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Perf rform rmance Evalu luatio ion of Se Sele lected Pla lants and Ir Iron Rich ich Media ia for r Removal l of f PPCP CPs s fr from Wastewater in Co in Constructed Wetl tlands oottatep, S. K. Cha Chapagain , V. H. N. Pho T.


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SLIDE 1

Perf rform rmance Evalu luatio ion of Se Sele lected Pla lants and Ir Iron Rich ich Media ia for r Removal l of f PPCP CPs s fr from Wastewater in in Co Constructed Wetl tlands

  • T. Koo
  • ottatep, S. K. Cha

Chapagain, V. H. N. Pho

hong, Pan anuvatvanic ich - AI AIT

  • K. H. Ahn

Ahn - KI KIST

  • C. Polpr
  • lprasert – Th

Thammasat Uni niversit ity

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SLIDE 2

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 In Introduction  Objective  Methodology  Results an and dis iscussion  Con

  • nclu

lusions

Outline

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SLIDE 3

In Introduction

Pharmaceuticals ls and personal care products ts (PPC (PPCPs) Dis ischar arge to to en environment WWTPs s ar are les ess s efficient

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SLIDE 4

Ozonation

(Andreozzi et al., 2005)

RO

(Kimura et al., 2009)

AOP

(Ternes et al., 2003)

Process optimization

(Carballa et al., 2007)

4/33

In Introduction

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SLIDE 5

5

WWTS: De Developin ing cou

  • untrie

ies

  • On

On-site san sanitation systems (O (OSS) or

  • r De

Decentralized wastewater tr treatment system (D (DEWATS) ar are commonly use sed.

  • Over 80

80% of

  • f domestic wastewater is

is tr treated OOS in in Thail iland

  • Per cap

apit ita con

  • nsumption of
  • f Anti

tibiotic an and pain ainkill iller ar are als also hig igh

In Introduction

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SLIDE 6

Alternatives

Constructed wetland H2O2 Fe source +

Fenton reaction

In Introduction

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SLIDE 7

Ch Characterize H2O2 gen eneration and PPCPs rem emoval

  • f
  • f sele

elected aquatic pla lants Examin ine per erformance ir iron-rich med edia in in PPCP CPs removal in in la lab-scale CW CWs

1 2

PPCPs CWs Removal Mechanism Effect of plant, media H2O2 Research gaps

Objectives

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SLIDE 8

1st

st stag

age experim iment 3rd

rd stage expe

perim iment 2nd

nd stag

age exp xperiment Batch mode Batch mode Continuous mode Hydroponic conditions Actual wastewater Actual wastewater Porous media

3. . Meth thodology

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SLIDE 9

Sy Synth thetic ic WW WW ACT, AMX, ß - EST T = 1, 1000 μg/l /l Actu tual WW WW

ACT, AMX, ß – EST & mixtur ure e = = 10,00 000 0 μg/l /l

BATCH MODE

  • Cattail

il (Typha sps sps), ),

  • Vetiv

tiver (Vetiv iveria ria zizanio ioid ides), ),

  • Reed (Ph

Phragmites au austra ralis is)

  • Bird
  • f
  • f

parad adise (Streli elitzi tzia re regin inae)

  • HR

HRT = 0, 3, 7 da days

  • End

Endogenous H2O2 in in pla plant

  • ACT, AMX, ß - EST removal

effi ficiency

  • Plan

lant evaluation

  • Endogenous and aqueous

H2O2

  • ACT, AMX, ß - EST removal

effi ficiency

  • Aqu

Aqueous H2O2

  • ACT rem

emoval

  • NH

NH4+

  • De

Degradation pa pathways

Phas Phase 1 1 Phas Phase 2 2 BATCH MODE

  • Pl

Plan ant sp specie ies: Vetiv tiver

  • HR

HRT = = 0, 0, 1, 1, 3, 3, 5, 5, 7 7 da days

  • Wi

With th & & wi with thout po porous me media ia CON ONTI TINUOU OUS S MOD ODE

  • 30

30 da days

  • 6

6 da days sam samplin ling interval

  • Pl

Plan ant sp specie ies: Vetiv etiver er

  • Wi

With th por porous me media ia Materia ial Exper Experim iments Out utcomes Ph Phas ase e 3 Actu tual l WW WW ACT conc. = = 10 10,000 μg/l /l

Conceptual fr framework

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SLIDE 10

10

H2O2

2 conc

  • nc.

