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

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

Flow Chart of Textile Processing:

Economic Water

Scarcity Little/ No Water

Scarcity Not Estimated

Physical Water

Scarcity Approaching Physical Water

Scarcity

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

Torres 2012

•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

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

•Red macro-algae, Palmaria mollis

•Brown macro-algae, Fucus vesiculosus

•Biochar, Red Alder char

Focus of Our Study

Palmaria mollis

Fucus vesiculosus

Algae

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

Binding Group

Structural Formula

Hydroxyl -OH

Carboxyl -C=O

I

OH

Sulfonate O

II

-S=O

II

O

Amine -NH2

Alginic Acid

Major Binding Groups for Biosorption

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

• Biosorption: The property of biomass to bind

and concentrate selected ions or other

molecules from aqueous solutions

Vocabulary

Hypothesis

• Algae and biochar can be used as an effective adsorbent for AG3 dye

Torres 2012

Objectives • Determine the

optimum pH, temperature and salinity conditions for maximum dye adsorption

• Conduct batch experiments to determine dye adsorption potential

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

0

10

20

30

40

50

60

0 15 30 45 60 90 150 210 330 450 570 1440 1500 1560 1620

Time (min)

Dye

Ad

sorb

ed

by

Alg

ae (

%)

pH2 pH3

Effect of pH on Dye Adsorption Rate by P. mollis

0

2

4

6

8

10

0 15 30 45 60 90 150 210 330 450 570 1440 1500 1560 1620

Time (min)

Dy

e A

dso

rbe

d b

y A

lgae

(%

)

pH6 pH7

Results: Palmaria mollis

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

Salt Distilled Media: water water

Salt Distilled water water

Salt Distilled water water

pH: 3

30°C

20g P. mollis

Duration: 8 hours

Results: Salinity Experiment (10g/L)

Effect of Salinity on Dye Adsorption Rate by F.

0%

10%

20%

30%

40%

50%

60%

70%

0 30 60 90 120 240 480

Time (min)

Dye

Ad

sorb

ed

by

ALg

ae

(%

)

Dye Adsorbed (Dist. Water) Dye Adsorbed (Salt Water) P-value: 0.0125

100% 68.3% 62.5% 60.1% 58.5% 40.1% 39.8%

Percent Dye Remaining for 10g/L in Salt Water With a Dilution Factor of 100

Results: Salinity Experiment (5g/L)

Effect of Salinity on Dye Adsoprtion Rate by F.

0%

10%

20%

30%

40%

50%

60%

70%

0 30 60 90 120 240 480Time (min)

Dye A

dso

rbed

by A

lgae

(%)

Dye Adsorbed (Dist. Water) Dye Adsorbed (Salt Water) P-value: 0.0168

Results: Salinity Experiment (2.5g/L)

Effect of Salinity on Dye Adsorption Rate by F.

0%

10%

20%

30%

40%

50%

60%

70%

0 30 60 90 120 240 480

Time (min)

Dy

e A

dso

rbe

d b

y A

lga

e (

%)

Dye Adsorbed (Dist. Water) Dye Adsorbed (Salt Water)

Torres 2012

Methods: F. vesiculosis

Experiment 2: Determine Optimum Temperature Condition Temperature: 30°C 35°C 40°C

2.5g/L 10g/L Salt water

2.5g/L 10g/L Salt water

Dye Conc.: 2.5g/L 10g/L Type of Media: Salt water

pH: 3

20g P. mollis

Duration: 8 hours

Results: Temperature Experiment

Effect of Temperature on Final Dye Concentration

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

30 35 40

Temperature (°C)

Fin

al D

ye

Con

cen

trat

ion

(g/L

)

2.5g/L Initial Dye Concentration 10g/L Initial Dye Concentration

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

Untreated Char 600°C Treated Char 600°C -pH: 3, 5, 7

-Media: 2.5g/L Dye in Salt Water

-Samples taken at

4 hrs and 24 hrs

-pH: 3, 5, 7

-Media: 2.5g/L Dye in Salt Water

-Samples taken at

4 hrs and 24 hrs

Untreated Char 300°C Treated Char 300°C -pH: 3, 5, 7

-Media: 2.5g/L Dye in Salt Water

-Samples taken at

4 hrs and 24 hrs

-pH: 3, 5, 7

-Media: 2.5g/L Dye in Salt Water

-Samples taken at

4 hrs and 24 hrs

Methods

Results

High Temp Char Untreated

0

5

10

15

20

25

30

35

0 240

Time (min)

AG

3 D

ye U

pta

ke (

%)

pH7 pH5 pH3

240 1440

Results High Temp Char Treated with

0

2

4

6

8

10

12

0 240

Time (min)

AG

3 D

ye U

ptake (

%)

pH7 pH5 pH3

240 1440

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)

Clean wash water (lower volume)

Operating

Operating

Regeneration

Regeneration

Clean effluent water (No dyes)

Wash water (Dyes

concentrated)

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