Potential use of Eichhornia crassipes for treatment of highly toxic sulphur black effluent

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The potential of Eichhornia crassipes (water hyacinth) was explored for treatment of highly contaminated wastewater collected from a local garment processing industry at Mahestala Budge budge. The effluent contained sulphur black dye (C.I. Sulphur black1) which is one of the most important black dyes in the world and widely used for cellulosic fibers. In the traditional sulfur dyeing process, sodium sulphide is used as a reducing agent in the dyebath and a highly toxic effluent is generated. As a result, the entire area is under extreme environmental pollution. In the present study the feasibility of a biosorbent prepared from the roots of E. crassipes was determined for the treatment of sulphur black effluent. E. crassipes is a fast growing perennial aquatic weed and can grow in severe polluted waters. The roots of E. crassipes was collected and washed thoroughly in distilled water to remove the impurities The dried biomass was powdered and sieved to select particle sizes of about 100m to use as biosorbent in the batch studies. The raw effluent and the treated samples were characterized in terms of the dye removal, turbidity, TSS, COD, pH, Conductivity, TDS etc.

Dye removal was maximum(99.8%) at initial pH of 4 and 1g/l was found as an optimum dose of the adsorbent. The process was found highly efficient with removal of turbidity, TSS and COD as 99.8% and 69% respectively.

Biosphere is constantly under various threats from continuing environmental pollution. Man made activities on water and air by domestic, industrial, agriculture, burning of fuels have negative influence on abiotic and biotic components of environment. Different approaches have been implemented to tackle man-made hazards. Among the industries textile industry plays an important role in the economy of the country. 70% of pollution from textile industry is caused from chemical processes of textile industry. Textile industry involves wide range of raw materials, machineries and processes to engineer the required shape and properties of the final product. Waste stream generated in this industry is essentially based on water-based effluent generated in the various activities of wet processing of textiles. The main cause of generation of this effluent is the use of huge volume of

water either in the actual chemical processing or during re-processing in preparatory, dyeing, printing and finishing. Different types of dyes are used for colouring the textiles like azo, anthraquinone, acridine,etc. Sulphur dyes are a most common class of dyes having the best light fastness and low price among the dyes applied to natural fibres. They are cheap, generally have good wash-fastness and are easy to apply. The dyes are absorbed by cotton from a bath containing sodium sulfide or sodium hydrosulfite and are made insoluble within the fiber by oxidation [1]. During this process these dyes form complex larger molecules which is the basis of their good washfastness. The deep indigo blues of denim blue jeans are a product of sulfur dyes. The alkali metal thiolate is usually necessary as a reducing agent in the dyeing process of sulphur dyes, bring about serious environment pollution. And, the fiber dyed by this water-insoluble dye presents poor wet rub fastness. Sulfur dyes are water insoluble. They have to be treated with a reducing agent and an alkali at temperature of around 80 degrees Celsius where the dye breaks into small particles which then becomes water soluble and hence can be absorbed by the fabric [2]. Hence the effluents have to be treated before discharge to prevent pollution. Different methods have been used for treatment of dye effluent like oxidation, adsorbtion [3], photodetoxification [4], biological treatment [5], etc. Each of the processes has its own merits and limitations. In the present study ceramic membrane based microfiltration and an adsorbent

prepared from water hyacinth roots was used for treatment of sulphur black effluent. Low cost ceramic membranes developed by Central glass & Ceramic Research Institute [6] is explored for treating highly polluted sulphur black effluent. This membrane was used for treatment of reactive dye effluent in combination with coagulants based pre-treatment process [7]. Experimental Dyes Sulphur dye effluent was collected from Mahestala,Budge budge. Sulphur Black 1, in all its forms (C.I. Sulphur Black 1, C.I. Solubilised Sulphur Black 1 and C.I. Leuco Sulphur Black 1) is mostly used for dyeing process worldwide.

