Appendix

Appendix A.

1996 Pasig River Water Quality Data taken near Vargas Bridge and Sanchez Bridge
Fig. A-1 BOD levels of Pasig River water samples taken near the 2 bridges
For Vargas Bridge:
Date BOD (mg/L) Salinity pH DO(mg/L) Temp(C) NH3-N PO4-P NO3-N Total Coliforms MPN)
Jan 5 0 7.93 4.5 27.1 0.638 0178 0.458 170,000
Feb 40 0 7.17 5.4 27.3 1.646 0.343 0.010 800,000
Mar 24 0 7.17 1.0 29.7 2.465 0.848 0.031 1,600,000
April 11 0 7.49 2.7 30.7 0.609 0.417 0.375 2,400,000
May 17 0 6.48 1.1 30.8 1.905 0.583 0.010 1,700,000
Jun 21 0 6.78 1.7 31.4 2.720 0.623 0.018 9,000,000
July 41 0 6.98 1.8 29.5 1.420 0.661 0.010 2,400,000

For Sanchez Bridge:
Date BOD (mg/L) Salinity pH DO(mg/L) Temp(C) NH3-N PO4- P NO3-N Total Coliforms(MPN)
Jan 42 0 7.58 0.8 26.7 11.040 1.087 0.006 230,000,000
Feb 56 0 7.37 0.1 26.7 3.220 1.930 0.010 13,000,000
Mar 46 0 7.13 0.4 27.6 3.370 1.845 0.018 17,000,000
April 48 0 7.40 0.2 30.3 2.745 1.227 0.010 13,000,000
May 33 0 7.13 0.8 29.2 2.685 1.920 0.010 22,000,000
Jun 34 0 7.14 0.9 28.8 2.925 1.376 0.280 8,000,000
July 38 0 7.15 0.8 29.9 3.190 1.119 0.010 13,000,000


Appendix B

Determination of COD by the Open Reflux Method
(APHA-AWWA-WEF. 1995)
Reagents
A. 0.0417 M K2Cr2O7 - 24.518 g K2Cr2O7, dissolved and diluted to 2 L
B. H2SO4 reagent - 5.5 g Ag2SO4 dissolved in 1 Kg H2SO4
C. Ferroin Indicator - 1.485 g 1,10-phenanthroline•H2O
+ 695 mg FeSO4•7H2O, dissolved and diluted to 100 mL dH2O
D. HgSO4
E. Standard 0.25 M Ferrous Ammonium Sulfate (FAS) - 98 g Fe (NH4)2(SO4)2•6H2O
dissolved in d H2O + 20 mL conc. H2SO4, cooled and diluted to 1 L

Standardization of FAS:
5 mL std. 0.0417 M K2Cr2O7 reagent dissolved and diluted to 100 mL + 15 mL conc.H2SO4
+ ferroin indicator titrate with FAS

M of FAS = mL of 0.0417 M K2Cr2O7 x 0.25
mL of FAS

COD Open Reflux Method

Place 50.0 mL sample in a 500-mL refluxing flask . Add 1 g HgSO4 , several glass beads, and very slowly add 5.0 mL sulfuric acid reagent, with mixing to dissolve HgSO4. Cool while mixing to avoid possible loss of volatile materials. Add 25.0 mL 0.0417 M K2Cr2O7 solution and mix. Attach flask to condenser and turn on cooling water. Add remaining sulfuric acid reagent (70 mL) through open end of condenser. Continue swirling and mixing while adding the sulfuric acid reagent. CAUTION: Mix reflux mixture thoroughly before applying heat to prevent local heating of flask bottom and a possible blow-out of flask contents. Cover open end of condenser with a small beaker to prevent foreign material from entering refluxing mixture and reflux mixture and reflux for 2 h. Cool and wash down condenser with distilled water. Disconnect reflux condenser and dilute mixture to about twice its volume with distilled water. Cool to room temperature and titrate excess K2Cr2O7 with FAS, using 0.10 to 0.15 mL (2 to 3 drops) ferroin indicator. Although the quantity of ferroin indicator is not critical, use the same volume for all titrations. Take as the end point of the titration the first sharp color change from blue-green to reddish brown. The blue-green may reappear. In the same manner, reflux and titrate a blank containing the reagents and a volume of distilled water equal to that of sample.


