a broad
DSC peak around 300 � C, which may be related to the decomposition of 3.2. Optimization of dyeing conditions
a wide variety of secondary metabolites, mainly phenolic [51]. As the
plant extracts are composed of a mixture of substances in the plant Table 7 show the color strength (K/S) results at the wavelength of
matrix, their peaks are difficult to reproduce and their impurity level 400 nm for cotton and wool fabrics dyed with C. urucurana bark extract.
directly affects the enthalpy obtained and the width of the peak [51]. It is possible to observe that the values of color strength for both fabrics
In TG analysis, the cotton fabrics gave a large mass loss between 320 were higher when the variables were at level 1 (98 � C, 60 min and
and 370 � C. In the DSC curve, it was possible to observe an increase in concentration of the extract was 100%).
Table 8 show the ANOVA from dyed cotton and wool fabric. The p-

Fig. 7. Pareto chart showing the estimated effects of independent variables and their interactions on response factor, in (a) cotton dyeing and (b) wool dyeing. A –
Temperature; B – Time; C – Concentration of extract.

7
P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Fig. 8. Surface plots of (a) dyed cotton and (b) dyed wool.

value <0.05 indicated that the model terms were significant (95% However, there is a distinction between cotton and wool dyeing. For
confidence level). cotton dyeing, the most influential factor is the concentration of the
By multiple regression analysis on the experimental data, the models extract, while for wool dyeing, the temperature is the most important.
for the predicted responses could be expressed in the form of coded This shows that for the dyeing of the cotton fabric, the change in con­
values by Eq. (1), to cotton fabric, and Eq. (2), to wool fabric. centration has a more significant influence on the value of the color
strength. However, the color strength of wool fabric tends to change
K/S ¼ 0.757 þ 0.278A þ 0.054B þ 0.473C þ 0.041AB þ 0.158AC þ much more with temperature variation.
0.033BC þ 0.023ABC, with R2 ¼ 0.995 and R2 adj ¼ 0.993 (1)
The time has a lower effect on the color strength than the variables
K/S ¼ 1.726 þ 1.119A þ 0.284B þ þ 0.774C þ 0.289AB þ 0.629AC þ temperature and concentration and the interaction between them,
0.174BC þ 0.139ABC, with R2 ¼ 0.948 and R2 adj ¼ 0.934 (2) indicating to be the variable with less influence in the increase of the
color strength of the dyed fabrics. In addition, it is possible to observe
It is possible to observe in the Pareto chart (Fig. 7) the variables or that the interaction between the three studied variables presents less
interactions that have greater influence on the color strength of the dyed influence than the isolated variables and the second order interactions in
fabrics. The temperature and concentration of the extract, as well as the the coloristic force. In dyeing the wool fabric with both extracts the
interaction between these two variables, are the most significant, indi­ interaction between these three factors is not significant.
cating that they are the most important for the response variable. In the surface plots (Fig. 8) it is possible to observe that with increase

8
P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Fig. 9. Resulting colors in the wool and cotton fabrics by dyeing with the extract of C. urucurana without and with mordants. (For interpretation of the references to
color in this figure legend, the reader is referred to the Web version of this article.)