Fig-1 Structure of sulphur Black 1

In the present study raw sulphur black effluent was collected and initial characterisation i.e pH, TSS, turbidity, COD, conductivity, TDS, colour etc. of effluent was done which is shown in Table-1. Turbidity was measured in 2100AN IS Turbidimeter, Hach, pH, TDS, conductivity was measured in multiparameter made of Hach, COD was measured in COD digestor by Spectralab 2015M. Absorbtion of samples were measured in UV-VIS spectrophotometer by Varian.

Table-1: Characterization of raw black sulphur effluent

pH Conduct ivity (ms/cm) 49.5 TDS (mg/l) 31,100 Turbidi ty (NTU) 5505 Dye concentrati on (mg/l) 612.5 COD (mg/l) 3915 TSS (mg/l) 5568

obtained from the batch study was used for membrane study. Microfiltration Membrane study of effluent using selected dose of adsorbent was conducted. Microporous low cost ceramic support element made of alumina and clay was fitted in crossflow microflitration unit. In the study uncoated porous support tube in tubular multichannel configuration was used (od 35 mm; channel diameter 4 mm, length 200 mm, apparent porosity 36%, filtration area 0.0501 m2). Experiments were conducted using feed volume of 6l and at varying transmembrane pressure of 4-1.2 kg/cm2 to observe the effect of pressure on permeate flow and characteristics . Effect of time was observed by operating the experiment at a constant pressure of 1 TMP for 2 hours. The permeate flux was measured at specific intervals and characterization of permeate samples were done for pH, turbidity, conductivity, dye concentration. The ceramic element and unit was thoroughly cleaned with deionised water before each run and after the experiment was over. The tube was cleaned with dilute nitric acid. Results and Discussion Determination of optimum pH The effect of variation of pH on dye removal of the effluent sample was determined (Fig-2). The pH range for the study varied in the range of 4-12.

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Adsorbent Eichhornia crassipes (Water hyacinth) are free floating water plant and is also one of the most notorious weeds worldwide. It can vary in size from a few inches tall to over three feet. This plant has blue-green leaves, thick stalks and a showy purple or lavender flower. It thrives in tropical regions and in waters that are high in nutrients. Water hyacinth is also known for its ability to grow in severe polluted waters. Roots of hyacinth are known to acculmulate heavy metals like Zn, Cd, Ni, Cu [8]. In the present study water hyacinth was collected from nearby locality pond. Roots were washed thoroughly with distilled water to free from any impurities and dried. Adsorbent had the following characteristics: bulk density - 133 kg/m3, moisture - 9.6%, ash - 44%, particle size - 0.038mm. Adsorbent prepared from the roots were further study for its removal efficiency of sulphur black dye. Batch study Batch scale study was conducted on sulphur black effluent at different pH (4-12) and different dose (0.5 -2g/l) of adsorbent. The optimum dose and pH

Maximum dye removal of about 84% and COD removal of 68.1% was observed at pH 4. Dye removal at pH 12 was least i.e 61% and for pH 8 & 6 dye removal was about 66-78%. Turbidity and TSS removal was 59% and 64% respectively, in the batch study.
140 120 100

Microfiltration study Membrane filtration study was conducted using adsorbent dose of 1g/l. The pH of the feed was adjusted at 4. After 15 mins dye removal was 97.7% which increased to 98.5% after 120 minutes. COD, TSS removal were 66% and 94% respectively after 15 mins of membrane filtration. It was increased to 79% and 96% respectively after 120 minutes. The permeate flux was 60 LMH initially which reduced to 43 LMH after 120 mins. The reduction in flux value was due to the concentration polarization across the membrane surface. Turbidity was reduced below 1NTU (Fig 4-5).
120 110 100 90 COD TSS D ye c o n c e n tra tio n

COD Dye concentration TSS Turbidity

% Removal

80 60 40 20 4 6 8 10 12

pH

Fig-2: Effect of pH in batch study of sulphur black effluent (dose 1g/l).