COD as mg O2/L =

Where: A= mL FAS used for blank
B= mL FAS used for sample
M= molarity of FAS
X= mL sample


Appendix C

Table C-1 Summary of Isotherm Equations and Constants for Phenol Adsorption in Wang’s study (1997)

Isotherm equation Constant R-Square

Langmuir
Q=290.12 0.9909
b=2594.20


Freundlich
Kf = 1214.62 0.9734
n=0.308


Jossens (1978)
J1 = 1.46 x 106 0.9944
J2 = 3207.59
J3 = 0.898


Weber-Vliet (1980)
W1 = 1.26x10-10
W2 =-1.225

W3 = -0.27 0.8473

W4 = 3.479








Appendix D

IODINE NUMBER DETERMINATION
(Culp and Culp Method of 1971)

Iodine no. – defined as the milligrams of I2 adsorbed by one grams of carbon when the iodine concentration of the residual filtrate is 0.02 N.

I. Preparation of Reagents

A. Preparation of approximately 0.1 N I2 solution
1. Weigh 19.1 g KI crystals and place in a 1000-mL glass stoppered volumetric flask.
2. Weigh 12.7 g of I2 crystals.
3. Mix (1) and (2) in the 1000-mL volumetric flask. Add 10 mL of dH2O (distilled water) and place glass stopper immediately. Allow crystals to dissolve by stirring for several minutes.
4. When most of the crystals dissolve, add an additional 20 mL of dH2O and mix the solution thoroughly
5. When no crystals are available, add dH2O to make 1.0 L of solution and mix the solution thoroughly.
6. Immediately place the solution in dark colored bottles, carefully marked and store in a cool, dry and dark place.

Notes:
a. I2 dissolves slowly in the concentrated KI solution. Thus the KI / I2 mixture should be stirred several minutes before transferring to storage bottles.
b. Any solid I2 that is transferred to the storage bottle will cause the normality of the solution to increase gradually. Filtration to a sintered glass crucible will eliminate this source of difficulty.
c. To prepare 500 mL of I2 solution, the weights of above may be halved. Note that the above I2 solution has a normality of approximately 0.1 N. To determine the exact normality, the solution has to be standardized with Na2S2O3 (sodium thiosulfate).

B. Preparation of 0.1 Na2S2O3 solution
1. Boil about 1000mL of dH2O for at least 5 minutes .Let it cool for a while.
2. Weigh 25 g of Na2S2O3 crystals (Na2CO3 and H2O) and 0.10 g of Na2CO3 and place in 1000-mL volumetric flask. Add dH2O to the flask to make 1000-mL solution with occasional stirring.
3. Transfer to a clear stoppered bottle and store in a dark place. Keep for further standardization.

C. Preparation of starch indicator
1. Boil 1000 mL of dH2O .
2. Make a paste by rubbing about 2.0 g of soluble starch in about 30 mL of dH2O.
3. Pour the above mixture into the 1000-mL boiling water.
4. Heat the mixture until clear solution results.
5. Cool the mixture and set the volume to 1000 mL.
6. Store the solution in stoppered bottles.
7. For most titration, 3-5 mL of indicator should be sufficient.
8. A fresh solution should be prepared every few days.

D. Preparation of 5% HCl (500 mL)
1. Measure 66.8 mL of 37.4 % concentrated HCl (approximately 12 M).
2.Transfer the measured HCl in a 500 mL volumetric flask containing about 400 mL of dH2O.
3. Add the acid and fill to the brim.

E. Preparation of 6 M HCl (100 mL)
1. Measure 50 mL of 37.4 % concentrated HCl (approximately 12 M).
2. Add the concentrated HCl to a 100-mL volumetric flask containing about 40mL dH2O.
3. Fill to 100-mL mark with dH2O.