. lacks lacks of

  • f cl

clear ear tren ends ds High ighes est H2O2

2 in

in bir bird d of

  • f par

paradise, adise, follo

  • llowed

ed by ree eed, d, vetiver iver and and cattail. ail. H2O2 conc

  • nc.

. were hig highe her at lo low dose dose of

  • f PPCPs (1

s (1 ppb ppb) ) exce cept vetiver iver and and cattail. ail. Lo Low le levels els of

  • f H2O2 at hig

high h le level el of

  • f PPCPs d

s dose

  • se is

is lik likely ely due due to

  • it

its i s involvem

  • lvemen

ent in in PPCPs r s remo emoval. al. H2O2 was as ob

  • bser

erved ed rela elativ ively ely high high conc.

  • nc. feedi

eeding ng ACT, , wher hereas eas, , ele elevated ed H2O2 le level el was as ob

  • bser

erved ed in in vetiver iver plan plants u s unde nder hig high h dose dose of

  • f ACT (10

(1000 00 ppb ppb). ). ACT is is a a reac eactive ive and and mor

  • re

e stress essful ful PPCP to

  • plan

plant, , whe hereas, eas, vetiver iver plan plants s reac eact ACT stress ess mor

  • re

e sensit sensitively ively.

Results: 1st

st phase

0,5 1 1,5 2 2,5 3 3,5 1 ppb 1000 ppb 1 ppb 1000 ppb 1 ppb 1000 ppb Acetaminophen Amoxicillin β-estradiol Catatil Reed Vetiver Bird of Paradise

  • Conc. H2O2 (µmol/g FW)

H2O2 conc. . in n pla plant

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SLIDE 11

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PPC PPCP rem emoval l by y pla plants

95 95% removal for both low and high high doses

  • f
  • f ACT in

in 7 da days, Removal of

  • f AMX was lower than ACT

CT, fluctuated 31 31-96 96% in in high high dose (100 000 ppb), and 54 54-96 96% feeding in in low dose (1 pp ppb). In In low dose of

  • f feeding,

g, majority of

  • f plants

except typha removed AMX AMX almost at at 95 95% in in 7 da days. AM AMX is is rec ecalcitrant (Zh Zhan ang et et al al., 2014 2014). Removal

  • f
  • f

β-EST was

  • ccurred

at at smoothly, which was removed for 95 95-99 99% in in 7 da day ACT and β-EST were removed efficiently by by all all 4 ch chosen pla lants.

20 40 60 80 100 Day 0 Day 3 Day 7

Removal percentage (%)

20 40 60 80 100 Day 0 Day 3 Day 7

Removal percentage (%)

20 40 60 80 100 Day 0 Day 3 Day 7

Removal percentage (%)

20 40 60 80 100 Day 0 Day 3 Day 7

Removal percentage (%)

20 40 60 80 100 Day 0 Day 3 Day 7

Removal percentage (%)

20 40 60 80 100 Day 0 Day 3 Day 7

Removal percentage (%)

1 1 ppb ppb 1000 pp ppb

β-EST AMX ACT

Results: 1st

st phase

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SLIDE 12

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H2O2 concentratio ions in n water

2 4 6 8 10 12 14

without media with media without media with media without media with media without media with media Acetaminophen Amoxicillin Bata-estradiol Hospital wastewater with 3 PPCPs Day 0 Day 1 Day 3 Day 5 Day 7

  • Conc. H2O2 (µmol/L)

Hig igh le levels of

  • f H2O2 wer

ere ob

  • bse

served in in reactors op

  • perated with

ithout me media H2O2increased in in the consecutive sampling event (3 day), and then declined in in the sub subsequent sa sampling da day (5 da days and and 7 da days) s). In In contrast, H2O2 conc. in in reactors containing iron rich media was raised continuousl sly for

  • r 7 da

days, s, except reac eactor fed edding with ith ho hosp spital al was astewater. A relatively low level of

  • f H2O2in

in use of

  • f media use was likely due to

to Fenton reaction catalyzed by by ir iron.

