Biosorption Studies of Acid Green 3 Dye Martine Torres Department of BioResource Research Oregon State University Physical Water Scarcity Approaching Physical Water Scarcity Economic Water Scarcity Little/ No Water Scarcity Not Estimated Background • Textile industry uses 80-200 m3 of water per ton of product • Producing 1,650 m3 of wastewater per day • In 2008, global textile production was more than 66 million tons of fabric, consuming 6-9 trillion liters of water Adverse Effects From Dye Effluent • Negatively affect photosynthetic activity of aquatic life • Textile dyes discolor water, making it aesthetically unappealing • Health effects include allergic dermatitis, skin irritations and cancer Flow Chart of Textile Processing: Input/Raw Materials →→ →→ Processing Steps → →→→→→ Output Textile Fibers →→→→→→ Yarn Manufacturing →→→→→→ Yarn (Spinning Mill) ↓ ↓ Yarn→→→→→→→Fabric Manufacturing→→→→→Grey Fabrics (Weaving/Knitting Industry) ↓ ↓ Grey Fabrics→→→→→→Wet Processing →→→→→Finished Fabrics (Dyeing, Printing & Finishing Industry) ↓ ↓ Finished Fabrics→→→→ →Garment Manufacturing→→→→→ Garments (Garment Industry) Source: http://textilelearner.blogspot.com/2012/02/what-is-textile-basic-textiles-uses-of.html#ixzz1w17tFwQr Physical Water Scarcity Approaching Physical Water Scarcity Economic Water Scarcity Little/ No Water Scarcity Not Estimated Bangladesh •Garment industry contributes 80% of foreign exchange earnings •Industrial pollution accounts for 60% in Dhaka watershed •Groundwater supply drinking water for 80% of Dhaka population India •Textile industry employs 38 million people, largest source of industrial employment •Water scarcity is so severe in Tirupur, industries are forced to buy water •Discharged effluents are detectable in the food chain in Sanganer Textile Industry Is Not Sustainable Groundwater sources are going to be depleted Water costs will increase Textile production costs will increase Growing need for new technology Recycle wastewater Reduce pollution Current Technology •Current technologies to treat textile effluent include, reverse osmosis, oxidation, and activated carbon • These methods suffer from high energy demand, high cost, slow dye removal process and hazardous by products Torres 2012 Dead Biomass • Not affected by toxic waste, does not require continuous nutrient supply • Can be recycled and accumulates contaminants better than living cells • Examples include banana peels, coconut husks, charcoal and algae Focus of Our Study •Red macro-algae, Palmaria mollis •Brown macro-algae, Fucus vesiculosus •Biochar, Red Alder char Algae Palmaria mollis Fucus vesiculosus Biochar Red Alder Char Acid Green 3 (AG3) as Model Dye • Acid dyes are commonly used in the textile industry • Most difficult type of dye to treat • Anionic triphenylmethane dye main offenders of pollution • Animal carcinogen and promotes tumor growth in fish Major Binding Groups for Biosorption Binding Group Hydroxyl Structural Formula -OH Carboxyl -C=O I OH O II -S=O II O -NH2 Sulfonate Amine Alginic Acid Agar Collection and Pretreatment of Algae • P. mollis and F. vesiculosus were collected at the Hatfield Marine Science Center • Algae was treated with distilled water and 0.1M HCl • Algae was dried in an oven and ground to less than 2mm size using a knife mill Vocabulary • Biosorption: The property of biomass to bind and concentrate selected ions or other molecules from aqueous solutions Hypothesis • Algae and biochar can be used as an effective adsorbent for AG3 dye Objectives • Determine the optimum pH, temperature and salinity conditions for maximum dye adsorption • Conduct batch experiments to determine dye adsorption potential Torres 2012 Palmaria mollis • Initial batch experiments conducted were to determine optimum pH for adsorption – pH influences functional groups on algae and the dye solution chemistry • Palmaria mollis will adsorb AG3 dye better in an acidic environment (pH2-3) Methods: P. mollis Experiment 1: Determine Optimum pH Condition pH: 2-7 30°C 1g/L dye in 150mL dye solution 0.5g P. mollis Duration: 27 hours *Only graphed pH 2, 3, 6 and 7 Results: Palmaria mollis Effect of pH on Dye Adsorption Rate by P. mollis pH2 Dye Adsorbed by Algae (%) 60 pH3 50 40 30 20 10 0 0 15 30 45 60 90 150 210 330 Time (min) 450 570 1440 1500 1560 1620 Results: Palmaria mollis Dye Adsorbed by Algae (%) Effect of pH on Dye Adsorption Rate