3.3. Dyeing under optimized conditions

Table 9
Color reading in CIELAB space for cotton and wool fabrics dyed with
Fig. 9 shows the resulting colors in the wool and cotton fabrics by
C. urucurana bark extract.
dyeing with the extract of C. urucurana without and with mordants. The
Substrate Mordant L* a* b* ΔE* K/S CIELAB color coordinates and color strength (K/S) of the dyed fabrics
Cotton – 61.69 14.22 17.90 38.71 1.62 under the optimized conditions are presented in Table 9. It was possible
KAl(SO4)2 63.31 12.27 16.28 36.01 1.41 to observe that the colors of the wool fabrics were more intense than
FeSO4 48.46 2.64 5.56 46.06 2.54
those of the cotton fabrics. Lightness values (L*) were lower for wool
Wool – 47.02 19.64 18.40 45.28 4.80
KAl(SO4)2 55.78 15.69 19.29 35.73 3.49 fabrics than for cotton fabrics under all conditions. As for the colors, it
FeSO4 40.79 2.05 5.91 47.88 5.31 was possible to observe that the values of the coordinates a* and b* were
higher for the fabrics dyed only with the extract and with the alum
mordant, indicating that these fabrics obtained more red and yellow
of the values of the variables - temperature, concentration and time - character. The coordinates a* and b* of the iron mordant dyed cotton
there is the increase of the color strength, for all the dyeing. Thus, it is and wool fabrics are close to the achromatic point (0.0), showing that
possible to determine that the best dyeing with C. urucurana bark extract the colors resulting from dyeing with that mordant are less saturated,
in cotton and wool fabrics was at 98 � C, 60 min and 100% of extract thus having a higher amount of gray. In addition, the lightness of the
concentration. The results obtained with the present study agree with colors dyed with this mordant is lower than those of the dyed fabrics in
the results of studies found in the literature on the dyeing of textile other conditions, which corroborates with the literature, which in­
substrates with tree bark extracts [23,55,56]. Nevertheless, based on the dicates that iron salt mordants make the colors darker [59].
graphs (Fig. 8) and results obtained, it is possible to verify that, for the As for the color difference (ΔE*) between the dyed fabrics and the
variable time being the least significant, if it were reduced to 40 min, undyed cotton and wool fabrics, it was possible to observe that the iron-
both for the dyeing of the cotton and wool fabric, the color strength mordant dyed fabrics had the highest values. Concerning the coloristic
obtained would be comparable to the color strength obtained under best strength (K/S), it was possible to observe that the lowest values were for
dyeing conditions. Coupled with this change, the decrease in tempera­ cotton fabrics. The highest values of color strength were observed in the
ture for dyeing the cotton fabric to 80 � C and adjusting the concentration wool fabrics dyed only with the extract and with the iron mordant.
of the extract for the dyeing of wool to 80% would also allow the In order to perform dyeing under optimized conditions with the use
resulting color strength to be comparable to the color strength obtained of mordants, the meta-mordanting was selected, once pre- and post-
under the best conditions dyeing, constituting more economical pro­ mordanting require a separate dyeing bath, where the substrate will
cesses. In addition, other changes could result in medium color strength be treated with the mordant, thus necessitating a greater amount of
values, which may be useful and economical depending on the final water and energy. The meta-mordanting process enables natural dyeing
application of the dyed fabric. to be performed with just one bath. By reducing the stages of dyeing, it is
Greater color intensity was observed on dyed wool fabric compared considered a more economical process [59].
to dyed cotton fabric. The presence of amino and carboxyl groups in Owing to the absence of direct affinity between most natural dyes
wool’s molecular structure provide bonding sites for natural dye mole­ and cotton fibers, mordants are used to help link these dyes to cellulose
cules [57]. It is known, for instance, that 1 mol of tannin can bind to chains. The typical dye–fiber interactions involve coordination bonds
12 mol of protein substrates [58]. This helps account for the affinity of illustrated in Fig. 10, for linking a flavonoid dye to cellulose in cotton
the present tree bark extract for wool, as the bark is rich in tannin and fibers using a metal ion (e.g. Al3þ, Fe2þ). These interactions are also
this is extracted into water [24,25,27]. essential to obtaining good fastness to light and water exposures.

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

caused by the alkaline detergent solution [60].

The grades of color fastness to rubbing (Table 10) varied from 4 to 5
to 5 for the dry test and 2–3 to 4–5 for the wet test. For the wool fabric,
the mordants aided in increasing color fastness. As for the cotton fabric,
the grades were, in general, kept. For color fastness to perspiration
(Table 11) the grades of color change varied from 2 to 3 to 4–5 for
alkaline perspiration, while for acid perspiration, the grades varied from
3 to 5. As for the grades of color staining, with exception of the dyed
cotton fabrics without mordant, all samples obtained grades between 4
and 5 and 5.

3.5. UV protection properties

The UV protection factor (UPF) of the cotton and wool fabrics before
and after dyeing with C. urucurana extract is shown in Table 12. It was
observed that there was a significant increase in UPF of the fabrics after
dyeing. According to ASTM D 6630:2019, the cotton and wool fabrics
Fig. 10. Representation of natural dye–mordant interactions on cotton, where without dyeing cannot be classified as UV protective since they have a
Met is a metal ion. UPF value for label less than 15.
The presence of an aryl-hydroxyl group ortho to the carbonyl group
3.4. Color fastness in flavonoid compounds contributes to colorfastness to light, through

The grades of color change to light (Table 10) ranged from 2 to 3 Table 12
(“poor to fair”) to 5 (“very good”). With the exposure to the light, the UV protection properties of the cotton and wool fabrics before and after dyeing.
fabrics tended to become weaker and yellower. In wool dyeing, the Substrate Mordant UPF UPF value for UV-protection
mordants increased the color fastness. In cotton dyeing, the aluminum value label category
mordant decreased the color fastness when compared with the cotton Non-dyed – 8.50 – –
fabric without dyeing. cotton
Color staining to the wash of the dyed fabrics (Table 10) was rating as Dyed cotton – 213.0 50þ Excellent
KAl 126.6 50þ Excellent
“very good” (5) for all the fibers of the multifiber fabric, under all
(SO4)2
conditions evaluated. The color change was between 2-3 and 4–5. The FeSO4 172.8 50þ Excellent
use of the alum mordant increased the grades of color fastness of both Non-dyed – 17.0 – –
fabrics. In the cotton fabric the iron mordant maintained the grades of wool
the non-mordanted fabric, while in the wool fabric the grade was rating Dyed wool – 118.8 50þ Excellent
KAl 57.2 40–50 Excellent
as “poor to fair” (2–3). Some fabrics tended to become redder after
(SO4)2
washing. In these cases, a bathochromic change in the absorption FeSO4 151.9 50þ Excellent
spectrum of the dye molecules may have occurred due to their ionization

