Characterization and dyeing potential of colorant-bearing plants ofthe Mayan area in Yucatan Peninsula, Mexico
Manuel Jesús Chan-Bacab a, Patricia Sanmartín b, c, Juan Carlos Camacho-Chab a,Kahlia Beatriz Palomo-Ascanio a, d, Hesby Emmanuel Huitz-Quim�e a, d,Benjamín Otto Ortega-Morales a, *
a Departamento de Microbiología Ambiental y Biotecnología, Universidad Aut�onoma de Campeche, Av. Agustín Melgar s/n, Buenavista,C.P. 24039 Campeche, Mexicob Laboratory of Applied Microbiology, School of Engineering and Applied Sciences, Harvard University, 58 Oxford St., Cambridge, MA 02138, USAc Departamento de Edafología y Química Agrícola, Facultad de Farmacia, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spaind Facultad de Ciencias Químico-Biol�ogicas, Universidad Aut�onoma de Campeche, Av. Agustín Melgar s/n, Buenavista, C.P. 24039 Campeche, Mexico
a r t i c l e i n f o
Article history:Received 8 July 2014Received in revised form18 November 2014Accepted 1 December 2014Available online xxx
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a b s t r a c t
Natural dyes are receiving increasing attention from researchers and manufacturers, given its perceivedeco-friendly nature. Yet, adjunct agents known as mordants that help bond the molecules of the fabricbeing dyed and the colorant used to dye it are often toxic. There is scant published informationdescribing the dyeing potential and toxicity of colorant-bearing plants and the dye uptake with respectto the mordant treatments. A preliminary survey based on a range of sources of information showed thatof the Yucatan peninsula harbors 23 plants showing dyeing properties. Four of them (Justicia spicigera,Bixa orellana, Bougainvillea glabra and Rhoe discolor) were selected to extract their natural dyes, whichwere chemical and toxically characterized. B. orellana was successfully employed to dye the fabric, viz.ordinary cotton cloth, manta. The dye baths without mordant only present low toxicity, the J. spicigeraand B. glabra dyes being the most toxic. The B. orellana dye was less toxic, although its toxicity isincreased when mordants are used. Regarding color performances of the dyed fabrics, mordantinginfluenced the depth of the shades, improving dyeing and light fastness. Nevertheless, mordants had nosignificant effects on color values.
Mesoamerican civilizations such as Olmecs, Mayas, Aztecs andTeotihuacans have been reported using natural substances for thedyeing production (Guirola, 2010). During the Pre-Hispanic time(2000 B.C. e 1524 A.D.), the application of dyes, extracted fromplants and combined with several organic and inorganic elements,can be noticed in artistic pieces such mural paintings, decoratedmasks and stelas, and textile fragments (Cabezas, 2005). A widevariety of textile representations can be contemplated in thefamous murals of Bonampak (Chiapas, Mexico) one of the fewancient Maya archaeological sites still preserved. On those repre-sentations, the social class division was represented throught thetype of clothing weared by the characters. The Maya occupied the
30101.Morales).
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eastern third of Mesoamerica, and primarily the Yucatan peninsula(Mexico). It is one of the most emblematic civilizations of the worldnumbering millions of people that inhabited parts of the present-day Mexico, Guatemala, Belize, El Salvador and Honduras. TheMaya used natural dyes comprising both biological-derived (mainlyfrom plants) and inorganic dyes. In fact, the Maya Blue is perhapsthe most studied pigment due to its remarkable chemical stabilityand resistance in the aggressive tropical environment of CentralAmerica. Maya Blue is a combination of both inorganic and organicelements: palygorskite or attapulgite clay (also called yucatec saktu'lum in Maya) and a blue dye that is produced by the indigo plant(or ch'oh in Maya) (Chiari et al., 2003). On the contrary, theperishable nature of other dyes and colorants used by the Mayacivilization made it difficult for archeologists to find evidence oftheir use among the ancient Mayan remains and the extent of theiremployment remains uncertain. Some investigators argue that thefirst evidence of the use of dyes in the area was found among hu-man groups that used the pigments as body paintings, for ritual
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purpose and for environmental adaptation, probably using them asbug repellents (Ivic de Monterroso and Berger de White, 2008).Then, during the colonial period (from the Spaniards first settle-ment in 1524, to 1821) dyeing plants started to be traded as luxurygoods for a very high price. Their value was only exceeded by thegold and silver that was also found in the American continent. Theinterest that the Spanish had in the dyeing techniques used by theindigenous people, is also documented by the detailed registriesthat they made of such techniques. Unfortunately, in some parts ofMesoamerica there is still a lack of information about this topic(Guirola, 2010).
