May 9, 2013

REMOVAL OF PHARMACEUTICALS BY PAC ADSORPTION

Qianru Deng PNWS-AWWA 2013

Acknowledgements
North Carolina Urban Water Consortium for funding this research.

Co-author: Koichi Ohno and Detlef Knappe

Pre-research Questions

Why pharmaceuticals? Why PAC? What's new with PAC How well do PACs work for pharmaceutical removal?

Concern of Pharmaceuticals

Human Waste

Unused drugs

The drugs we use (or dispose improperly) may end up in our Sewage lakes, rivers and oceans, and potentially in our tap water. Wastewater Treatment Plant

Natural Water Body

Drinking Water Treatment Plant Tap Water

Concern of Pharmaceuticals
Concentrations: ng/L to g/L range

Eco-toxicological Effects
EDCs - Example: estrogenic hormones PhACs - Example: antibiotics X

Potential Human Health Risk

X

EPA's CCL
From On Tap Magazine Winter 2003

Removal of Pharmaceuticals from Drinking Water

Process Sedimentation Oxidation: Effectiveness Very low Medium - High

- Chlorine - Ozone - AOP

UV Light Adsorption: - GAC - PAC

High/Selective High/Selective High

Low Medium - High Medium - High Medium - High

Powdered Activated Carbon (PAC) Adsorption

A new type of PAC: sub-micrometer PAC, or S-PAC

Performance of PAC in coagulation/flocculation/ sedimentation process

Research Objectives

Assess the effectiveness of PAC adsorption process for pharmaceutical removal Identify factors that affect the removal
- pH - Background NOM - PAC particle size

Evaluate the application of PAC in conjunction with coagulants

Materials and Methods

Pharmaceuticals
O H2N S O N O NH
H3C H3C O
CH3

O H2N N N NH2
H2N

Cl NH

N CH3

CH3
O CH3

O O H3C

Sulfamethoxazole (SMX) pKa=5.8 (0/-)

O NH

Trimethoprim (TMP) pKa=7.2 (+/0)

Metoclopramide (MCP) pKa=9.7 (+/0)

Cl OH NH

H3C H3C
O

Cl O

CH3

O OH

O H3C

Cl

CH3

OH

Bezafibrate (BZF) pKa=3.3 (0/-)

Diclofenac (DCF) pKa=4.2 (0/-)

Ibuprofen (IBP)

pKa=4.4 (0/-)

Powdered Activated Carbons (PACs)

d50 (m)

PAC Name

Material

Activation Method

NuChar

Wood

Chemical

22-26

Hydrodarco B

Lignite Coal

Thermal

18

WPH

Anthracite Coal

Thermal

17.2

S-WPH

Anthracite Coal

Thermal

0.311

S-WPH was developed by wet-milling WPH

Experimental and Analytical Methods

Water
OWASA (University Lake/Cane Creek Reservoir blend, Carrboro, NC)
pH: ~7.2 pH: ~7.9 TOC: ~5.0 mg/L TOC: ~7.3 mg/L

Cary Wastewater Treatment Plant Effluent (WWTPE) (Cary, NC) Spiked pharmaceutical concentration: ~100 g/L

Experiments
Batch kinetic tests Batch isotherm tests Jar tests

Analytical Methods
High-performance liquid chromatography (HPLC) equipped with a dual-wavelength UV detector and a C18 column

Results and Discussions

1. Batch Tests

Sample residual pharmaceutical concentration as a function of time Kinetics tests: 0-2 hour contact time Isotherm tests: 2 week contact time

1. Adsorbability of Pharmaceuticals
PAC: NuChar
100 80

Dose: 10 mg/L
MCP TMP BZF DCF IBP SMX

Removal, %

60 40 20 0 0 50 100

150

Time, min

Most adsorbable: Trimethoprim (TMP) and Metoclopramide (MCP) Least adsorbable: Sulfamethoxazole (SMX) and Ibuprofen (IBP)