Table 10
Color fastness to light, wash and rubbing.
Substrate Mordant Light Wash Rubbing

Color change Color staining Wet Dry

CA CO PA PES PAC WO Warp Weft Warp Weft

Cotton – 3–4 W 4 5 5 5 5 5 5 4–5 4–5 4 4

KAl(SO4)2 2–3 W, Y 4–5 R 5 5 5 5 5 5 5 5 4 4
FeSO4 3–4 W 4R 5 5 5 5 5 5 5 4–5 4 3–4
Wool – 2–3 W, Y 3–4 R 5 5 5 5 5 5 4–5 4–5 2–3 2–3
KAl(SO4)2 3–4 W 4 5 5 5 5 5 5 4–5 4–5 4–5 4
FeSO4 5W 2–3 R 5 5 5 5 5 5 4–5 4–5 3–4 3–4

CA – Acetate; CO – Cotton; PA – Polyamide; PES – Polyester; PAC – Acrylic; WO – Wool; W – Weaker; Y – Yellower; R – Redder.

Table 11
Color fastness to perspiration.
Substrate Mordant Alkaline Acid

Color change Color staining Color change Color staining

CA CO PA PES PAC WO CA CO PA PES PAC WO

Cotton – 3 4 3–4 3–4 3–4 3–4 4 4–5 4–5 3–4 3–4 4 4 4

KAl(SO4)2 3–4 4–5 4–5 4–5 4–5 4–5 4–5 3–4 4–5 4 4–5 4–5 4–5 4–5
FeSO4 2–3 5 4–5 5 5 5 5 3 5 4–5 4–5 5 4–5 4–5
Wool – 4–5 4–5 4–5 4–5 5 4–5 4–5 5 4–5 4–5 4–5 4–5 5 4–5
KAl(SO4)2 4–5 5 4–5 4–5 5 5 5 4–5 5 4–5 4–5 5 5 5
FeSO4 4 5 4–5 5 5 5 5 3–4 5 4–5 5 5 5 5

CA – Acetate; CO – Cotton; PA – Polyamide; PES – Polyester; PAC – Acrylic; WO – Wool.

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P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Despite the present results obtained, previous studies have shown

that the C. urucurana bark extract has antibacterial activity. Peres et al.
[35] showed the antibacterial activity of the C. urucurana bark extract
obtained with water and ethanol against the bacteria Staphylococcus
aureus and Salmonella typhimurium. In the study by Oliveira et al. [36],
latex and bark extracts obtained with hexane, dichloromethane, ethyl
acetate, 75% ethanol and chloroform were evaluated for antibacterial
activity. The bacterial strains evaluated were: Enterococcus faecalis,
Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus pyogenes,
Fig. 11. UV light induced IPT, as exhibited in the flavonoid Morin. Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Salmo­
nella typhimurium e Shigella flexneri. Latex showed activity toward all
bacteria except E. coli, for which it was inactive. All bark extracts
intramolecular proton transfer (IPT) in the excited state – a non-
showed antibacterial activity against S. aureus. Only chloroform and
destructive mechanism for dissipating the energy of absorbed UV
ethyl acetate extracts showed activity toward the bacterium
light. This process is illustrated in Fig. 11. As previous reported, flavo­
K. pneumoniae. Simionatto et al. [62] examined the antimicrobial ac­
noids typically absorb UV light in the 280–315 nm region to afford UV-B
tivity of the essential oils from stem bark C. urucurana obtained by
protection [12]. Bearing in mind that the flavonoid (morin) in the pre­
hydrodistillation for 4 h using a modified Clevenger-type apparatus,
sent study is isomeric with quercetin in the previous study, probably for
followed by exhaustive extraction of the distillate with hexane. The
this reason the C. urucurana extract offers UV protection on the cotton
results reveal that the crude essential oil of C. urucurana bark inhibited
and wool fabrics.
the growth of all microorganisms and that S. epidermidis and E. coli
In addition, dyeing fabrics in dark colors improve their UV protection
(MIC ¼ 1.25 mg mL 1) were the most sensitive, while B. subtilis and
properties [61]. As can be seen from Fig. 9, the colors resulting from the
C. albicans were the most resistant microorganisms (MIC ¼ 10 mg mL 1).
dyeing of cotton and wool with the C. urucurana bark extract were
Furthermore, the microbial growth inhibition increases to 70–90%
deeper colors, which may have helped to considerably increase the
when alum and copper sulfate are used for mordanting in textile dye
protection factor of these fabrics.
[63]. However, the antimicrobial activity is completely lost when
ferrous sulfate is used [63]. In this study, no antibacterial activity was
3.6. Antibacterial activity assessment observed in fabric even with the use of alum mordant.

