pharmaceutical active compounds removal by constructed ... · removals •plant role in the...

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AHMED F. HAMADEH 1 PIET LENS 2 AND GARY AMY 1 1 KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY (KAUST), SAUDI ARABIA. 2 UNESCO-IHE INSTITUTE FOR WATER Pharmaceutical Active Compounds Removal by Constructed Wetlands Under Different Redox Conditions

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Page 1: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

AHMED F. HAMADEH1

PIET LENS2 AND GARY AMY1 1KING ABDULLAH UNIVERSITY OF SCIENCE AND

TECHNOLOGY (KAUST), SAUDI ARABIA. 2 UNESCO-IHE INSTITUTE FOR WATER

Pharmaceutical Active Compounds Removal

by Constructed Wetlands

Under Different Redox Conditions

Page 2: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Outlines

• Objectives and Methodologies

• Set-up preparation

• WW Composition

• Feeding water quality

• Organic matters and nutrients removal

• Organic matters characterization

• OMPs properties and removals

• Plant role in the treatment

• Conclusions

Page 3: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

• Study removal processes of nutrients (C, N & P) through CWs under different Redox conditions.

• Assess the removal efficiency of nutrients and selected group of Organic Micropollutants (OMPs) through CWs.

• Specify the plants role in the wastewater treatment during

horizontal Subsurface flow constructed wetlands.

• Build lab scale subsurface flow CWs

and study the performance for different

nutrients and OMPs present in

wastewaters, planted with Phragmites

australis plant and feed with 2° Eff.

synthetic ww.

Study Objectives

Methodology

Page 4: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Sand

Gravel

(Non-aeratedControl)

Sand

Gravel

SandGravel

W.Inffl

Air

Sand

Gravel

Sand

Gravel

Sand

Gravel

Sand

Gravel

Sand

Gravel

(AeratedControl)

CW3

CW2

CW1

Hydraulic Loading Rate: 4.6 cm/d Hydraulic Retention Time: 1 d/each

Flow direction

Page 5: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

C Setup Preparation

Page 6: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Phragmites australis plant harvesting

Page 7: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,
Page 8: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Synthetic WW composition

(Source: Jiang, T. (2007) Characterization and modelling of soluble microbial products in membrane bioreactors. PhD thesis, Ghent Un., Belgium.

Page 9: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Synthetic WW composition

(Source: Jiang, T. (2007) Characterization and modelling of soluble microbial products in membrane bioreactors. PhD thesis, Ghent Un., Belgium.

Page 10: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Feeding water quality

Parameter Unit Concentration

DOC mg/l 9.61 ± 1.5

TN mg/l 8.35 ± 0.87

NO3- as N mg/l 3.63 ± 0.25

NH4+ as N mg/l 1.98 ± 0.67

Organic N. mg/l 2.83 ± 0.87

SO4-2 mg/l 12.33 ± 2

Specific UV Abs. l/mg.m 0.23± 0.04

COD mg/l 41

Page 11: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

DOC and TN changes in the influents

Aerated influents

Influent DOC (mg/L)

TN (mg/L)

CW1

9.61

8.35

CW2

0.81

1.48

CW3

0.82

0.9

Non-aerated influents

Influent

DOC (mg/L)

TN (mg/L)

Cw1

9.61

8.35

CW2 0.59

2.17

CW3

0.74

1.34

FLOW

Page 12: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,
Page 13: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Total % Removal for DOC

78.00

80.00

82.00

84.00

86.00

88.00

90.00

92.00

94.00

96.00

98.00

Non Aerated CW3 Aerated CW3

% R

em

ova

l

Page 14: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Total % Removal for TN, NO3-, NO2

- and NH3+

-150.00

-100.00

-50.00

0.00

50.00

100.00

TN NO3-N NO2-N NH3-N

% R

em

ova

l

Non Aerated CW3

Aerated CW3

Page 15: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Organic Nitrogen % Removal

88

90

92

94

96

98

100

NA Control NA CW1 A. Control A. CW1

% R

emo

val

Page 16: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Total % removal of Phosphate & Sulfate

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

NA CW3 A. CW3

% R

emo

val

PO4

SO4

Page 17: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Fluorescence excitation and emission matrix (FEEM)

FEEM spectra analysis is a tool that helps to investigate which fractions of DOC are available in the water samples

Region Excitation (nm) Emission (nm) Description

1 320-350 400-480 Humic/Fulvic-

like organic

matter

fraction

2 240-280

430-480

Humic-like

organic matter

fractions

3 250-270 320-360 Protein-like

organic matter

fractions

Page 18: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

The organic matters fraction in the influent are proteins like only but the effluents are containing Humic/ Fulvic like organic matter fractions

A. CW3

Influent

NA CW3

Page 19: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Peak 3

Protein-like

organic

matter

fractions

Source Excitation

(nm) Emission

(nm) Intensity

Reduction in intensity

(%)

