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 To determine the water quality parameters of the Buriganga
river
 To predict the Humic Acid structure of the Buriganga River
bottom sediment
 To study the complexation behavior between HA- Metals
(Iron, Cadmium, Chromium, Manganese, Lead, Nickel and
Calcium)
SAMPLE COLLECTION SAMPLE ANALYSIS
 Nine sediment samples
were collected from the
Buriganga river.
 Eighteen water samples
were collected from the
Buriganga river.
 The water samples were
analyzed by AAS and UV-
Visible for metal ions and
anions
 Humic acid was extracted
from the sediments according
to IHSS
 Characterization and study
of complexation with metals of
extracted HA was carried out
with IR, FTIR, SEM, EDX and
CHNS analyzer.
Sampling stations:
a) First Buriganga Bridge
b) Arsene gate, Gudara Ghat
c) Sadar Ghat First Jetty
d) Shaym Bazar Ghat
e) Sadar Ghat Main Terminal
f) Sadar Ghat Fruit Bazar
g) Ahsan Manzil Ghat
h) Second Buriganga Bridge
i) Imamganj Paan Ghat
j) Dhaka Dockyard
k) Toil Ghat
l) Keraniganj Police Ghat
m) Kamrangir Chor Ghat
n) Shoari Ghat
o) Solimullah Medical
College Ghat
p) Jora bridge, Kamrangir
Chor
q) Forashganj Ghat
r) Faridabad Launch Terminal
River bottom sediments
Dried under sun for 5 hours + Broken piece of
shell & small dust removed
Dried sample (100g)
+ 1 M HCl (up to pH 1~2) + 0.1 M HCl (10mL
Liquid/ 1g dried sample)
Solution (pH=1 to 2)
Centrifugation
(700 rpm 5min)
Shaking for 1 hour
+1.0M NaOH (up to pH =7.0)
ResidueSupernatant
+ 0.1 M NaOH (at N2)
Solution (pH ~ 11)
Shaking for 4 hour + Settle overnight
Centrifugation
(1500 rpm 15
min)
Supernatant
Residue
+ 6 M HCl (up to pH = 1.0)
+ Stand for 12~16 hour
Centrifugation
(1000 rpm 10 min)
Supernatant-
Fulvic acid
Precipitate
+ 0.1 M KOH + solid KCl (0.3M [K+])
Centrifugation
(2000 rpm 10 min)
Liquid HA Precipitate
Dried in oven (50oC)
Solid HA
Figure 2: Flow Chart of extraction procedure of Humic Acid
Samples Fe2+/3+
mg/L
Pb2+
mg/L
Cd2+
µg/L
Cr3+/6+
mg/L
Ni3+
mg/L
Ca2+
mg/L
Mn2+
mg/L
Wa 0.08 0.13 4.00 0.01 0.04 33.38 0.03
Wb 0.06 0.12 2.00 0.06 0.07 52.56 0.01
Wc 0.1 0.15 3.00 0.03 0.07 22.68 0.02
Wd 0.12 0.12 0.80 0.02 0.04 24.34 0.04
We 0.04 0.11 8.00 0.03 0.03 22.56 0.01
Wf 0.04 0.12 2.00 0.01 0.06 22.62 0.07
Wg 0.14 0.12 1.00 0.01 0.04 19.04 0.05
Wh 0.22 0.20 0.75 0.02 0.01 20.58 0.04
Wi 0.04 0.002 7.50 0.08 0.06 49.30 0.01
Wj 0.32 0.04 2.00 0.04 0.07 31.50 0.11
Wk 0.26 0.02 4.90 0.02 0.06 19.22 0.03
Wl 0.1 BDL 0.40 0.01 0.05 14.70 0.01
Wm 0.12 0.004 12.00 0.01 0.05 59.00 0.05
Wn 0.18 0.04 8.50 0.03 0.04 14.66 0.01
Wo 0.04 0.02 6.00 0.01 0.07 25.22 0.02
Wp 0.22 0.03 16.70 0.09 0.06 20.76 0.03
Wq 0.30 0.03 5.80 0.01 0.05 27.78 0.09
Wr 0.28 0.04 2.00 0.03 0.02 21.04 0.02
WHO std (drinking) 0.30 0.01 5.00 0.05 - 200.00 0.10
Std. for Fishing water 0.30 0.01 5.00 0.10 - - 0.10
Table 1: Observed values of metal ions of Buriganga river with standard values
Figure 5: FTIR Spectrum of Extracted Humic
Acid
(d)
Wave no.(cm-1
) Region
(cm-1
)
Type of
vibration
3280(a),3300(d),3280(g),
3280(i)
3400-3200,
3570-3450
H- bonded OH
group
3000(i) 3050-3000 Aromatic C-H
stretching
2960(a),2920(d),2920(g),2960(i
)
2960-2850 Stretching of
CH2, CH3 group
2960(a),2930(d),2960(g),2560(i
)
3000-2500 OH stretch of H-
bonded –COOH
1550(a),1560(d),1580(g) 1610-1550 Carboxylate
anion
1650(a),
1650(d),1640(g),1655(i)
1650-1450 Aromatic C=C
stretching