Results from this assessment indicated the absence of antibacterial 3.7. Wastewater analysis
properties before and after dyeing cotton, as illustrated in Fig. 12
(against S. aureus) and in Fig. 13 (against K. pneumoniae), and in the From the data obtained by the wastewater analysis (Table 13), it can
aqueous extract and freeze-dried extract, as illustrated in Fig. 14. be observed that, according to the criteria determined by the Brazilian

Fig. 12. Assessment of antibacterial properties against Staphylococcus aureus during the various stages of dyeing cotton using C. urucurana without and
with mordants.

11
P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Fig. 13. Assessment of antibacterial properties against Klebsiella pneumoniae during the various stages of dyeing cotton using C. urucurana without and
with mordants.

Regarding the quantity of wastewater solids, CONAMA defines that the

quantity of sedimentable materials in 1 h test in Imhoff cone should be
determined, being the limit of 1 mL L 1 [64]. However, it was possible to
observe, from the total dissolved solids (TDS) test, that the amount of
TDS in the wastewaters is high, mainly due to its high organic load,
arising from different components present in the extract and possibly
from residues of textile fibers.
The parameters for turbidity in wastewater, according to CONAMA
[65], will depend on the body of water in which the wastewater will be
released. For freshwater bodies, depending on the class, the turbidity
should be up to 40 or 100 NTU [65]. It is possible to verify that the
turbidity of the analyzed wastewater was well above this value. In some
cases, the turbidity was above the capacity of the equipment (4000 NTU)
or the equipment could not register. The high turbidity value of these
wastewaters is related to the high presence of suspended solids in them,
mainly organic compounds.
According to Sperling [66], BOD of textile wastewater can vary from
200 to 5000 mg L 1, depending on the textile process evaluated. For
textile dye wastewater, Sperling [66] indicates that the BOD concen­
tration varies from 2000 to 5000 mg L 1. According to Table 12, it is
possible to observe that the BOD of the wastewater ranged from 221 to
4055 mg L 1, being close to the value found in the literature. In addition,
it was possible to observe that the BOD of the evaluated wastewater
exceeded the limits determined by CONAMA, which establishes the limit
of 120 mg L 1 [64].
Fig. 14. Assessment of antibacterial properties against Staphylococcus aureus According to Ammayappan and Jose [67] the ratio of the BOD to
and Klebsiella pneumoniae in the aqueous extract and freeze-dried extract; (1) COD concentration in the natural dye wastewater is approximately 1:2.
negative control, (2) positive control. This shows that these wastewater are highly biodegradable and treat­
able in treatment plants [67]. This relationship was observed for all
National Environment Council (CONAMA) for the pH of wastewater to evaluated wastewaters, indicating that they can be treated by biological
be released into receptor bodies, only wastewater containing iron sulfate processes so that they could be released into receiving bodies.
did not reach the allowed limit, which should be between 5 and 9 [64]. As for dissolved metals, Brazilian legislation determines the

12
P.M.S. Silva et al. Dyes and Pigments 173 (2020) 107953

Table 13
Characteristics of the wastewater from dyeing cotton and wool substrates with C. urucurana bark extract.
1 1
Substrate Mordant pH Turbidity (NTU) TDS (mg L ) BOD (mg L ) COD (mg L 1) Iron (mg L 1) Aluminum (mg L 1)

Cotton – 5.92 3580 1086 4055.0 7128.2 – –

KAl(SO4)2⋅12H2O 5.72 þ 1996 221.0 408.0 – 126
FeSO4⋅7H2O 4.49 n 1660 293.0 511.2 409 –
Wool – 6.36 2673 1153 212.0 390.0 – –
KAl(SO4)2⋅12H2O 6.05 þ 2020 2340.0 3963.6 – 118
FeSO4⋅7H2O 4.86 n 1557 266.0 482.7 495 –

NTU – Nephelometric Turbidity Units; TSD – Total Dissolved Solids; BOD – Biochemical Oxygen Demand; COD – Chemical Oxygen Demand; “n” – The equipment could
not register the value; “þ” – The equipment extrapolated the capacity of 4000 UNT.

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