Biodegradation Studies of Selected Polymers of Carbohydrate Origin

 

J. R. Dontulwar* and D. K. Borikar

Department of Chemistry, Priyadarshini Institute of Engineering and Technology, Hingna Road, CRPF Gate, Nagpur, Maharashtra-440 019, India.

*Corresponding author: jdontulwar@yahoo.co.in

 

ABSTRACT:

The carbohydrates polymers with components white dextrin, sorbitol and maleic anhydride as batch-1, starch, glycerol, maleic anhydride as batch-2 and starch, glycerol, sorbitol and maleic anhydride as batch-3 were synthesized using simple laboratory technique. These polymers have shown hydrophilic- liphophilic balance (HLB) in the range 11.88 to 12. The HLB data of batch 1, batch 2 and batch 3 indicates the suitability of the polymers for detergent formulation. The biodegradation study of all these polymers were done in detail prior to its application in the detergent formulation. The biodegradation studies of polymers 1,2, and 3 were carried using changed method of BOD and COD. The BOD/COD ratio value for polymers 1,2, and 3 were found to be favourable and well within the requisite data required for biodegrading. The values of BOD/COD ratio for polymers 1, 2, and 3 was found to be 1.14, 0.6075 and 0.5965 respectively.

 

 


 

INTRODUCTION:

Interest in biodegradable polymers has been growing at a very fast rate as our society becomes increasingly sensitive to the harmful side effects of the traditional applications of such chemicals. Great pressure is being put on researchers to device a way of implementing biodegradable polymers into waste management1.

 

Applications of synthetic polymers were mostly based on their relative inertness to the elements and their biodegradation in comparison with natural macromolecules such as cellulose and proteins. In recent years many important applications require biodegradable polymers. Successful applications include sutures, surgical implants, agricultural mulches and controlled release formulations of drugs and agricultural chemicals.

 

The nature of the chemical structure of the polymer determines the biodegradability whereas the physical properties of the polymer affect the rate of biodegradation. Biological systems degrade large natural molecules  such as starch, cellulose, proteins etc. by hydrolysis followed by oxidation. Polymer based on such molecules have been synthesised recently6,7.

 

Most of the known biodegradable polymers contain hydrolysable groups along the polymer main chains. Only a few high molecular weight carbon chains containing polymers are biodegradable2. Polysaccharides react with small carboxylic acids to produce derivatives that are biodegradable.3,4

 

experimental:

In the present work the B.O.D. and C.O.D. method of biodegradation was used5. The determination of B.O.D. involves the determination of the dissolved oxygen used by microorganisms in the biochemical oxidation of organic matter. To ensure that meaningful results, the sample was suitably diluted with specially prepared dilution water so that adequate nutrients and oxygen were available during the incubation period. Normally several dilutions were prepared to cover the complete range of possible values.

 

The dilution water was seeded with a bacterial culture that has been acclimated to the organic matter present in the water. The seed culture that was used to prepare the dilution water for BOD test was a mixed culture of a large number of saprophytic bacteria and other organisms that oxidized the organic matter. The incubation period was 10 days at 20oC. The temperature was constant throughout the test. After incubation, the dissolved oxygen of the sample was measured and the B.O.D. was calculated using formula (1)

 

B.O.D. in mg/gm = {(D0 - D1)} - {(Co - C1)} x (decimal fraction of sample used)

.... (1)

 

 

Where,

D0 = Dissolved oxygen in sample on 0 day.s

D1, D2……, D10  = D.O. in sample on 1st , 2nd,………… 10th day respectively

Co = D.O. in blank on 0 day

C1, C2, ...C10 = D.O. in blank on 1st, 2nd, ...10th day respectively

 

Preparation of dilution water

Required quantity of distilled water was taken and aerated at 20oC with clean compressed air. 1 ml of CaCl2, MgSO4, FeCl3 and phosphate buffer solution per litre of the above distilled water was added and mixed thoroughly. This standard dilution was prepared just before the use. The addition of small measured volume of water containing a good bacterial population to the dilution water is called seeding. In this experiment acclimated seeds are used for B.O.D.

 

Pre -Treatment method

Necessary quantity of 1 normal H2SO4 or 1 N NaOH was added in the sample to bring the pH  in a range of 6.5 to 8.5. Sample was thoroughly shaken just before dilutions were made. Series of dilutions for a sample were made such that at least three of the dilutions should deplete 20% to 90% of initial D.O. The C.O.D. value was treated as guideline for the purpose of dilution.

 

The prepared dilution water was transferred into one litre graduated cylinder until it was half full, without any air entrapment. Then appropriate quantity of sample was added into the cylinder without producing any air bubbles. The volume was then made up using dilution water and mixed well with glass rod without any air entrapment. The two BOD bottles were filled carefully without any air bubbles inside it. The bottles were stoppered and the other dilution of sample were prepared in similar manner. Similarly standard dilution water was taken into BOD bottle and stoppered it after filling completely.

 

One set of entire series of dilution prepared was utilized for immediate determination DO and kept the other set in a BOD incubator maintained at 20ºC for 1, 2, 3..........10 days. After 1st day to 10th day the D.O. and concentration of all the incubated sample of the set was determined.

 

Preparation of Seed

Bacteriological seed was brought from biological reactor of food industry and preserved at 37ºC in laboratory. The seed was activated by adding nutrients, phosphate buffer, dextrose and ammonium chloride in sufficient quantity. It was then aerated for 48 hours and multiplied and activated seed was inoculated to dilute resin sample taken for B.O.D. analysis. By making above changes in the selection of seeds, BOD experiments were carried.

