Potency of Avicennia marina (Forssk.) vierh and Bruguiera gymnorrhiza L (Lam) mangrove extracts as natural batik dye

Mangroves have many environmental, ecological, economic, health and industrial benefits. One of the applications of mangroves in industry is as a natural dye for textile materials. The aim of the study was to determine the potential application of mangrove extract as a natural dye for batik, to determine the pigment content of the test sample, and to test the fastness of natural color made from leaves and bark of Avicennia marina and Bruguier gymnorrhiza, at plant ages of 5 and 10 years. Sample collection was done by picking leaves and collecting the bark of Avicennia marina and Bruguier gymnorrhiza. Color fastness to detergent washing test, wet and dry rubbing test were carried out with a crockmeter, using the Staining Scale and Gray Scale standards. UV Vis Spectrophotometry Analysis was employed to determine the pigment content. The results showed that leaf and bark extracts of Avicennia marina and Bruguiera gymnorrhiza mangroves have the potential to be applied as natural dyes for batik. Mangrove natural dyes showed scores of 3, 4, and 5 on the fastness tests of dry rubbing, wet rubbing and detergent washing. These findings indicate that the natural dyes in this study have met the Indonesian National Standard, which requires a minimum score of 3.


Introduction
Mangroves provide many benefits such as an ecological perspective, mangroves provide a place to live, spawn, and find food for animals that live in the ecosystem [1,2].Mangroves also protect the surrounding environment by becoming shielding from waves [3] and preventing coastal abrasion [4].The application of mangroves continuously become a significant development subject, among which the resulting products are flour, chips, syrup, treatment for hematuria (occurrence of blood or red blood cells in the urine), to natural dyes in the industrial sector [5].
Natural dyes are dyes obtained from nature by extracting or boiling plant parts such as leaves, fruit, flowers, bark, stems and roots.Mangrove has many chemical contents such as tannin [6], amino acids [7], and antimicrobial potency [8].Natural dyes are considered to be more environmentally friendly and non-toxic to humans, which gives them a special appeal.Mangrove have been known to be processed into natural dyes for batik production.Parts of mangrove trees such as roots, leaves, propagules, fruit, bark, and roots can be used in the manufacture of natural dyes [9].
2 Several mangrove species have been successfully applied as natural dyes for batik.The study on 6 species of mangrove, Rhizopora sp., Soneratia alba, Ceriops decandra, Lumiceara sp., and Avicennia sp.Yielded almost similar hue, ranging from light brown to dark brown [10].Natural dye from leaves and bark of Rhizopora sp. is applied to batik using fixation method.Fixation process is achieved by using an agent, compounds that bind the pigments to the batik fabric.The compounds used in this process are alum, lime, and ferrous sulfate, which creates variation in color.Alum commonly produces medium brightness, whereas lime creates brighter colors.Fixation with ferrous sulfate usually results in darker shades [10].It is also found that the application of different parts of mangrove as a material for a natural dye results in various coloration, which is further enriched by using alum, lime and ferrous as fixation agents [11].Based on the information, it is believed that the colors produced from mangrovebased natural dye would also be affected by plant age.The species B. gymnorrhiza and A. marina are abundant in the area of Mangkang, Tugu district, Semarang city, Indonesia.This study aims to determine the potential application of mangrove extract as a natural dye for batik, to test the color fastness the dye made of leaves and bark of Avicennia marina and Bruguier gymnorrhiza mangrove leaves at 5 and 10 years of plant age, and to determine the pigment content of the test samples.Samples were collected by picking leaves and bark of Avicennia marina and Bruguier gymnorrhiza mangrove trees.

Study area
Samples of leaves and bark of A. marina and B. gymnorrhiza with plant ages of 5 and 10 years from the mangrove area of Mangkang, Tugu District, Semarang were used as material for this study.Mangrove plant age was determined by recording the year of planting, which were in 2010 and 2015 [12].The sample collection was carried out in March 2020 in the Mangkang Mangrove Area, Semarang, Central Java.The samples consisted of bark and leaves of A. marina and B. gymnorrhiza.Leaf samples were taken from leaves located on the old twig (base), a total of 100 grams in each sample.Bark samples were obtained by peeling the bark of A. marina and B. gymnorrhiza with a width of ± 10 cm and a weight of 100 gr for each sample [13].Leaves and bark samples were cut into pieces of less than 2 cm [11] and dried.