In Europe, during the XIX century, the textile industries ac-quired huge quantities of dyes that were easily available. Thissituation triggered the invention of synthetic dyes, offering a vastrange of new colors at a lower-cost, and imparting better prop-erties to the dyed materials (Garfield, 2000). In many Mayan re-gions the incursion of such dyes partially, and sometimes fully,replaced the use of local dyeing, although the original dyingsubstances remained. Nowadays synthetic dyes are still the pri-mary option chosen to dye textiles, in spite of the potential healthand environmental risks, as some of them have been reported tohave carcinogenic and other cytotoxic effects (Sewekow, 1998).Yet, in some region this discovery has prompted a resurgence ofthe use of dyes derived from natural to replace, at least partially,synthetic dyes. This renewed interest in plant dyes goes in linewith a worldwide concern for the development of eco-friendlyand sustainable productions (Padhy and Rathi, 1990; Garg et al.,1991; Eom et al., 2001), including in the textile field (Guinotet al., 2006; Bechtold et al., 2007; Islam et al., 2013). However,contrary to dominant public opinion, natural dyes are neithersystematically safer nor more ecologically sound than syntheticdyes. A few natural dyes, such as logwood (Haematoxylum cam-pechianum), which contains hematin and hematoxylin, arethemselves significantly poisonous (Buchanan, 1987). Adjunctagents known as mordants, applied in conjunction with the nat-ural dye to increase its affinity, substantivity and fastness prop-erties, may be toxic at different levels (Haar et al., 2013). Mostmordanting agents are metallic salts of chromium, tin, iron,copper, and aluminum; heavy metals significantly toxic andharmful to the environment and human health. Copper andchromium containing compounds (viz. copper sulfate and potas-sium dichromate) were widely used as mordants, but their usagehas declined because of their toxicity (Cardon, 2007; Haar et al.,2013), and so as iron and tin mordants. The aluminum-mordanting agents are considered among the safest in theapplication of natural dyes to fabric materials and is the mostcommonly used in dyeing techniques.
There are very limited published studies that describe thedyeing potential of colorant bearing plants and the dye uptakewithrespect to the mordant treatments. However, natural dyes arereceiving increasing attention from researchers andmanufacturers.Thus, for example, natural pigment extracted from waste chestnutshell was successfully applied in dyeing of cellulase-treated flaxfabric (Zhao et al., 2014). Similarly in previous studies by Mirjaliliet al. (2011) and Komboonchoo and Bechtold (2009), weld extractwas used inwool dyeing and indigo carmine as a source of blue dyefor wool. Extraction of dye, colorimetric assessment and antimi-crobial properties of silk yarn dyed with extracts from two nativeplants, viz. Saraca asoca and Albizia lebbeck was carried out byBaliarsingh et al. (2012). In the same year, Boonsong et al. (2012)studied the pigments from six species of Thai plants to generateeco-friendly dyes. In the study carried out by Bulut and Akar (2012)some plant wastes such as rosemary, rose, lavender and mate teaextracts were used to obtain ecological dyeing on cationized cottonfabric and woolen yarn without metal salts.
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Modern Maya artisans use both synthetic and plant-derivedcolorants to dye textiles and vegetable fibers to craft hats anddecorative items. In the Campeche region (one of the statescomprising the Yucatan peninsula), where this study was carriedout, some of the rural craftsmen extract dyes from the leaves, roots,flowers or bark of some plant species mostly by boiling and byperforming other procedures that they are reluctant to disclose. It isapparent that countless natural resources that have been used inMesoamerica since the Pre-Hispanic epoch and some are still usedthanks to the oral transmission of this knowledge. But there isinsufficient information regarding the characterization of manyplant species used for dyeing purposes.
This studyaims at characterizing somenatural dyes derived fromplants used in different areas of the Yucatan peninsula (Mexico) andwill hopefully contribute to spread safe and sustainable ancestraltechniques of hand-crafted productions essential to rural livelihood.Thus, the objectives of our studywere to: (1) carry out a preliminaryplant inventory and ethnobotanical study of the traditional dyeingresources from this region (Yucatan peninsula), (2) extract thenatural dyes from the four most used plant species, (3) determinethe main chemical constituents of these natural selected dye ex-tracts, (4) assess the potential toxicity of these selected natural dyeextracts through bioassays of Artemia salina and Lactuca sativa, and,lastly (5) to dye ordinary cotton cloth (manta) with Bixa orellana dyeextract (one of the four selected), analyze the fabric dyed and toexamine the color properties. Note that traditional studies at labo-ratory scale has been carried out several times for the evaluation ofnovel natural dyes in different fabrics, like wool, cotton, leather, etc.even fairly recently (e.g., Erdem Ismal et al., 2014; Ghaheh et al.,2014). Furthermore, toxicity studies on natural dyes for textile ap-plications are almost non-existent. Despite textile workers and afew studies (e.g. Erdem Ismal et al., 2014) have reported that whenmetal mordants, such as Fe, Al, Cu, Pb or Sn are used, natural dyeingprocesses typically generate wastewater containing residual toxicmetal ions frommetal saltmordantswhich have negative impact onthe environment and public health. The present work is therefore apioneer effort in this regard, while it is also the first report whereplants of the Mayan area in Yucatan Peninsula, used in cottondyeing, has been shown as a source of natural dye.