1400(a),1400(d),1400(g),1400(i
)
1485-1340 CH deformation
of CH3
1260(i) 1265-1200 Symmetric –
COO-
stretching
1120(a),1130(i) 1126-1100 C-O stretching of
COOH
1070(a) ~1100,~10
50
-C-O stretching
in aliphatic OH
700,830,880(a),700,860,880(d) 840-690 Aromatic
disubstituted
Table 2: FTIR analysis of extracted
Humic Acid
Figure 8: SEM image of extracted
Humic Acid (Buriganga River)
Figure 7: SEM image of Standard
Humic Acid
Element CHNS Analysis
(% Weight)
EDX (%
Weight)
C 63.25 62.36
H 4.514 Not
quantified
N 0.75 3.16
S 0.763 3.71
O 30.72 25.88
Table 3: Elemental Composition of
extracted HA with CHNS and EDX
analyzers
Figure 9: EDX Spectrum of Extracted HA
Figure 6: Proposed structure of Extracted Humic Acid
OH
COOH
HO
OH
COOH
O
HO
O
N
CH
COOH
R
O
O
O
NH
O
H
CH
CH
R
O
CH
CH
N
O
CH2
CH
O
O
O
O
OH
COOH
COOH
OO
O
OH
H
Figure 10: SEM image of Humic
Acid and Fe Complex
Figure 11: EDX Spectrum of HA-Iron (II)
Complex
pH
1 2 3 4 5 6 7 8 9 10 11 12 13
Transmitance%
75
80
85
90
95
100
Removal%
88
90
92
94
96
98
100
102
Tranmitance % vs pH
Removal % vs pH
pH
1 2 3 4 5 6 7 8 9 10 11 12 13
Transmitance%
88
90
92
94
96
98
100
102
Removal%
88
90
92
94
96
98
100
102
Transmitance % vs pH
Removal % vs pH
Figure 12: Complexation study of HA
with Iron (II) Sulphate at different pH at
254 nm
Figure 13: Complexation study of HA with
Iron (II) Sulphate at different pH at 436 nm
Concentration of Iron (II) X 10
-3
M
0.1 0.3 0.5 0.7 1.0 1.3 1.5 1.7
pH
5.2
5.4
5.6
5.8
6.0
6.2
6.4
6.6
6.8
ConductanceX10-2
S
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
Concentration of Fe vs pH
Concentration of Fe vs Conductance
OCC
RC
a b
Concentration of Iron X 10-3
M
0.1 0.3 0.5 0.7 1.0 1.3 1.5 1.7
DegreeofComplexationat254nm
70
75
80
85
90
95
100
DegreeofComplexationat436nm
30
40
50
60
70
80
90
100
Conc of Fe vs at 254
Conc of Fe vs at 436
Figure 15: Degree of Complexation in
percentage with the variation of
concentration of Iron (II) Sulphate
Figure 14: Jar test of Iron (II) - HA
complexation
Metal - HA Complex Optimum pH
values
Optimum concentrations X 10-3
M
By Jar test By Spectrophotometric test
Iron (II) - Humic Acid 7 0.70 - 1.00 0.70
Cadmium (II) - Humic
Acid
9 0.45 - 0.70 0.55
Chromium (III) -
Humic Acid
3 0.48 - 0.70 0.44 - 0.50
Manganese (II) -
Humic Acid
9 0.70 - 1.19 1.50 - 1.51
Lead (II) - Humic Acid 6 - 10 0.45 - 0.70 0.46 - 0.50
Nickel (II) - Humic
Acid
10 0.67 - 1.00 0.70 - 1.45
Calcium (II) - Humic
Acid
8 1.18 - 1.50 1.24 - 1.30
Table 4: Summary of Metal - HA Complexation study
The formation of Metal - Humic acid complex is controlled by
the number of coagulant (metal ion) species and two dynamics
aspects:
(i) the reconformation of humic network
(ii) the collision rate of destabilized particles.
An overall shrinkage of anionic humic network is indeed
expected upon binding of cationic coagulant species which promotes
the formation of intra- and inter-particle hydrophobic domains
according to the extent of charge neutralization.
The collision rates determines the variations in precipitation
volume in the range of optimal concentration of coagulants.
MECHANISM OF METAL - HUMIC ACID
COMPLEXATION
 The Buriganga river water is highly polluted
 The Humic Acid Structure of Buriganga river sediment is slightly
different than of other places. It contains aromatic hydrocarbons,
large amount oxygen containing groups
 The Buriganga river Humic Acid makes complexes with the
metals.