Natural dye extraction
Extraction of natural dyes from the leaves and bark of the tested mangroves was carried out by boiling.Each sample weighing 100 grams was boiled in 1000 mL of clean water.Boiling was carried out at 90 0 C to concentrate the pigment, then stirred regularly for 1 h [10].Batik Painting and Dyeing and dye binding as well as nglorod (The process of removing wax from painted Batik fabric) was carried out according to [11].Testing the quality of dyeing on the fabric is carried out after the batik fabric had gone through the dyeing and painting process, to determine the quality of the results.The color fastness test, detergent washing test, and dry rubbing test were performed using a crockmeter and Staining Scale and Grey Scale standards.Detergent solution at ratio 5 g -1 L of aquadest was used in the detergent washing test.AATCC-standard detergent was used, with a maximum content of non-hydrate detergent of 85%.To determine the pigment contents of the sample mangroves, a UV Vis Spectrophotometry analysis was performed in accordance to Pringgenies et al. [11].Pharo 300 spectrophotometer was used with 300-800 mm wavelength setting.

Data analysis
The tests in this study yielded Staining Scale score from wet and dry rubbing, Grey Scale score from detergent washing, and UV Vis spectrophotometry analysis results in Evaluation evaluation Laboratory of Islamic University of Indonesia.

Results and discussion
Extraction of leaves and bark of mangrove A. marina and B. gymnorrhiza of all plant ages produced filtrate in the form of light brown, dark brown, reddish brown, and yellowish brown solutions.The highest solution yield, as much as 0.5 l, was obtained from the extraction of 5 years old B. gymnorrhiza.UV Vis spectrophotometry did not find peaks at the wavelength setting of 300-800 nm in A. marina and B. gymnorrhiza of all plant ages.Batik fabric fixated with Alum (AI2(SO4)2), lime (CaCO3), and ferrous sulfate (FeSO4) tested in color fastness to dry and wet rubbing yielded scores of 3, 4, and 5 accross the tests.Table 1 Color fastness to fabric rubbing and detergent washing test results.The score variations for dry rubbing test were 3-4 (sufficient), 4 and 4-5 (good), and 5 (very good).Whereas the wet rubbing test yielded variations of 2-3 (poor), 3 (sufficient), 3-4 (sufficient to good), and 4 to 4-5 (good).Color fastness test to washing test of batik fabric of all fixation agents resuled in variations of Grey Scale score in the categories of poor (2), Sufficient (3), And good (4).The results of color fastness to detergent washing test is presented in Table 1.The Grey Scale score yielded on batik fabrics of all fixation agents ranged from 2-3 (Poor), 3 (sufficient), 3-4 (sufficient to good), to 4 and 4-5 (Good).