2. Materials and methods
2.1. Plant inventory and ethnobotanical study
An ethnobotanical inventory, in which we related the plantspecies and their utilization by the local people inhabiting in theregion, was conducted in the Mayan area from Yucatan peninsula(Mexico). Three main sources of information were used to conductthe inventory: (i) analysis of regional herbaria data, (ii) biblio-graphic studies, and (iii) a number of interviews with craftsmenand herbalists. The data collected also included the local names ofthe plants and the parts of the plant used to prepare the dye.
2.2. Dye extraction procedure
The extraction of dyestuffs was carried out using four plantspecies of all native plants inventoried in the previous Section 2.1.These plants were selected, taking into account their common useby local rural handicraftsmen, and abundance in the region, asevidenced by the survey that was conducted. An additional crite-rion was that the local Ministry of Commerce and IndustrialDevelopment expressed its interest in performing research thatmay reach eventually application in local hand craftsmanship.
Plant samples were purchased in the local market. A botanistfrom the Autonomous University of Campeche (Mexico) confirmed
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their identity. The four plant species selected were Justicia spicigera,Bixa orellana, Bougainvillea glabra and Rhoeo discolor. The part of theplants employed for extraction included leaves, seeds, bracts andleaves, respectively. The material was dried at room temperature,stored in the dark, and extracted through two methods: a tradi-tional (hot water extraction) and an alternative modern method(microwaves). Two solvents were employed for each method: wa-ter and ethanol diluted to 10% strength. All the experiments werecarried out in duplicate.
2.2.1. Decoction or hot water extractionA known amount (20 g) of dry plant material was extractedwith
400 ml of boiled distilled water, following the standard procedurein which the ratio of plant biomass to solvent volume is 1:20.Extraction was performed for 60 min at 100 �C in an open beaker.Extracts were cooled at room temperature (26 �C) and filtered usingWhatman No. 40 filter paper. Samples were frozen and freeze-dried(Labconco). The same extraction procedure was performed using10% ethanol as extraction solvent.
2.2.2. Microwave-assisted extractionThe process of microwave assisted extraction method was per-
formed in a domestic microwave oven (Sharp model R-501CW)with the power of 800 W and the frequency set on 2450 MHz. Aweighted amount (20 g) of dry plant material was subjected toextraction by adding 400 ml distilled water in a 1000 ml glassbeaker. The glass beaker was placed in the center of the microwaveoven. Samples were exposed to microwave irradiation during fivecycles (one cycle equals 1 min of duty cycle followed by minutebreak to avoid overheating, i.e. 1 min on/1 min off). Extracts werecooled at room temperature and filtered using Whatman filterpaper No. 40. Samples were frozen and lyophilized to dryness andstored at room temperature (26 �C).
2.3. Chemical characterization of the extracted dyes
The aqueous extracts of J. spicigera, B. orellana, B. glabra and R.discolor were chemically characterized by spectroscopic and chro-matographic techniques. The dye extracts were subjected to UV-VISspectrophotometer (UNICO SQ-2800) after suitably diluting theextracted dye with water (1 mg/ml). The UV VIS spectra of thenatural dyes from the four plant species were obtained in visibleregion of 400e750 nm and the peak absorbance (lmax) wasmeasured and recorded. Additionally, all samples were examinedby thin-layer chromatography (TLC) on silica gel 60 G F-254 plates(Merck). Chromatography was performed in following solventsystems: ethyl acetate-formic acid-water (33:7:10) and benzene-acetone (95:5). The chromatograms were observed first withoutchemical treatment, under UV 254 and UV 365 nm light, and sub-sequently using the spray reagents, namely, Dragendorff reagentfor alkaloids, Borntr€ager reagent for antraquinones, Liebermann-Buchard reagent for triterpenes, and natural products and poly-ethylenglycol (NP/PEG) reagent for flavonoids.
2.4. Toxicity study of the extracted dyes
In order to assess the potential toxicity of the four extracteddyes, bioassays with the microcrustacean A. salina (brine shrimp)and the annual plant L. sativa (lettuce) were carried out. TheA. salina assay was performed according to the modified method ofSolis et al. (1993). Larvae of A. salina (24 h old) were exposed todifferent concentrations of the J. spicigera, B. orellana, B. glabra andR. discolor residual dyeing baths at 25 �C for a period of 24 h. Thedyeing baths were tested in a concentration series of 50%, 25%,12.5% and 6.25%, in the 96-well microplates in triplicate. Negative
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controls were performed in parallel using an artificial marine saltsolution (38 g/l). After an incubation of 24 h, the number of deadlarvae was counted and the percentage of dead nauplii calculated.The L. sativa seeds (germination) assay was performed accordingto Pal�acio et al. (2009) in Petri dishes, where filter paper disks(Whatman No. 5) were placed and wetted with 5 ml of theJ. spicigera, B. orellana, B. glabra and R. discolor residual dyeingbaths. In this case, the dyeing baths were tested in a concentrationseries of 100% and 50%. Negative controls were performed inparallel using distilled water (5 ml). A total of twenty lettuce seedswere distributed in each dish. The dishes were incubated forgermination at 24 ± 1 �C under 12 h light/12 h dark cycles. After anincubation of 96 h, the germination percentage and radical lengthwere recorded to calculate the germination index (GI). Thegermination index (GI) was calculated according to the formulaGI ¼ G/G0 � L/L0 � 100, where G0 and L0 are respectively thegermination percentage (number of seeds germinated) and rootgrowth (radical length) of the 100%, distilled water control. Theglobal germination index (GI) was the GI averages of the 100% and50% extract treatments. This last bioassay was not used for theresidual dyeing baths from the pre-mordanting method assays(see Section 2.5), because the simultaneous mordanting or ‘single-bath method’ (see Section 2.5) is used in most of studies on seedsgermination of L. sativa.