2. Effect of pH
PAC: NuChar
100

Dose: 20 mg/L
pH 4 pH 5.5 pH 7

100

PAC: NuChar

Dose: 5 mg/L
pH 7 pH 5.5 pH 4

SMX Removal, %

80 60 40 20 0 0 50 100

TMP Removal, %

80 60 40 20 0

Anionic fraction decreases

Cationic fraction decreases

150

50

100

150

Time, min Removal of acidic compounds increases with decreasing pH. Time, min Removal of basic compounds increases with increasing pH.

pKa of SMX: 5.8

pKa of TMP: 7.2

3. Effect of natural organic matter (NOM) in background water

OWASA-NuChar-20 mg/L Cary WWTPE-NuChar-20 mg/L

100

100

SMX Removal, %

80 60 40 20 0 0 50 100 150

TMP Removal, %

80 60 40 20 0 0 50 100 150
OWASA-NuChar-10 mg/L Cary WWTPE-NuChar-10 mg/L

Time, min

Time, min

OWASA: pH ~7.2 Cary WWTPE: pH ~7.9

TOC ~ 5.0 mg/L TOC ~ 7.3 mg/L

Background NOM adversely affected pharmaceutical adsorption.

4. Effect of PAC particle size

PAC Dose: 10 mg/L
100
S-WPH WPH

100

SMX Removal, %

80

SMX Removal, %

80 60

15 min 120 min 2 Weeks

60
40 20 0 0 50 100 150

40
20 0
WPH S-WPH

Time, min

SMX kinetics: S-WPH>>WPH SMX capacity: S-WPHWPH S-WPH almost reached adsorption equilibrium at ~15 min!

4. Effect of PAC particle size

PAC Dose: 5 mg/L
100
S-WPH

100

TMP Removal, %

60

TMP Removal, %

80

WPH

15 min 120 min 2 Weeks

80 60 40 20 0
WPH S-WPH

40
20 0 0 50 100 150

Time, min

TMP kinetics: S-WPH>>WPH TMP capacity: S-WPHWPH S-WPH almost reaches adsorption equilibrium at ~15 min!

4. Effect of PAC particle size

PAC Dose: 10 mg/L
50
120 min 2 Weeks

50

120 min 2 Weeks

UV 254 Removal, %

DOC Removal, %

40

40 30 20

30
20

10 10 S-PAC greatly enhanced pharmaceutical and NOM removal.

How to utilize it? 0

WPH

0
S-WPH
WPH S-WPH

NOM capacity: S-WPH>>WPH S-WPH provides better NOM removal (S-WPH2WPH)!

Control DBP Formation?

Control Membrane Fouling?

2. Jar Tests

Rapid mixing: 100 rpm for 30 seconds (Coagulation) Slow mixing: 25 rpm for 36 minutes (Flocculation) Settling: 3.5 minutes (Sedimentation)

5. Effect of PAC particle size and timing of PAC addition

Coagulant: Alum
100

Dose: 55 mg/L

pH: 6.2
WPH

PAC Dose: 5 mg/L

100

PAC Contact time: ~40 min

WPH S-WPH

SMX Removal (%)

80 60 40 20 0 Coagulant Alone PAC Alone PAC 5 min Before Coagulant PAC together with Coagulant PAC 9 min After Coagulant

TMP Removal (%)

S-WPH

80 60 40 20 0 Coagulant Alone PAC Alone PAC 5 min Before Coagulant PAC together with Coagulant PAC 9 min After Coagulant

SMX removal: S-WPH2-3WPH TMP removal: S-WPH1.5-3WPH Aluminum hydroxide floc adversely affected TMP removal. The interference was largest when PAC was added together with alum.

5. Effect of PAC particle size and timing of PAC addition

Coagulant: Alum
100

Dose: 55 mg/L

pH: 6.2
WPH S-WPH

PAC Dose: 5 mg/L

100

PAC Contact time: ~40 min

WPH S-WPH

UV254 Removal (%)

80 60 40 20 0
Coagulant PAC Alone PAC 5 min PAC PAC 9 min Alone Before together After Coagulant with Coagulant Coagulant

DOC Removal (%)

80 60 40 20 0
Coagulant Alone PAC Alone PAC 5 min Before Coagulant PAC together with Coagulant PAC 9 min After Coagulant

Coagulant primarily contributed to NOM removal. Timing of PAC addition did not affect NOM removal.