Results: 2nd

nd phase

All l pla plants dem demonstr trated well ell po potentia ial of

  • f H2O2

pr production. . Robust roo

  • ot,

t, Veti tiver pla plant was as sel selected

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SLIDE 13

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 High High con

  • nc. H2O2 was

as ob

  • bserv

rved in in pl plants in in reactor

  • r wi

without med media ia  Increased conc. of

  • f H2O2 wit

ith in increasing HRTs (i (i.e. 5 and 7 days), ), could ld be be due due to to acc accumula lation of

  • f H2O2 pr

prod

  • duced in

in resp esponse to to str tress  Lo Low le levels ls of

  • f H2O2 observed in

in reactor havin ing media ia, li likely resu sult lt of

  • f advance

Fen enton reac eactio ion

0,5 1 1,5 2 2,5

without media with media without media with media without media with media without media with media Acetaminophen Amoxicillin Bata-estradiol Hospital wastewater

Day 0 Day 1 Day 3 Day 5 Day 7 Concentration H2O2 (µmol/g FW)

En Endogenous H2O2 in n pla plant

Results: 2nd

nd phase

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SLIDE 14

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Con Continuous fee eeding for

  • r 1 mon
  • nth

 It It sho hows the the inc ncreased rem emoval ACT wi with inc ncreasin ing op

  • per

eratio ion ti time Rem emoved >99 99% in in 12 12 da days of

  • f op
  • per

eratio ion.

0% 20% 40% 60% 80% 100% Day 0 Day 6 Day12 Day 18 Day 24 Day 30

Removal (%)

Operation time (days)

Results: 3rd

rd phase

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SLIDE 15

23/09/59 Degradation of ACT to end product

CH3-CO-NH2 + ·OH → CH3-COO- + NH4

+

NH NH4

+

in increase aft fter day 12 12

5 10 15 20 25 30 2 4 6 8 10 12 Day 0 Day 6 Day 12 Day 18 Day 24 Day 30

NH4

+ concentration (mg/L)

H2O2 concentration (μM) Operation time (days)

H2O2 NH4+

H2O2 con

  • ncentratio

ion in n pl plan ant t rhiz hizosphere (con

  • ntin

inuous mod mode)

Results: 3rd

rd phase

15

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SLIDE 16

16

 Veti tiver pla plants was as a mos

  • st ap

appropria iate  Levels ls of

  • f H2O2 was found hig

igher in in water, and pla lant le leaves in in reactor without med edia  H2O2 was lo low observ rved in in water and pla lants in in use use of

  • f media

ia, indicated the

  • cc
  • ccurrence of
  • f Fenton rea

eaction  ACT CT was removed more effic icie iently (i.e. 98 98.4 % and 97 97.5%) than AMX and β- EST (73 73 -92 92%), ), whereas, positi tive role le of

  • f iron-rich media

ia was observ rved in in PPC PPCPs rem emoval.  Ir Iron rich media ia couplin ing Fenton reactio ion was promis ising ,favored the advanced degradati tion of

  • f ACT

CT, yie ielding inorganic and le less toxic ic final products suc such as as NH NH4

+-N

Conclusions

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SLIDE 17

Thank you very ry much

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SLIDE 18

18

 Cos Costl tly to to analy lyze PPCP CPs  Oper erati tion in in th the actu ctual scale le for long long per eriod  Contribution of

  • f different componen

ents ts of

  • f CWs in

in PPCP removal ( Plant, media, phot

  • tolysis etc)

 Ch Characterization of

  • f end

nd product of

  • f PPCP

CP

Li Limitations and fu futu ture works

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SLIDE 19

Supporting Sli lides

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SLIDE 20

20

Fe2+ + H2O2 → Fe3+ + HO- + ·OH ………………(Eq. i) Fe3+ + H2O2 → Fe2+ + HO2 + H+ ………………..(Eq. ii)

Th Ther ere ar are repo eports on

  • n pr

prod

  • ductio

ion of

  • f reac

eactiv ive oxygen spe pecie ies (R (ROS) S) suc uch as as: : hydr droxyl l rad adic ical l (·OH OH) ) and and hydrogen per peroxid ide (H (H2O2) ) in n resp espon

  • nse to
  • en

envir iron

  • nmental

l str tress by y aqu aquatic ic pl plants, whe whereas, H2O2 is pr pre-requis isit ite of

  • f Fenton

reac eactio ion.