2.5. Dyeing fabric with B. orellana dye extract
The ordinary cotton cloth (manta) was the fabric selected for thestudy. It was scoured in an aqueous solution containing 0.5 g/lsodium carbonate and 2 g/l non-ionic detergent at 50 �C for 25min.The scoured fabric was thoroughly washed with deionized waterand soaked in clean water for 30 min. Subsequently, circular piecesof fabric material between 33.20 cm2 (6.5 cm aprox. of diameter)and 38.50 cm2 (7 cm aprox. of diameter) were prepared for dyeingand mordanting.
Dyes from J. spicigera, B. glabra, and R. discolor without mordantdemonstrated to be adjectives, since they had poor fixation to thefabric, whereas the B. orellana dye adhered to the fabric withoutlosing much dye during the rinse. Based on these results, theextracted dye solution from Bixa orellana (Rajendran, 1990; Sinhaet al., 2013; Tamil Selvi et al., 2013) was employed to dye cottoncloth (manta). The fabric was dyed with the B. orellana extractcolorant without the use of mordants (Fig. 1) in open beakers withmanual agitation of the material. The dye (2.5% w/v) was dissolvedin water with increasing temperature up to 50 �C. The fabric sam-ples were submerged in the solution, which was further heated to80 �C. The temperature was maintained with continuous agitationfor 1 h. After dyeing, the dye surplus was removed from the dyedmaterials by rinsing three times with water at 50 �C. Furthermore,mordants such as tannic acid (0.2% w/v), sodium citrate (2.9% w/v),aluminum potassium sulfate (0.625% w/v), and ferrous sulfate (0.1%w/v) were used to mordant the fabric (Fig. 2). Two mordantingprocesses were used: pre-mordanting, a process in which thesample is first mordanted and after dyed, and simultaneous mor-danting or co-mordanting, where the sample is treated simulta-neously with dye and mordant. For the pre-mordanting method,the fabrics were first immersed in the aqueous solutions of eachone of the aforementioned mordants at 50 �C for 30 min. Thesamples were then removed and without drained were immersedin a water extract of B. orellana (2.5% w/v) at 80 �C for 1 h withconstant stirring. Subsequently the pre-mordanted fabrics werewashed twice (1 min each) at 50 �C with distilled water. For thesimultaneous mordanting (i.e. dyeing in the presence of mordants),the fabrics were immersed in a bath containing a mordant and thedye extract of B. orellana at room temperature (26 �C). Undyed
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Fig. 1. Picture of the ordinary cotton cloth (manta) undyed (left) and dyed using B. orellana extract colorant without the use of mordants (right).
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fabric samples were used as controls. Experiments were performedby triplicate.
2.6. Colorimetric and fastness properties of fabric dyed withB. orellana dye extract
Dyed fabrics with B. orellana processed in this study (see Section2.5) were subjected to the reflectance color measurements using aKonica Minolta colorimeter with a CR-300 measuring head (8-mm-diameter viewing area). The following measurement conditionswere selected: illuminant D65, which represents a phase ofdaylight, with a CCT of approximately 6500 K, including the
Fig. 2. Several pictures of the dyed fabrics with mordanting. A: pre-mordanting with tanncitrate, D: simultaneous mordanting with sodium citrate, E: pre-mordanting with aluminumpre-mordanting with ferrous sulfate, H: simultaneous mordanting with ferrous sulfate. Con
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ultraviolet region spectrum, and 2� observer (CIE 1931). The mea-surements were made by spectral reflectance, using the diffuseillumination geometry with an integration sphere, covered with awhite material, so that the light is uniformly diffuse in all directionsilluminating the sample, and is observed with the specularcomponent included in 8� in relation to normal (d/8�). The colormeasurements were analyzed by considering the CIE L*a*b* orCIELAB color system (CIE 1986), which is widely accepted by boththe scientific community and industry, since is the most perceptu-ally uniform of the color spaces (Berns, 2000; V€olz, 2001). Percep-tually uniform means that a change of the same amount in a colorvalue should produce a change of about the same visual
ic acid, B: simultaneous mordanting with tannic acid, C: pre-mordanting with sodiumpotassium sulfate, F: simultaneous mordanting with aluminum potassium sulfate, G:trols appear on the left in the pictures.
and dyeing potential of colorant-bearing plants of the Mayan area inx.doi.org/10.1016/j.jclepro.2014.12.004
Table 1Plants identified with dyeing potential that are of common use in the YucatanPeninsula. The four plant species selected for this study are indicated in bold.