This complexation or coagulation process can be used to
remove the high concentration of metals from the surface water of
this river.
THANK YOU

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Buriganga River Water Quality and Humic Acid Analysis

  • 1.
  • 2.  To determine the water quality parameters of the Buriganga river  To predict the Humic Acid structure of the Buriganga River bottom sediment  To study the complexation behavior between HA- Metals (Iron, Cadmium, Chromium, Manganese, Lead, Nickel and Calcium)
  • 3. SAMPLE COLLECTION SAMPLE ANALYSIS  Nine sediment samples were collected from the Buriganga river.  Eighteen water samples were collected from the Buriganga river.  The water samples were analyzed by AAS and UV- Visible for metal ions and anions  Humic acid was extracted from the sediments according to IHSS  Characterization and study of complexation with metals of extracted HA was carried out with IR, FTIR, SEM, EDX and CHNS analyzer.
  • 4. Sampling stations: a) First Buriganga Bridge b) Arsene gate, Gudara Ghat c) Sadar Ghat First Jetty d) Shaym Bazar Ghat e) Sadar Ghat Main Terminal f) Sadar Ghat Fruit Bazar g) Ahsan Manzil Ghat h) Second Buriganga Bridge i) Imamganj Paan Ghat j) Dhaka Dockyard k) Toil Ghat l) Keraniganj Police Ghat m) Kamrangir Chor Ghat n) Shoari Ghat o) Solimullah Medical College Ghat p) Jora bridge, Kamrangir Chor q) Forashganj Ghat r) Faridabad Launch Terminal
  • 5. River bottom sediments Dried under sun for 5 hours + Broken piece of shell & small dust removed Dried sample (100g) + 1 M HCl (up to pH 1~2) + 0.1 M HCl (10mL Liquid/ 1g dried sample) Solution (pH=1 to 2) Centrifugation (700 rpm 5min) Shaking for 1 hour +1.0M NaOH (up to pH =7.0) ResidueSupernatant + 0.1 M NaOH (at N2) Solution (pH ~ 11) Shaking for 4 hour + Settle overnight Centrifugation (1500 rpm 15 min) Supernatant Residue + 6 M HCl (up to pH = 1.0) + Stand for 12~16 hour Centrifugation (1000 rpm 10 min) Supernatant- Fulvic acid Precipitate + 0.1 M KOH + solid KCl (0.3M [K+]) Centrifugation (2000 rpm 10 min) Liquid HA Precipitate Dried in oven (50oC) Solid HA Figure 2: Flow Chart of extraction procedure of Humic Acid
  • 6.
  • 7. Samples Fe2+/3+ mg/L Pb2+ mg/L Cd2+ µg/L Cr3+/6+ mg/L Ni3+ mg/L Ca2+ mg/L Mn2+ mg/L Wa 0.08 0.13 4.00 0.01 0.04 33.38 0.03 Wb 0.06 0.12 2.00 0.06 0.07 52.56 0.01 Wc 0.1 0.15 3.00 0.03 0.07 22.68 0.02 Wd 0.12 0.12 0.80 0.02 0.04 24.34 0.04 We 0.04 0.11 8.00 0.03 0.03 22.56 0.01 Wf 0.04 0.12 2.00 0.01 0.06 22.62 0.07 Wg 0.14 0.12 1.00 0.01 0.04 19.04 0.05 Wh 0.22 0.20 0.75 0.02 0.01 20.58 0.04 Wi 0.04 0.002 7.50 0.08 0.06 49.30 0.01 Wj 0.32 0.04 2.00 0.04 0.07 31.50 0.11 Wk 0.26 0.02 4.90 0.02 0.06 19.22 0.03 Wl 0.1 BDL 0.40 0.01 0.05 14.70 0.01 Wm 0.12 0.004 12.00 0.01 0.05 59.00 0.05 Wn 0.18 0.04 8.50 0.03 0.04 14.66 0.01 Wo 0.04 0.02 6.00 0.01 0.07 25.22 0.02 Wp 0.22 0.03 16.70 0.09 0.06 20.76 0.03 Wq 0.30 0.03 5.80 0.01 0.05 27.78 0.09 Wr 0.28 0.04 2.00 0.03 0.02 21.04 0.02 WHO std (drinking) 0.30 0.01 5.00 0.05 - 200.00 0.10 Std. for Fishing water 0.30 0.01 5.00 0.10 - - 0.10 Table 1: Observed values of metal ions of Buriganga river with standard values
  • 8. Figure 5: FTIR Spectrum of Extracted Humic Acid (d) Wave no.(cm-1 ) Region (cm-1 ) Type of vibration 3280(a),3300(d),3280(g), 3280(i) 3400-3200, 3570-3450 H- bonded OH group 3000(i) 3050-3000 Aromatic C-H stretching 2960(a),2920(d),2920(g),2960(i ) 2960-2850 Stretching of CH2, CH3 group 2960(a),2930(d),2960(g),2560(i ) 3000-2500 OH stretch of H- bonded –COOH 1550(a),1560(d),1580(g) 1610-1550 Carboxylate anion 1650(a), 1650(d),1640(g),1655(i) 1650-1450 Aromatic C=C stretching 1400(a),1400(d),1400(g),1400(i ) 1485-1340 CH deformation of CH3 1260(i) 1265-1200 Symmetric – COO- stretching 1120(a),1130(i) 1126-1100 C-O stretching of COOH 1070(a) ~1100,~10 50 -C-O stretching in aliphatic OH 700,830,880(a),700,860,880(d) 840-690 Aromatic disubstituted Table 2: FTIR analysis of extracted Humic Acid