 

Chemical Oxygen Demand5

Chemical oxygen demand was determined by refluxing the sample with a known excess of potassium dichromate in a 50% H2SO4 solution in presence of AgSO4 (as catalyst) and HgSO4 (to eliminate interference due to chloride). The organic matter of the sample was oxidized to water, CO2 and NH3. The unreacted dichromate in the solution was titrated with a standard ferrous ammonium sulphate (FAS) solution. The COD of the sample was calculated using equation (2)

              

.... (2)

 

 
                           (B-S) ml x 8 x 1000

COD in mg/l =

                                       X

 

Where B and S are the volumes of FAS run down in the blank and test experiments respectively and X is the volume of sample taken for the test.

 

RESULTS AND DISCUSSION:

The polymers synthesized in laboratory as batch 1,2 and 3, showed the HLB ratio as 12, 12.39 and 11.88. This values are well within the range so that the polymers can be used in detergent formulation (Table 1).

 

Table 1. Hydrophilic- Liphophilic balance

Sr. No.

Polymer Batch

H.L.B.

Remarks

1

1

12

Suggests Its Use in detergent formulation

2

2

12.39

Suggests Its Use in detergent formulation

3

3

11.88

Suggests Its Use in detergent formulation

 

Table 2. BOD and COD Analysis of Batch 1

Sr. No.

Particulars

Concentrations (mg/g)

BOD at 200C

COD

BOD: COD

1

After 1st Day

113207

10,88,000

0.1040

2

After 2nd Day

169811

--

0.1560

3

After 3rd Day

311320

--

0.2861

4

After 4th Day

424528

--

0.3901

5

After 5th Day

509433

--

0.4682

6

After 6th Day

679245

--

0.6243

7

After 7th Day

849056

--

0.7803

8

After 8th Day

1245283

--

1.14

9

After 9th Day

1075471

--

0.9884

10

After 10th Day

1018867

--

0.9364

 

 

Table 3. BOD and COD Analysis of Batch 2

Sr. No.

Particulars

Concentrations ((mg/g))

BOD at 200C

COD

BOD: COD

1

After 1st Day

104803.49

970305.67

0.1080

2

After 2nd Day

209606.98

--

0.2160

3

After 3rd Day

393013.10

--

0.4050

4

After 4th Day

445414.84

--

0.4590

5

After 5th Day

563318.77

--

0.5805

6

After 6th Day

576419.21

--

0.5940

7

After 7th Day

589519.65

--

0.6075

8

After 8th Day

550218.34

--

0.5670

9

After 9th Day

524017.46

--

0.5400

10

After 10th Day

235807.86

--

0.2430

 

 

 

Table 4. BOD and COD Analysis of Batch 3

Sr. No.

Particulars

Concentrations ((mg/g))

BOD at 200C

COD

BOD: COD

1

After 1st Day

248962.65

1124829.87

0.2213

2

After 2nd Day

298755.18

--

0.2656

3

After 3rd Day

622406.63

--

0.5533

4

After 4th Day

634854.77

--

0.5644

5

After 5th Day

647302.90

--

0.5754

6

After 6th Day

672199.17

--

0.5976

7

After 7th Day

647302.90

--

0.5754

8

After 8th Day

622406.63

--

0.5533

9

After 9th Day

398340.20

--

0.3542

10

After 10th Day

373443.98

--

0.3320

 

Table 5. B.O.D./C.O.D. Ratio of Carbohydrate Polymers

Sr. No.

Batch Type

BOD/

COD Ratio

Remarks

1

Batch 1 (white dextrin, sorbitol maleic anhydride)

1.14

Biodegradable

2

Batch 2 (starch, glycerol and maleic anhydride)

0.6075

Biodegradable

3

Batch 3 (starch glycerol, sorbitol, maleic anhydride

0.5976

Biodegradable

 

The BOD and COD studies explain the biodegradability of the polymers. It was found that the BOD to COD ratio for batch-1 was highest on 8th day (Table 2) i.e. the highest biodegradation would take place on 8th day. This is also evident from  8th day BOD of the sample. The BOD to COD ratio for batch-2 was highest on 7th  day. i.e the highest biodegradation would take place on 7th day, which is evident BOD of (Table 3). It was also found that the BOD to COD ratio for batch-3 was highest on 6th day. i.e. the highest biodegradation would take place on 6th day which is evident from 6th day BOD of sample (Table 4).

 

CONCLUSION:

The measure of biodegradability is the ratio of BOD/COD (Table 5). Using thumb rule of the ratio value equal to 0.6 and above then the polymer is considered to be biodegradable. The polymers of present study are found to be biodegradable as these polymers give this ratio within 8 days.

              

REFERENCES:

1)       Milgrom J., Polym Plast Technol. Engg., p.p.18. 167, 1982.

2)       Bitritto M.M., Bell J.P., Brenchle G.M., Huang S.J., Knox J.R., J.applied

3)       Ferruti. P.  Vaecaroui F. and. Makromol Tuzi M.C.chem, pp180, 375. 1979.

4)       Wirick. M.G.  J. Polym. Sci. Part A. p.p. 1, 6, 1705, 1965.

5)       Dara. S.S., “Experiments and calculations in Engineering Chemistry”  p.p.45, S.Chand, 2001

6)       Dontulwar, J.R., Borikar, D.K, Gogte, B.B., Carbohydrate Polymers, 63(2006)  375-378

7)       Dontulwar, J.R., Borikar, D.K, Gogte, B.B., Carbohydrate Polymers, 65(2006) 207-210

 

 

 

 

 

 

Received on 14.07.2011         Modified on 05.12.2011

Accepted on 15.12.2011         © AJRC All right reserved

Asian J. Research Chem. 5(2):  February 2012; Page 197-199