Scientific name Family Local name (Mayanand Spanish languages)
DCA: decoction with distilled water; DCE: decoction with 10% ethanol; MCA: mi-crowave with distilled water; MCE: microwave with 10% ethanol.
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importance. The CIELAB color system is organized with three axesin a spherical form: L*, a* and b*. The L* axis is associated with thelightness of the color and moves from top (value: 100, white) tobottom (value: 0, black), whereas the a* and b* axes are associatedwith changes in redness-greenness (positive a* is red and negativea* is green) and in yellowness-blueness (positive b* is yellow andnegative b* is blue); both move in the two axes that form a planeorthogonal to L*, and do not have specific numerical limits.Furthermore, the color parameters most closely related to thepsychophysical characteristics of color, i.e. more related to colorperception, and which correspond to the angular coordinates C*aband hab were also calculated. C*ab is the chroma or saturation ofcolor (C*ab ¼ [a*2 þ b*2]1/2) measured as the length of the line fromthe neutral point to the sample point in the a*b* plane, and hab isthe hue angle or tone (hab ¼ arctan (b*/a*)) refers to the dominantwavelength, as is the CIELAB color parameter that represents themajor color perception attribute, indicating redness, yellowness,greenness, or blueness in a circular scale that starts at 0� and in-creases counter clockwise to 360� (Wyszecki and Stiles, 1982;Boonsong et al., 2012). Likewise, the partial (DL*, Da* and Db*)and the total (DE*ab ¼ [(DL*)2 þ (Da*)2 þ (Db*)2]1/2) color differ-ences between the textile samples were calculated. The samplescompared were: (i) the dyed with the undyed samples, (ii) the dyedsamples with and without the use of mordant, and (iii) the pre-mordanting and simultaneous mordanting dyeing samples. Like-wise, both sides of the same textile sample were compared usingDE*ab. With the purpose of establishing the minimum number ofmeasurements required to quantify the color of the dyed textilematerial under study, ten measurements at random positions ontocircular areas of the textile material have been previously carriedout. From them the minimum number of measurements requiredwas analyzed by taking into account the cumulative averages of theCIELAB color system coordinates: L*, a*, and b* (Prieto et al., 2010a).Furthermore, fastness properties to washing and light of dyedsamples were assessed according to ISO Test methods (ISO105C06-at 40 �C for 30 min) and (ISO 105 BO2), respectively (such as inErdem Ismal et al., 2014; Haddar et al., 2014).
3. Results and discussion
With ever-increasing demand for eco-friendly, non-toxic color-ants, dyes derived from natural sources have emerged as a potentialalternative to relatively toxic synthetic dyes. The current marketvalue of commercially used carotenoids was estimated at nearly$1.2 billion in 2010 (BBC Research, 2011). Thus, it is expected thatthe market niche for colorants derived from natural sources isconsiderable higher that the above cited figure, showing theimportance of these biomolecules in modern bioeconomies.
In this context, the list of dyeing plant species inventoried in theethnobotanical study is arranged in alphabetical order using thebotanical family as a reference (Table 1). The most prevalent fam-ilies are Fabaceae followed by Rubiaceae. A total of twenty-threedifferent plants were identified as common sources of dyes;although other plants appeared to be also a source of dyes, theywere not used as much and therefore they are not included in thisstudy. Leaves are the most prevalent type of biomass material thatis used to obtain dyes, followed by bark. Most of the plants werereadily identified by their Mayan names by local handicraftsmenworking with them. Taking into account the criteria explainedpreviously (see Section 2.1) four of these plants were selected forthe extraction of dyes, namely J. spicigera, Bixa orellana, B. glabraand Rhoeo discolor.
A comparative study of the effects of processing parameters ofextraction on the yield of J. spicigera, B. orellana, B. glabra andR. discolor dyes revealed that in all cases the yield of extractmaterial
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was better using the traditional heating method (decoction) thanthat from the microwave method. In contrast, the study on pome-granate (Punica granatum L.) rind by Sinha et al. (2012) reported thatthe application ofmicrowave irradiationmethod improved the yieldof dye. This diversity within the natural dyes probably results fromdifferences in the main chemical constituents and morphology.Moreover for the dye extraction Sinha et al. (2012) used statisticalanalyses (response surface optimization and artificial neuralnetwork modeling), which predict the optimal experimental con-ditions for maximum extraction of dye. More recently, the sameauthors (Sinha et al., 2013) published a study inwhichused the sametwo statistical analyses for simulation and optimization of the dyemicrowave-assisted extraction process from B. orellana, one of thespecies selected by this study. Unfortunately decoction extractionwas not included in their study. In addition, in our study, a binarysolvent extraction system (water and ethanol) was superior to amonosolvent system (water) in most cases. The four plant speciesincrease the percentage of extracted matter (from 20 g of plantsample) in the order of J. spicigera > B. glabra > B. orellana andR. discolor (Table 2).