  • 9. Figure 8: SEM image of extracted Humic Acid (Buriganga River) Figure 7: SEM image of Standard Humic Acid
  • 10. Element CHNS Analysis (% Weight) EDX (% Weight) C 63.25 62.36 H 4.514 Not quantified N 0.75 3.16 S 0.763 3.71 O 30.72 25.88 Table 3: Elemental Composition of extracted HA with CHNS and EDX analyzers Figure 9: EDX Spectrum of Extracted HA
  • 11. Figure 6: Proposed structure of Extracted Humic Acid OH COOH HO OH COOH O HO O N CH COOH R O O O NH O H CH CH R O CH CH N O CH2 CH O O O O OH COOH COOH OO O OH H
  • 12. Figure 10: SEM image of Humic Acid and Fe Complex Figure 11: EDX Spectrum of HA-Iron (II) Complex
  • 13. pH 1 2 3 4 5 6 7 8 9 10 11 12 13 Transmitance% 75 80 85 90 95 100 Removal% 88 90 92 94 96 98 100 102 Tranmitance % vs pH Removal % vs pH pH 1 2 3 4 5 6 7 8 9 10 11 12 13 Transmitance% 88 90 92 94 96 98 100 102 Removal% 88 90 92 94 96 98 100 102 Transmitance % vs pH Removal % vs pH Figure 12: Complexation study of HA with Iron (II) Sulphate at different pH at 254 nm Figure 13: Complexation study of HA with Iron (II) Sulphate at different pH at 436 nm
  • 14. Concentration of Iron (II) X 10 -3 M 0.1 0.3 0.5 0.7 1.0 1.3 1.5 1.7 pH 5.2 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 ConductanceX10-2 S 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 Concentration of Fe vs pH Concentration of Fe vs Conductance OCC RC a b Concentration of Iron X 10-3 M 0.1 0.3 0.5 0.7 1.0 1.3 1.5 1.7 DegreeofComplexationat254nm 70 75 80 85 90 95 100 DegreeofComplexationat436nm 30 40 50 60 70 80 90 100 Conc of Fe vs at 254 Conc of Fe vs at 436 Figure 15: Degree of Complexation in percentage with the variation of concentration of Iron (II) Sulphate Figure 14: Jar test of Iron (II) - HA complexation
  • 15. Metal - HA Complex Optimum pH values Optimum concentrations X 10-3 M By Jar test By Spectrophotometric test Iron (II) - Humic Acid 7 0.70 - 1.00 0.70 Cadmium (II) - Humic Acid 9 0.45 - 0.70 0.55 Chromium (III) - Humic Acid 3 0.48 - 0.70 0.44 - 0.50 Manganese (II) - Humic Acid 9 0.70 - 1.19 1.50 - 1.51 Lead (II) - Humic Acid 6 - 10 0.45 - 0.70 0.46 - 0.50 Nickel (II) - Humic Acid 10 0.67 - 1.00 0.70 - 1.45 Calcium (II) - Humic Acid 8 1.18 - 1.50 1.24 - 1.30 Table 4: Summary of Metal - HA Complexation study
  • 16. The formation of Metal - Humic acid complex is controlled by the number of coagulant (metal ion) species and two dynamics aspects: (i) the reconformation of humic network (ii) the collision rate of destabilized particles. An overall shrinkage of anionic humic network is indeed expected upon binding of cationic coagulant species which promotes the formation of intra- and inter-particle hydrophobic domains according to the extent of charge neutralization. The collision rates determines the variations in precipitation volume in the range of optimal concentration of coagulants. MECHANISM OF METAL - HUMIC ACID COMPLEXATION
  • 17.  The Buriganga river water is highly polluted  The Humic Acid Structure of Buriganga river sediment is slightly different than of other places. It contains aromatic hydrocarbons, large amount oxygen containing groups  The Buriganga river Humic Acid makes complexes with the metals. This complexation or coagulation process can be used to remove the high concentration of metals from the surface water of this river.