A CW1 275 355 8250 85

NA CW1 275 355 8250 85

A Control 275 355 6250 89

NA Control 275 355 17250 69

A CW3 275 355 11250 80

NA CW3 275 355 7500 86

Fluorescence EEM analysis of influent and effluent

Page 20: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Specific UV Abs. Changes

0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

Inffl1 NA CW1 NA CW2 NA CW3 A CW1 A CW2 A CW3

SUV

A (

L/m

g.m

)

Page 21: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Chloride concentrations changes through CWs

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

NA CW3 NA CW2 NA CW1 Inffluent A.CW1 A.CW2 A.CW3

Effl

ue

nt/

Inff

lue

nt

Because of 1. Plant water uptake

2. Evaporation

Page 22: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Physical-chemical properties of OMPs

No OMPs Name Conc (ng/l) M. Wt (g/mol) Kow pka

1 Acetaminophen 268 151.2 0.46 9.38

2 Atenolol 1927 266.34 0.16 9.6

3 Caffeine 831 194.1 -0.07 10.4

4 Fluoxetine 225 309.1 4.05 10.3

5 Sulfamethoxazole 322 253.3 0.89 5.5

6 Trimethoprim 651 290.1 0.91 7.12

7 Atrazine 546 215.7 2.61 1.7

8 Carbamazepine 649 236.1 2.45 13.9

9 DEET 387 191.1 2.18 0.67

10 Dilantin

248 252.3 2.47 8.33

Page 23: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

% Removal of OMPs through CW1 (1)

40.00

50.00

60.00

70.00

80.00

90.00

100.00

% R

emo

val

A. CW1 (d1)

NA. CW1 (d1)

A. CW1

NA. CW1

Page 24: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

% Removal of OMPs through CW1 (2)

-10.00

0.00

10.00

20.00

30.00

40.00

50.00

60.00

Atrazine Carbamazepine DEET Dilantin

% R

emo

val

A. CW1 (d1)

NA. CW1 (d1)

A. CW1

NA. CW1

Page 25: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Total % Removal of OMPs (1)

60.00

65.00

70.00

75.00

80.00

85.00

90.00

95.00

100.00

% R

emo

val

Aereated (d1)

Non- Aereated (d1)

Aereated

Non- Aereated

Page 26: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Total % Removal of OMPs (2)

-10.00

10.00

30.00

50.00

70.00

90.00

110.00

% R

emo

val

Aereated (d1)

Non- Aereated (d1)

Aereated

Non- Aereated

Page 27: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

% Removal of OMPs in Un-Planted CWs (1)

-20.00

0.00

20.00

40.00

60.00

80.00

100.00

Acetaminophen Atenolol Caffeine Sulfamethoxazole Trimethoprim

% R

emo

val

NA Control (d1)

A. Control (d1)

NA Control

A. Control

Page 28: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

% Removal of OMPs in Un-Planted CWs (2)

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

Atrazine Carbamazepine DEET Dilantin Fluoxetine

% R

emo

val

NA Control (d1)

A. Control (d1)

NA Control

A. Control

Page 29: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

What is the plant role Phragmites australis in CWs???

Page 30: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Nutrients reduction by the plant

0

10

20

30

40

50

60

70

80

90

100

NO3 TN Org. N PO4 SO4

% R

emo

val

NA Control

NA CW1

Reduction by plant

Page 31: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Ammonia reduction by the plant

-180

-130

-80

-30

20

70

120

170

220

270

NA Control NA CW1 Reduction by plant

% R

emo

val

Page 32: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

OMPs reduction by the plant

-20

0

20

40

60

80

100

120

% R

emo

val

NA. CW1

NA Control

Reduction by plant

Page 33: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Conclusions (1) Achievable Removals are: DOC (95%), TN (75%),

NH3+(99%), org N.(98%), and PO4

-3 (73%).

Plants “e.g. phragmites australis” in CWs play an essential role in the treatment especially for nitrogen and phosphates removals during secondary wastewater treatment. It removes; 15% (TN), 55% (Org. N.), 38% (NO3

-), and phosphate (22%).

The Plant also contributes effectively in removals of some OMPs such as: Acetaminophen, Caffeine, Fluoxetine, Sulfamethoxazole, and Trimethoprim.

Page 34: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Conclusions (2) Caffeine, Atrazine, Carbamazepine and Dilantin

showed better removals under Non Aerated conditions.

Humics and fulvic like organic matter where found in the effluents (especially in aerated row because of plant degradation.

Providing air gas to CWs systems enhances phosphate removal.

Page 35: Pharmaceutical Active Compounds Removal by Constructed ... · removals •Plant role in the treatment ... PhD thesis, Ghent Un., Belgium. Synthetic WW composition (Source: Jiang,

Thank You

and

Any

Question?