Thin-layer chromatography (TLC) profiles of natural dyes fromthe four plant species were similar (data not shown), which isconsistent with the results obtained in the absorption spectra
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(Fig. 3). In all extracts obtained from J. spicigera, B. glabra, and R.discolor were detected flavonoids as metabolites responsible ofcoloration. It has been previously reported that both J. spicigera as R.discolor contain flavonoids, particularly anthocyanins, which maybe responsible for the signals observed in the absorption spectra(Asen et al., 1972). Signals of betalains in B. glabra extracts weredetected at 535 nm (betacyanins), although from previous studiesthe occurrence of flavonoids in the bracts of this plant is known(Kumar et al., 2013). We expected the presence of bixin or norbixinbut they were not actually detected in B. orellana extracts. This isprobably due to the extraction procedure itself, as these moleculeswere probably eliminated when the extracted plant material wasfiltered to obtain a water soluble dye (Figs. 3 and 4).
In order to assess the toxicological response of the residuarydyeing baths on living organisms, A. salina and L. sativa were usedas toxicity level models due to their fast response to concentratedand diluted by-product solutions. The dye residual baths withoutmordant did not show any toxic activity against nauplii of A. salina,but exhibited certain phytotoxic activity on L. sativa seeds to con-centrations of 100% and 50%, the J. spicigera and B. glabra dyes beingthemost toxic (Table 3). The B. orellana dyewas less toxic in the testof L. sativa seed germination, though its toxicity increasedwhen thecolorant was mixed with the corresponding mordant used in thedyeing process (Table 4). This result was also observed with A.salina in some combinations. The combination of B. orellana dyeand aluminum potassium sulfate was the most toxic for themicrocrustacean A. salina. The combination of B. orellana dye andsodium citrate was the most toxic for L. sativa seeds (Table 4).
In previous studies with leather fabrics, B. orellana extractappeared to be a viable option to natural dyed process (Tamil Selviet al., 2013) and the same result is achieved for the ordinary cottoncloth (manta). Importantly, cotton fiber has very low affinity formost of the natural dyes (Shahid et al., 2013). Pieces of ordinary
Fig. 3. Absorption spectra for extracts of (a) J. spiciger
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cotton cloth (manta) colored using B. orellana extract have beensubjected to reflectance measurement. The color measurementparameters L*, a*, b*, C*ab and hab were recorded. The minimumnumber of measurements required to characterize these parame-ters in each sample of dyed textile material was defined from thesteady section of the inverted exponential decay graph, obtained byplotting the cumulative averages of Cartesian CIELAB coordinates(L*, a* and b*) against number of measurements (Prieto et al., 2010a,2010b, 2011). Thus, it was 8 measurements to characterize an areabetween 33.20 and 38.50 cm2 approximately, with an 8-mmviewing aperture diameter. Once the measuring protocol wasdefined, the color of each dyed textile sample with B. orellanaextract was characterized by carrying out eight measurements atrandom positions on three replicates of each type of sample,following the conditions described in Section 2.6. The values of theCIELAB color coordinates: L*, a* and b*, C*ab and hab for the dyedfabrics processed in this study shown in Table 5. The L* parameter(color lightness) varied between 74.17 and 62.32 CIELAB units fordyed samples, 80.60 CIELAB units was the L* value of the control(undyed fabric, U), indicating a clearly perceptible darkening of thefabric due to dye, i.e. DL* > 6 CIELAB units, perceptible difference incolor (Hardeberg, 1999; Giacomucci et al., 2012). The value of a*(associated with greenness (�) to redness (þ) changes) variedfrom �0.11 (U) to 3.22 (DSF) and 24.63 (DSC) range of data,conferring the fabric a reddish color. The changes in b* (associatedwith blueness (�) to yellowness (þ) changes) and C*ab (colorchroma) were very similar except for DSC; in both cases theyincreased by at least 11 CIELAB units, whichmeansmore yellow andchromatic colors. The hue angle, hab, for dyed fabrics with andwithout mordant, fell within the interval 83.87� (DSA) and 60.90�
(DSC), so theywere located in the yellow, yellow-orange hue area. Itwas observed, therefore, that color components isolated from BixaOrellana led to a specific toasted color. All the mordants influenced
a, (b) B. orellana, (c) B. glabra, and (d) R. discolor.
and dyeing potential of colorant-bearing plants of the Mayan area inx.doi.org/10.1016/j.jclepro.2014.12.004
Fig. 4. Chemical structure of the flavonoid pigments, main colorants present in the extracted plant materials.