Dyeing using A. marina and B. gymnorrhiza natural dye
Dyeing with natural dyes from the leaves and bark of A. marina at the age of 5 and 10 years showed that the yield from the leaves was of better quality than the dye produced from the bark.The results using dye from A. marina leaves of 5 years plant age, fixated using lime produced the most vivid hue compared to the the one of 10 years plant age (Figure1a and Figure 1b).Dye made of B. gymnorrhiza plant of 10 years yielded better brightness and hue compared to the results using dye from A. marina extracts.This dye also resulted in darker colors when fixated with lime and ferrous sulfate, compared to the results from alum fixation (Figure .2a, (Figure 2b and Figure 2c).Of all the natural dye made of B. gymnorrhiza extracts, the dye made of bark showed the most vivid colors.Extraction of leaf and stem bark samples produced dyes with variation in shades and brightness of brown.Mangrove bark is rich in tannins, ranging from 15-36%, and the resulting brown color comes from this compound.Mangrove bark produces a thick dye solution [14].Tannins are polyphenolic compounds that have high molecular weight and hydroxyl groups, in addition to other groups (such as carboxyl), so that they can form complexes with proteins and other macromolecules under certain environmental conditions.Tannins have a molecular mass such as condensed tannins (1,000 to 20,000 Da) and hydrolysable tannins (500 to 3,000 Da) [15].
It was also found that the extract solution contained the most extracts in 10-year-old mangroves, which all samples yielded more than 0.4 l.The total tannin content in mangrove plants estimated between 0.59-158.96kg/trees (bark and stem) and 0.20-91.65 kg/trees (leaves) [16].The research, which was conducted in Rembang and Pemalang, concluded that the older the mangrove plant, the more tannin it contained.B. gymnorrhiza bark extract from 5 and 10-years-old plants produced a more intense color than its leaf extract.On the other hand, extract of leaves from 5 and 10-year-old A. marina produced more intense color than its bark extract.According to Dewi et al. [13], extraction of natural dyes in mangrove leaf litter Rhizophora mucronata produced a more concentrated color than that produced in the extraction of its bark and propagules.The variation in color is thought to be caused by the tannin content in the mangrove, which is correlated to the plant age.It was found that the older the plant, the more intense the color of its extract.
The results of the spectrophotometric analysis on the leaves and bark of mangroves did not show peaks at a 300-800 nm of wavelength.This finding indicated that no pigment content was detected on all test samples.Since the pigment in the samples were diluted in water solution, due its polar nature and water being an effective solvent, the test failed to detect any trace of pigment.Tannin compounds in the natural pigment of Rhizopora mucronata [11].Moreover, found that the red pigment in Rhizopora mucronata was an indication of flavonoids and quinone contents and that the greenish black color showed tannin content in the species [10].
Color fastness can be broken down into fastness to sunlight exposure, to washing, and to rubbing.This study performed color fastness test to dry and wet rubbing as well as fastness to detergent washing.All of the tests in this study concluded that the colors resulted from mangrove natural dye is permanent.The fixation treatment using alum (AI2(SO4)2), lime (CaCO3), and ferrous sulfate (FeSO4) allowed the fabric to retain its colors during the tests.Fixation agents helps the fabric to absorb the dye and enhance color retention by molecular bonding process.Dyeing auxiliaries play an important role in the determination of the final dyeing quality dan can assist in achieving outstanding dyeing performance [17].The Staining and Gray Scales obtained from color fasteness to dry rubbing test on fabric fixated with alum (AI2(SO4)2) were between 3 and 5.This finding showed that the product of this study has met Indonesian National Standard for textile color fastness, which is 3.
Likewise, the color fastness to detergent produced varying score with different dye extract and fixation agents.However, most mangrove dye extract in this studies passed Indonesian National Standard with a minimum score of 3. One exception to this case was found in dye made of 5-year-old A. marina, which showed a score 2-3 in all three iterations of the tests.This finding is thought to be caused by the lack of maturity of the pigments contained in 5-year-old A. marina plants, because of all samples fixed using alum yielded scores ranging from 3 to 3-4.In addition, alum is naturally easy to dissolve in and purify water.It is believed that the dye fixated by alum loses its fastness when it reacts with water and a detergent solution.
The batik dye with the best value was found in the cloth fixed with lime (CaCO3), which was between 3-4 (good) to 5 (very good).Therefore, this study found that the fixation of mangrove natural dye using lime is more effective than those using alum and ferrous sulfate.Fixation by ferrous sulfate in color fastness tests to rubbing (dry and wet) and detergent washing resulted in scores ranging from 3 to 4. All samples using a ferrous sulfate fixator on the dry rubbing test showed a score of 3-4 (sufficiently good).In the wet rubbing test, all samples scored between 3 (sufficient) and 3-4 (sufficiently good) varying in the first, second and third tests.Meanwhile, in the detergent washing test yielded a value of 4 (good).Staining Scale scores on the dry and wet rubbing tests showed value variations, which correlated to the fixation agent used [18].