by P. mollis pH6 10 pH7 8 6 4 2 0 0 15 30 45 60 90 150 210 330 450 570 1440 1500 1560 1620 Time (min) Discussion • P. mollis effectively adsorbs AG3 dye at pH2 (52.8%) and pH3 (42%) compared to pH 4-7 (>10%) • Adsorption rate decreases with increasing pH • As pH increases, the number of negatively charged sites on algae increases • P-value comparing adsorption rate of pH2 and pH3 was (0.14), so subsequent experiments use pH3 Fucus vesiculosus • Switched focus to brown macro-algae • Two experiments were conducted: – Determine optimum salinity condition – Determine optimum temperature condition Methods: F. vesiculosis Experiment 1: Determine Optimum Salinity Condition Dye Conc.: 2.5g/L 5g/L 10g/L Media: Salt water Distilled water Salt water pH: 3 30°C 20g P. mollis Duration: 8 hours Distilled Salt water water Distilled water Results: Salinity Experiment (10g/L) Effect of Salinity on Dye Adsorption Rate byF. Dye Adsorbed (Dist. Water) Dye Adsorbed (Salt Water) P-value: 0.0125 70% Dye Adsorbed by ALgae (%) 60% 50% 40% 30% 20% 10% 0% 0 30 60 90 Time (min) 120 240 480 Percent Dye Remaining for 10g/L in Salt Water With a Dilution Factor of 100 100% 68.3% 62.5% 60.1% 58.5% 40.1% 39.8% Results: Salinity Experiment (5g/L) Effect of Salinity on Dye Adsoprtion Rate byF. Dye Adsorbed (Dist. Water) Dye Adsorbed (Salt Water) Dye Adsorbed by Algae(%) 70% P-value: 0.0168 60% 50% 40% 30% 20% 10% 0% 0 30 60 90 Time (min) 120 240 480 Results: Salinity Experiment (2.5g/L) Effect of Salinity on Dye Adsorption Rate byF. Dye Adsorbed (Dist. Water) 70% Dye Adsorbed (Salt Water) Dye Adsorbed by Algae (%) 60% 50% 40% 30% 20% 10% 0% 0 30 60 90 Time (min) Torres 2012 120 240 480 Methods: F. vesiculosis Experiment 2: Determine Optimum Temperature Condition Temperature: 30°C 35°C 40°C Dye Conc.: Type of Media: 2.5g/L 10g/L Salt water 2.5g/L 10g/L Salt water pH: 3 20g P. mollis Duration: 8 hours 2.5g/L 10g/L Salt water Results: Temperature Experiment Effect of Temperature on Final Dye Concentration 5 2.5g/L Initial Dye Concentration 10g/L Initial Dye Concentration Final Dye Concentration (g/L) 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 30 35 Temperature (°C) 40 Discussion • Temperature (30-40°C) does not significantly affect dye uptake by the algae • Dye uptake appears to be associated with salinity of the solution • Total amount of dye adsorbed by algae was independent of initial dye conc. (56-57% for distilled water, 44-60% for salt water) Biochar • Studies indicate that chars formed at low temperatures (300-400°C) have lower surface area than chars at high temperatures (500-700°C) • Red Alder at 600°C will adsorb AG3 dye better than Red Alder at 300°C • Determine optimum pH for adsorption Collection and Pretreatment of Biochar • Donated from Mr. John Miedema in Philomath, Oregon • One batch of high and low temperature Red Alder Char was washed with distilled water and 0.1M HCl • Treated Char was then dried in an oven before use Methods Untreated Char 600°C -pH: 3, 5, 7 -Media: 2.5g/L Dye in Salt Water -Samples taken at 4 hrs and 24 hrs Treated Char 600°C -pH: 3, 5, 7 -Media: 2.5g/L Dye in Salt Water -Samples taken at 4 hrs and 24 hrs Untreated Char 300°C -pH: 3, 5, 7 -Media: 2.5g/L Dye in Salt Water -Samples taken at 4 hrs and 24 hrs Treated Char 300°C -pH: 3, 5, 7 -Media: 2.5g/L Dye in Salt Water -Samples taken at 4 hrs and 24 hrs Results High Temp Char Untreated pH7 pH5 pH3 35 AG3 Dye Uptake (%) 30 25 20 15 10 5 0 240 0 1440 240 Time (min) Results High Temp Char Treated with pH7 pH5 pH3 AG3 Dye Uptake (%) 12 10 8 6 4 2 0 240 0 1440 240 Time (min) Discussion • High temperature Red Alder char adsorbs more AG3 dye than low temperature • No significant pH difference for Red Alder char to adsorb AG3 dye • Treated char adsorbed less dye (11%) than untreated char (32%) • Red Alder char adsorbed less AG3 dye than P. mollis and F. vesiculosus Future Work Effluent water (high volume) Wash water (Dyes concentrated) Operating Regeneration Operating Regeneration Clean wash water (lower volume) Clean effluent water (No dyes) Acknowledgements • Oregon State University Subsurface Biosphere Initiative (SBI) • United States Department of Agriculture (USDA) • Gail Hanson and John Meidema for providing the biomass used in the experiments • Dr. Murthy for supporting my research • Dr. Kleber and Dr. Stubblefield • Wanda and Dr. Field • My friends and roommate