Table 4
M.J. Chan-Bacab et al. / Journal of Cleaner Production xxx (2014) 1e10 7
the depth of the shades, which suggests that the mordants allowthe fixation of B. orellana dye to the natural fibers of cotton cloth(manta) by the formation of a chemical bridge between the dye andthe fiber. This result is similar to that achieved byMeksi et al. (2012)in wool fabrics colored using olive mill wastewater, in whichmordanting gave higher dyeability. The fabrics dyed withoutmordant (DWM) showed lighter shades, i.e. higher values of L*,except those dyed with aluminum mordant (DPA and DSA). How-ever values of hab in DWM moved away control (undyed fabric, U)almost as much (DSC and DPC is further away) or even more thatthe cotton fabrics with mordant (Table 5). The value of hab repre-sents the major color perception attribute therefore these resultsled us to conclude that mordant had no significant effect on colorvalues (Boonsong et al., 2012). Simultaneous mordanting with so-dium citrate (DSC) showed a deeper maximum color than the restof fabrics dyed did, with a maximum value of a* (associated withredness increase) and b* (associated with yellowness increase) andC*ab (color chroma), and a minimum value of L* (color lightness)and hab (hue angle). It was only surpassed in L* parameter by thesimultaneous mordanting with ferrous sulfate (DSF), which isrelated with darkening of the color. In all cases the partial and totalcolor differences between the dyed fabrics (Table 6), with respect tothe control (undyed fabric), surpassed the visual threshold of 3CIELAB, perceptible to the human eye (Wyszecki and Stiles, 1982;V€olz, 2001). The greatest difference was observed in the simulta-neous sodium citrate-mordanted fabrics (DSC). Themordants in theorder of DPC < DST < DPA < DPT < DSA < DPF < DSF < DSCincreased the color change of the dyed fabrics. From the results, itwas also confirmed that the premordanting method versus the
Table 3Toxicity of plant dyes assessed in this study.
Plant dye Target organism
Artemia salina Lactuca sativa
Tested concentrations
6.25% 12.5% 25% 50% 50% 100%
J. spicigera dye 0a 0 0 0 52.9b 28.0B. glabra dye 0 0 0 0 58.6 29.9R. discolor dye 0 0 0 0 69.5 59.8B. orellana dye 0 0 0 0 82.9 63.1Artificial sea water e e e 0 e e
Distilled water e e e e e 100
a Dead nauplii percentage.b germination index percentage.
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simultaneous mordanting gave rise to fabrics colored with aperceptibly different color, with the exception of tannic acid-mordanted (DPT and DST) fabrics. Finally to analyze color varia-tions between both sides of the dyed fabric, the total color differ-ences (DE*ab) between both sides for each dyed textile sample werecalculated and their average values were plotted in Fig. 5. Thegreatest differences were observed with the simultaneous mor-danting with aluminum potassium sulfate (DSA) and the simulta-neous mordanting with ferrous sulfate (DSF), which reached valuesof 1.34 and 1.82 CIELAB units, respectively. However these values donot exceeded 2 CIELAB units, considered imperceptible to the hu-man eye (Wyszecki and Stiles, 1982; V€olz, 2001; Giacomucci et al.,2012). In all other cases, DE*abwas less than 1 CIELAB unit, definedas the visual color difference threshold or just noticeable difference(jnd) which constitutes the lowest limit of perception for an indi-vidual with normal color vision (Wyszecki and Stiles, 1982; V€olz,2001; Prieto et al., 2010a, 2011).
Wash and light fastness values with a brief description of theassessment of fastness are seen in Table 7. B. orellana extractcolorant itself, without the use of mordants (DWM), resulted inhigher or equivalent wash fastness properties (4e5) to the dyedfabrics with mordanting. Its light fastness (2e3) did not differnegatively from those of the most of samples. Light fastness resultswere only improved with pre-mordanting with tannic acid (DPT)and simultaneous mordanting with ferrous sulfate (DSF), whichhad a one point or two points higher light fastness than that of theB. orellana extract colorant without the use of mordants (DWM).
Toxicity of different combinations of B. orellana dye and mordating agents.
Data are the mean of 8 measurements, done at random points on three replicates (standard deviation between brackets).Undyed (U), Dyed using B. orellana extract colorant without the use of mordants (DWM), Pre-mordanting with tannic acid (DPT), Simultaneous mordanting with tannic acid(DST), Pre-mordanting with sodium citrate (DPC), Simultaneous mordanting with sodium citrate (DSC), Pre-mordanting with aluminum potassium sulfate (DPA), Simulta-neous mordanting with aluminum potassium sulfate (DSA), Pre-mordanting with ferrous sulfate (DPF), Simultaneous mordanting with ferrous sulfate (DSF).
Table 6Partial color differences (DL*, Da* and Db*) and total color difference (DE*ab) between the dyed fabrics.