Natural dyes made from the leaves and bark of A. marina and B. gymnorrhiza with fixation of alum (AI2(SO4)2), lime (CaCO3), and ferrous sulfate (FeSO4) produced different colors.Cotton is made of natural fiber, making it the ideal material for batik fabrication.The wax used in batik production can be retained well by the fabric, resulting in precise and fine patterns.The dying of batik involves the process of swelling, which acts to enlarge the pores in the fabric and ease the absorption of the dye and dye solution.The dye absorbed by the fabric fibers undergoes an adsorption process and is bound by a reactive group on the cellulose fiber in the form of a hydroxyl group (OH) and forms hydrogen bonds.The fabric is then dried in the open air, without being exposed to the sun directly.After dyeing, comes the fixation process.Fixation is one of the steps in the batik production process which functions to retain and enhance the resulting color.Fixation in principle is to condition the dye that has been absorbed for a certain time so that a reaction occurs between the fabric, the dye, and the fixation agent used [13].
Alum (AI2(SO4)2), lime (CaCO3), and ferrous sulfate (FeSO4) are selected as fixation agents because they are naturally occurring solution in the immediate environment, easy to obtain and can be used with minimal impact to the environment.All of these compounds have been used in many iteration of studies on textile fixation agents.Different body parts of mangrove and fixation process will result in different shades of color [19].Fixation using ferrous sulfate, lime and alum resulted in shades of gray, pink or squash, and tangerine respectively.However, this paper found different resulting colors from extraction and fixation process.This is perhaps due to the different species being studied which this report studies, namely 5 to 10-year-old A. marina and B. gymnorrhiza.The comparison of color variation resulted from differences in fixator used can be observed visually.Fixation process is utilized in the production to enhance the colors natural dye and enhance its retention in the fabric [20,21].In this study, alum-fixated products were painted with shrimp pattern, lime-fixated fabric were decorated with floral pattern, and ferrous sulfate-fixated fabric were embellished with clam shell pattern.The application of pattern can add artistic value.Alum produced brighter colors, lime produced less vivid/washed-out like effects, and ferrous sulfate provided darker hues.
Extracts from 5-year-old A. marina leaves produced bright brown with alum fixation, off brown with lime fixation, and dark brown with ferrous sulfate fixation.Extracts from 10-year-old A. marina leaves produced yellowish-brown with alum fixation, off brown with lime fixation, and ash brown with ferrous sulfate fixation.Extracts from 5-year-old A. marina bark produced light brown with alum fixation, off brown with lime fixation, and dark peat with ferrous sulfate fixation.Extracts from 10-year-old A. marina bark produced light brown with alum fixation, off brown with lime fixation, and ash brown with ferrous sulfate fixation.Lime fixation produced consistent color regardless of what extract were used.Alum fixation gave the brightest and clearest pattern line on the fabric.Ferrous sulfate fixation on A. marina extract with 10 years old of plant age produced hues of brown which were darker and deeper.
Extracts from 5-year-old B. gymnorrhiza leaves produced yellowish brown with alum fixation, off brown with lime fixation, and ash brown with ferrous sulfate fixation.Dyeing with 10-year-old B. gymnorrhiza leaves extract produced yellowish brown using alum fixation, off brown using lime fixation, and light brown using ferrous sulfate fixation.Dyeing with 5-year-old B. gymnorrhiza bark extract produced off brown using alum fixation, bright brown using lime fixation, and dark peat using ferrous sulfate fixation.Dyeing with 10-year-old B. gymnorrhiza bark extract produced bright brown using alum fixation, light brown using lime fixation, and dark peat using ferrous sulfate fixation.Application of B. gymnorrhiza extract as the base for natural dye produced variation in hues, enhanced with different usage of fixation agents.Extract made of 5-year-old B. gymnorrhiza with lime and alum fixation produced more intense colors.
This finding supports the one in a study by Lin et al. [22] which reported that fixation agents enhanced the color retention on textile fabrics.Lime fixation can enhance the bond in color molecules.Lime, in its natural state, occurs in irregular clumps, and white or grayish white in color.The use of lime in fixation solution is the addition of chloride salts or oxalates from organic bases, which can enhance the affinity of the dye to the cellulose/fabric/cotton. Alum fixation is characterized by its color retention to fabric, which may not be as strong in one material compared to the other.This may be caused by the release of dye molecules during dipping/fixation process.Ferrous sulfate as fixation agent produces change in hue after the fabric has gone through the initial dyeing/dipping process.This fixation agent is found to produce darker colors.Ferrous sulfate contains Fe + ions which can form metal complex useful in enhancing the color fastness of a textile material.A study by Sarwono et al. [23] found that alum fixation produced light brown color.It also mentioned that lime fixation produced brown, similar to the color displayed before fixation, and that ferrous sulfate fixation produced dark peat.However, this research only applied fruits of Rhizophora mucronata as the base for its natural dye extract.The other study showed that the mangrove symbiont bacteria had antibacterial potential [24].

Conclusions
Mangrove natural dyes are plant-based pigments and friendly to the environment.Avicennia marina and Bruguiera gymnorrhiza are species commonly found in the Mangkang Mangrove Area, Tugu District, Semarang with varying plant age.This study concluded that the mangrove extracts of A. marina and B. gymnorrhiza with plant ages of 5 and 10 years had the potential to be applied as natural dyes for batik production.The color fastness score of mangrove dyes from leaf and stem bark samples of both species obtained scores ranging from 3 and 5, which means that the dye products tested were suitable for use in batik production because they have met the Indonesian National Standard for garment.

Figure 1 .
Figure 1.Dyeing results using natural dye of A. marina, fixated with lime, plant age of 5 years (a) and 10 years (b).