% Removal

Determination of optimum dose The effect of varying dose of adsorbent was determined (Fig-3). The dose was varied from 0.5-2g/l. It was observed that maximum dye removal of 84% was obtained at dose 1g/l. COD reduction was maximum compared to other three doses (0.5, 1.5, 2g/l). Hence for membrane study 1g/l dose of adsorbent was selected.
140 120 100 COD Dye concentration TSS Turbidity

80 70 60 50

20

40

60

80

100

120

T im e (m in )

Fig-4: Effect of time variation in microfiltration study of sulphur black effluent at 1 TMP (adsorbent dose 1g/l, pH-4).
100 80 F lux T urbidity

Flux (LMH), Turbidity (NTU)

60 40 20 0 -20

%Removal

80 60 40 20 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

20

40

60

80

100

120

Adsorbent dose (g/l)

Tim e (m in )

Fig-3: Effect of adsorbent dose in batch study of sulphur black effluent (pH-4).

Fig-5: Variation of turbidity and permeate flux with time (adsorbent dose 1g/l, pH-4).

The effect of varying transmembrane pressure (0.4-1.2 kg/cm2) was observed. As expected the flux rate increased with increasing pressure due to increase in driving force. Maximum flux of about 65LMH was observed at 1.2 kg/cm2 TMP (Fig 6-7). Turbidity also decreased with increasing TMP. The removal of turbidity, COD, TSS, dye concentration etc. was enhanced in the combination process of adsorption followed by microfiltration.
12 0 11 0 10 0 90 COD TSS D ye co nc en tration

Conclusion The experiments showed that effective treatment of highly polluting sulphur black effluent is possible using ceramic membrane based process in combination with bioadsorbent. The bioadsorbent was prepared from easily grown and abundantly found water hyacinth roots. Dye removal was 99%, COD, TSS removal was 79% and 96.5 respectively. The permeate flux was about 43LMH. Turbidity of the permeate samples were <1 NTU.

% Removal

References [1] Wang,W. Li., Zhang,S. F., Yang J. Z., State Key Laboratory of Fine Chemicals, Study on Dyeing Performance of Cationic Water-soluble Sulphur Black on Silk, Dalian University of Technology. [2] Mondal, S., Methods of Dye Removal from Dye House Effluent: An Overview, Environmental engineering science, 2008, pp. 383-396, [3] Laasri, L., Elamrani, M.k., Cherkaoui, O., Removal of two cationic dyes from a textile effluent by filtration-adsorption on wood saw dust, Environmental Science and Pollution Research, 14 (2007) 237-240. [4] Emanuel,N.,Kumar,G., Photo detoxification of solubilized vat dye effluent using different pH ranges, Springerlink,2008 .

80 70 60 50 0.4 0 .6 0 .8 1 .0
2

1.2

T ra ns m e m b ra ne p re s sue (kg /cm )

Fig-6: Effect of transmembrane pressure in microfiltration study of sulphur black effluent (adsorbent dose 1g/l, pH-4).

100 80 F lux T urbidity

Flux (LMH), Turbidity (NTU)

60 40 20 0

-20 0.4 0.6 0.8 1.0

2

1.2

Transm em brane p ressure (kg/cm )

Fig-7: Variation of turbidity and permeate flux at different transmembrane pressure (adsorbent dose 1g/l, pH-4).

[5] Erkurt, E.A., Unyayar, A., Kumbur, H., Decolorization of synthetic dyes by white rot fungi, involving laccase enzyme in the process, Elsevier, Process Biochemistry, vol-42, October 2007, 1429-1435. [6] Bandyopadhyay,S., Kundu, D., Roy, S.N., Ghosh, B.P., Maiti, H.S.,Process for preparing water having an arsenic level of less than 10 PPB, United States Patent [7] Bandyopadhyay, S., Ghosh, S., Sahoo, G.C., Maiti, H.S., International Workshop on R&D Frontiers in water and wastewater Management, Treatment of a Textile Dye-Bath Effluent Using Coagulant Followed by Microfiltration. [8] Cordes, K.B., Mehra, A., Farago, M.E., and Banerjee, D.K, 2000, Uptake of Cd, Cu, Ni and Zn by the Water Hyacinth, Eichhornia crassipes
(Mart.) Solms from pulverised fuel ash (PFA) leachates and slurries,

Springerlink .