5. Effect of PAC particle size and timing of PAC addition

Coagulant: Alum
100

Dose: 55 mg/L

pH: 6.2
WPH S-WPH

PAC Dose: 5 mg/L

100

PAC Contact time: ~40 min

WPH S-WPH

Turbidity Removal (%) 3.5 min settling

Turbidity Removal (%) 10 min settling

80 60 40 20 0
Coagulant Alone PAC 5 min Before Coagulant PAC together with Coagulant PAC 9 min After Coagulant

80 60 40 20 0 Coagulant Alone PAC 5 min Before Coagulant PAC together with Coagulant PAC 9 min After Coagulant

S-WPH was incorporated into settleable floc, but floc settleability was adversely affected. PACs were better incorporated into floc when added before or together with coagulant.

6. Effect of PAC dosage

Coagulant: Alum
100

Dose: 55 mg/L
100

PAC contact time: ~40 min

SMX Removal (%)

IBP Removal (%)

80 60 40 20 0 0 20 40 60 80
S-WPH NuChar WPH Hydrodarco-B 5

80 60 40 20 0 0 20 40 60 80
S-WPH NuChar WPH Hydrodarco-B 5

100

120

140

100

120

140

PAC Dose (mg/L)

PAC Dose (mg/L)

Required dosage for 90% SMX and IBP removal: ~ 25 mg/L for S-WPH 100 mg/L for normal PACs

6. Effect of PAC dosage

Coagulant: Alum
100

Dose: 55 mg/L

PAC contact time: ~40 min

100 80 60 Alum Alone 40 20 0 0 20 40 60 80 S-WPH NuChar WPH Hydrodarco-B 5 100 120 140

UV254 Removal (%)

60 40 20 0 0 20 40 60 80

Alum Alone

S-WPH NuChar WPH Hydrodarco-B 5 100 120 140

PAC Dose (mg/L)

DOC Removal (%)

80

PAC Dose (mg/L)

Alum primarily contributed to NOM removal. Required dosage for extra 10% NOM removal: 5 mg/L for S-WPH 40-60 mg/L for normal PACs

Conclusions
How well did PACs do for pharmaceutical removal? PACs effectively removed some pharmaceuticals.
- At 1-h contact time, 10 mg/L of PAC removed 95% TMP, but only 17% SMX - In jar tests, required dose of PAC for 90 % SMX and IBP removal was 100 mg/L

New PAC: sub-micrometer PAC (S-PAC)?removal. S-PAC greatly enhanced pharmaceutical

- At 1-h contact time, 10mg/L of S-PAC removed 60% SMX - In jar tests, required dose of S-PAC for 90 % SMX and IBP removal was 25 mg/L

How tocan separate S-PAC from water? S-PAC be incorporated into settleable floc, but with poorer settleability. PAC Where should and when be added to add before PAC into coagulant. the train?
- Higher TMP removal - Lower settled water turbidity

Questions?

Removal of Pharmaceuticals by PAC Adsorption

Qianru Deng: Qianru.Deng@mwhglobal.com Koichi Ohno: ohnok@eng.hokudai.ac.jp Detlef Knappe: knappe@ncsu.edu

PNWS-AWWA 2013 Spokane, WA

NOM Adsorption Mechanism

NOM is able to penetrate only certain distance into PAC particles. (Matsui et al., 2009)

Normal PAC

Sub-micrometer PAC

Jar Test Kinetics

Coagulant: Alum
100 S-WPH WPH 80

Dose: 55 mg/L
100

pH:6.2

PAC Dose: 5 mg/L

80

SMX Removal, %

60

TMP Removal, %

60 40

40

20

20 S-WPH WPH 0 10 20 30 40 50

0 0 10 20 30 40 50

PAC

Time, min

PAC

Time, min

Alum

Alum

Flocculation

Sedimentation

Flocculation

Sedimentation

Pharmaceutical removal in jar tests occurred mostly in flocculation process.