II. Standardization of Na2S2O3 against KIO3 (Potassium Iodate)

1. Dry primary standard grade KIO3 for at least an hour and cool in a dessicator.
2. Wash 0.6 g of KIO3 and place in a 250-mL volumetric flask.
3. Dissolve the KIO3 sample in the dH2O and fill to the 250-mL mark.
4. Measure the 50-mL of this sample and place in a 250 mL E. flask.
5. Add 2.0 g of iodateful KI to the E. flask containing KIO3 solution and 20 mL of 6.0 M HCl.
6. Titrate immediately with Na2S2O3 until the color of the solution becomes pale yellow.
7. Add 5 mL of starch indicator and titrate to the disappearance of the blue color.
8. The normality of the Na2S2O3 solution is calculated as follows:

N= wt. KIO3 in g x ______ 1_______ x vol. aliquot used
214.0 g / 6000 eq vol. Na2S2O3 used 250 mL


III. Procedure for Iodine Number Determination

1. Grind a representative sample of a carbon until 90 % or more will pass a 100-mesh sieve.
2. Dry the sample for a minimum of 3 hours in an electric oven maintained at 150  C or for 3 hours at 110  C.
3. Weigh 1-5 g of dried pulverized carbon. Use 1 g for high quality carbon and 5 g for lower quality.
4. Transfer the weighed sample into a dry glass stoppered 250-mL E. flask.
5. To the flask, add 100 mL of 5 % weight HCl per gram of carbon used and swirl until the carbon is wetted.
6. Place the flask in a hot plate, bring the contents to a boil and allow boiling for 30 minutes.
7. Allow the flask and the contents to cool to room temperature and add 100 mL of standardized 0.1 N I2 solution.
8. Immediately stopper the flask and mix the contents vigorously for 6 minutes or using a stirring magnet.
9. Filter by gravity immediately after the 6-min. shaking period through a Whatman folded filter paper.
10. Discard the first 20-30 mL of the filtrate and collect the remainder in a clean beaker. Do not wash the residue on the filter paper.
11. Mix the filtrate in the beaker with a stirring rod and pipette 50 mL of the filtrate into a 250-mL E. flask.
12. Titrate the 50-mL samples with a standardized 0.1 N sodium thiosulfate solution until the yellow color has almost disappeared.
13. Add about 2-5 mL starch solution and continue titrating until the blue indicator disappears.
14. Record the volume of Na2S2O3 solution used.
15. Calculate the iodine no. as follows:


X/M = A – [(2.2B * vol. thiosulfate used) / wt. sample]

C = N2 * mL of thiosulfate used / 50 mL

Iodine no. = (X/M) * D

Where:
X/M = mg of iodine adsorbed per gram of carbon
N1 = normality of iodine solution
N2= normality of sodium thiosulfate solution
A= N1 *126 93.0
B= N2 *126.930
C= residual filtrate normality
D= connection factor




Appendix E
Statistical Analysis

Oneway

Test of Homogeneity of Variances
COD
Levene Statistics df1 df2 Sig.
5.30E+15 2 3 0.000

Checking of Assumption

Ho: Variances are equal
Ha: Variances are not equal
Ts: F- test
Dr: Reject Ho if sig ( p-value) < (α=0.05) Comp: Sig. = 0.000 Rec: Reject Ho Conc: Variances are not equal NPar Tests Kruskal- Wallis Test Ranks Time N Mean Rank COD 0.5h 2 1.50 1h 2 3.50 2h 2 5.50 Total 6 Test Statistics a,b COD Chi-Square 4.571 df 2 Asymp. Sig. 0.102 a Kruskal- Wallis Test b Grouping Variable: Time Ho: The different contact time have the same % COD reduction Ha: At least on of them has different COD reduction Ts: Kruskal- Wallis Test Dr: Reject Ho if sig ( p-value) < (α=0.05) Comp: Sig. = 0.102 > 0.05
Rec: Fail to reject Ho
Conc : The different contact time have the same % COD reduction


Appendix F

RAW DATA

Table F-1 Moisture content
T1 T2 T3
Initial wt (g) 6.0375 6.1627 6.1317
Final wt (g) 5.7162 5.8258 5.6935
Wt. lost 0.3213 0.3369 0.4382
Moisture content (%) 5.32 5.47 7.15
Ave. (%) 5.98 ± 0.66