DWM e U DPT e U DST e U DPC e U DSC e U DPA e U DSA e U DPF e U DSF e U
Undyed (U), Dyed using B. orellana extract colorant without the use of mordants (DWM), Pre-mordanting with tannic acid (DPT), Simultaneous mordanting with tannic acid(DST), Pre-mordanting with sodium citrate (DPC), Simultaneous mordanting with sodium citrate (DSC), Pre-mordanting with aluminum potassium sulfate (DPA), Simulta-neous mordanting with aluminum potassium sulfate (DSA), Pre-mordanting with ferrous sulfate (DPF), Simultaneous mordanting with ferrous sulfate (DSF).
M.J. Chan-Bacab et al. / Journal of Cleaner Production xxx (2014) 1e108
Considering these results, we may indicate that fastness propertieswere not significantly affected by the use of mordant and thereforethe use of the natural pigment without mordant is thoroughlyrecommended in this sense.
Fig. 5. Total color difference (DE*ab) between both sides for the dyed fabrics processed in this(DWM), Pre-mordanting with tannic acid (DPT), Simultaneous mordanting with tannic acsodium citrate (DSC), Pre-mordanting with aluminum potassium sulfate (DPA), Simultaneosulfate (DPF), Simultaneous mordanting with ferrous sulfate (DSF).
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4. Conclusion
During the last two decades, natural dyes have become aninteresting subject of study due to their better properties in
study. Undyed (U), Dyed using B. orellana extract colorant without the use of mordantsid (DST), Pre-mordanting with sodium citrate (DPC), Simultaneous mordanting withus mordanting with aluminum potassium sulfate (DSA), Pre-mordanting with ferrous
and dyeing potential of colorant-bearing plants of the Mayan area inx.doi.org/10.1016/j.jclepro.2014.12.004
Table 7Wash and light fastness values for the dyed fabrics.
DPA 3e4 Slightly noticeableloss in depth,Reasonable
1e2 Great loss in depth,Poor - very poor
DSF 2e3 Notable loss in depth,Passing
4 Slight loss indepth, Good
DPF 4e5 Very slight loss indepth, Very good
2e3 Notable loss indepth, Passing
The acronyms for the samples are defined in Tables 5 and 6.
M.J. Chan-Bacab et al. / Journal of Cleaner Production xxx (2014) 1e10 9
comparison to their synthetic counterparts. They are considered ashealthier for humans and their environment, some of them withantibacterial properties, and therefore are sometimes preferred intextile industry. In this study, thepreliminary surveyof Yucatanflorabased on a range of sources of information showed its resourcefulpotential to obtain natural dyes. From the 23 plants included in theinventory and ethnobotanical study, four were selected to yieldnatural dyes. Dyes from J. spicigera, B. glabra, and R. discolorwithoutmordant demonstrated to be adjectives, contrary to fabrics dyedwith B. orellana extract without mordanting, which showed anadherence to the fabric material. In all cases the yield of extractedmaterial was betterwith the traditional heatingmethod (decoction)than with from the microwave method. Moreover, 10% ethanolreplacing distilled water proved to be more efficient. The dye bathswithout mordant only present low toxicity, the J. spicigera and B.glabra dyes being the most toxic. The B. orellana dye was less toxic,although its toxicity is increased when mordants are used. Conse-quently, caution should be takenwhen stating that natural-deriveddyes are safe to the environment and to the manufacturer or enduser, asmany of them require the use ofmordants that shows a levelof toxicity. Regarding the color performances of the dyed fabrics, asalready stated only the B. orellana dye was adhered to the fabricwithout losingmuch dye during the rinse, for this reason this speciewas employed to dye cotton cloth (manta). In the fabrics dyed withB. orellana, mordanting influenced the depth of the shades, althoughit had no significant effect on color values. Fastness properties werenot significantly affected by the use of mordant. All dyed fabrics hadsimilar color, with hue angle values indicating yellowish, orange-yellowish color. A perceptibly different color was obtained be-tween the pre-mordanting and simultaneous mordanting dye pro-cesses, except in tannic acid-mordanted fabrics. Testing biologically-derived mordanting agents from plants (specific lipids) is in prog-ress to develop a more ecologically-friendly approach that can besustainable among rural craftwomen, providing addedvalue to theirbackyard plant products. Further researches are required to enhancethe study of properties of the fabric dyed, especially its antibacterialactivity.
Acknowledgments
This study was supported by a research grant from FOMIXGobierno de Campeche CONACYT “Extracci�on optimizada,
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caracterizaci�on química y potencial tint�oreo de pigmentos natu-rales para uso textil artesanal en Campeche” 2011-C03-172468. Dr.Patricia Sanmartín is supported by a postdoctoral contract withinthe framework of the 2011e2015 Galician Plan for Research,Innovation and Growth (Plan I2C) for the year 2012. Fruitful dis-cussion and guide from the local minister of industrial and com-mercial development (SEDICO) Lic. Enrique Ariel Escalante Arceo isappreciated. Also, wewish to thank Aude Etrillard for her help withthe editing of manuscript.
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