Table F-2 Bulk Density
T1 T2 T3
Wt of grad cylinder (g) 39.6550 39.6170 39.4328
Wt of grad cyl + AC (g) 44.9031 45.2210 44.9676
Wt AC (g) 5.2481 5.604 5.5348
Volume occupied (mL) 8.90 9.80 9.60
ρ ( g/mL) 0.590 0.572 0.576
Ave. (%) 0.579 ± 0.007


Table F-3 Iodine Number
T1
T2 T3
Na2S2O3 used (ml) 13.70 17.25 16.80
C, residual filtrate (N) 0.0219 0.0276 0.0269
D, correction factor 0.9788 0.9563 0.9538
X/M 893 861 865

Iodine Number 874 823 825
Average
841 ± 22
Note:
Weight of AC used = 2.5 g
N of I2 solution = 0.08
N of Na2S2O3 solution = 0.08

Sample Calculations:

C = N2 * mL of thiosulfate used / 50 mL


X/M = A – [(2.2B * vol. thiosulfate used) / wt. sample]


Iodine no. = (X/M) * D = 893.01 * 0.9788 = 874 mg/g
Table F-4 Contact time Determination (Trial 1)
Contact time COD (ppm) % COD reduction pH initial pH final Turbidity
(NTU) Color
(PCU) Odor
0 h 81.40 - 7.61 7.61 14 35 objectionable
0.5 h 53.33 34.48 7.61 7.74 11 30 objectionable
1 h 44.29 45.59 7.61 7.87 10 25 objectionable
2 h 41.56 48.94 7.61 7.90 10 25 objectionable




Table F-5 Contact time Determination (Trial 2)
Contact time COD (ppm) % COD reduction pH initial pH final Turbidity
(NTU) Color
(PCU) Odor
0 h 77.90 - 7.61 7.61 14 35 objectionable
0.5 h 49.83 36.03 7.61 7.72 11 30 objectionable
1 h 47.69 38.78 7.61 7.87 9 25 objectionable
2 h 41.56 46.65 7.61 7.89 10 25 objectionable




Table F-6 Contact time Determination (Supplementary trials)
contact time COD (ppm) % COD reduction Chloride content
(mg Cl-/L)
Trial 1

0 83.23 - 23.58
3h 42.96 48.38
4h 42.96 48.38 23.16
5h 40.28 51.60 19.08
Trial 2

0 83.23 - 22.11
3h 45.65 45.15
4h 42.96 48.38 22.34
5h 46.18 44.52 19.08




Table F-7 Optimum pH Determination (Trial 1)
sample
pH initial COD (ppm) % COD reduction pH final Turbidity
(NTU) Color
(PCU)
C0 7.1 82.21 0 7.1 26 40
C1 7.1 46.33 43.64 7.3 14 25
L1 6.5 45.38 44.80 7.0 12 20
L2 5.5 22.69 72.40 6.3 7 15
U2 8.5 46.03 44.01 7.8 9 25







Table F-8 Optimum pH Determination (Trial 2)
sample
pH initial COD (ppm) % COD reduction pH final Turbidity
(NTU) Color
(PCU)
C0 7.1 80.92 0 7.1 14 40
C1 7.1 55.03 32.00 7.3 11 25
L1 6.5 45.97 43.19 7.2 10 20
L2 5.5 29.78 63.20 6.4 9 20
U2 8.5 48.24 40.39 7.8 9 25




Table F-9 Kinetics of Adsorption of Organics
COD
cod - cod eq
dC/dt
ln(c- ce)
ln dc/dt

80.84 40.56 101.05 3.702782359 4.615615444
60 19.72 62.18 2.981633349 4.130033405
52 11.72 31.9 2.461296784 3.46260601
48 7.72 10.96 2.043814364 2.394252282
46 5.72 6.58 1.743968805 1.884034745
45 4.72 3.75 1.5518088 1.32175584
44 3.72 1.67 1.313723668 0.512823626
41 0.72 0.87 -0.328504067 -0.139262067





Table F-10 Minimum amount that will give satisfactory COD reduction
mg AC COD filtrate (mg/L) COD adsorbed
(mg/L) % COD Reduction
0 83.23 0 0
22 32.11 51.12 61.42
76 31.59 51.64 62.04
105 26.32 56.91 68.38
200 11.06 72.17 86.71