Supporting slides

23/09/59

Acetamide Acetate CH3-CO-NH2 CH3-COO

slide-21
SLIDE 21

Parameters Value (n=3) Unit ACT

  • 3. ± 0.8

μg/L pH 7.4 ± 0.4 DO 0.8 ± 0.9 mg/L SS 500 ± 240 mg/L COD 350 ± 160 mg/L NH4-N 25 ± 6.4 mg/L NO2

  • 4.7 ± 2.3

mg/L NO3

  • 1. ± 0.6

mg/L TKN 36.6 ± 12.6 mg/L TP 7.9 ± 4.3 mg/L

Table 2. Characteristics of hospital wastewater

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SLIDE 22

Hospital wastewater Synthetic wastewater Sand 5 cm Porous media H=60 cm 1 m

0.65 cm porous media+ 5 cm sand 0.8 m height and 0.45 m dia.

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SLIDE 23

A liter of water sample was collected, subsequently acidified to pH 3 by EDTA to minimize microbial activity and filtered by GF/B (Whatman). Solid-phase extraction was conducted with Oasis HLB sorbent

  • cartridges. The cartridges were pre-

conditioned with 6 mL DI water (pH=3.5) and the samples were percolated through the cartridges at a flow rate of 5 mL/min. After percolation, the cartridges were washed with 2 mL of DI water-methanol (95:5) and the eluent was discarded. The cartridges were finally wrapped by aluminum foil and stored in freezer. PPCPs determination by HPLC-MS/MS

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SLIDE 24

24

  • The generation of reactive oxygen species (ROS) such as H2O2 is a

common event associated with normal plant biochemical processes.

  • Plants also generate these ROS when exposed to a number of different
  • stresses. Thus, increased accumulation of H2O2 alerts the plant cell of

environmental stresses (Maksymiec and Krupa, 2006).

Plants, due to their ability to grow using sunlight and nutrients and due to their robust biomass are preferred as bioremediation agents for xenobiotic

  • pollutants. Vetiver (Vetiveria zizanoides L. Nash) is a high biomass, fast

growing grass species known for its massive root system and is recognized as a suitable plant for solving many of the environmental problems (Truong, 2000). The plant is known to be tolerant to toxic metals (Pang et al., 2003; Chen et al., 2004; Boonyapookana et al., 2005) and is used for rehabilitation

  • f mine wastes. There are reports on the use of this plant for phytoremediation
  • f soils contami- nated with heavy metals (Chen et al., 2004), polycyclic

aromatic hydrocarbons (Paquin et al., 2002), petroleum (Brandt et al., 2006) and 2,4,6-trinitrotoluene (Markis et al., 2007a, b). To the best of our knowledge, there are no reports on the use of V. zizanoides for the remediation of phenol and its influence on antioxidant enzymes.

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SLIDE 25

25

Peroxides (PO) and Peroxidase enzyme: A peroxidase is one of a number of enzymes that act as catalysts to allow a variety of biological processes to take place. Specifically, they promote the oxidation of various compounds using naturally occurring peroxides, especially hydrogen peroxide (H2O2), which are reduced, forming water. Peroxides are created as byproducts of various biochemical reactions within organisms, but can cause damage as they are oxidizing agents. Peroxidases break these compounds down in to harmless substances by adding hydrogen, obtained from another molecule — known as a donor molecule — in a reduction-oxidation (redox) reaction in which the peroxide is reduced to form water, and the other molecule is oxidized. There are a large number of these enzymes, and they are found in plants and animals, including humans.

Role in Biological Systems A number of peroxidases are found in plants, where they may help minimize damage caused by stress factors or insect pests. When plants are subjected to stress — such as drought or high temperatures — or to attack by pests, this tends to result in the release of reactive oxygen species (ROS). These are forms of oxygen, or compounds of this element, including hydrogen peroxide, in which the oxygen is very reactive, and can damage or kill cells. It is thought that peroxidases remove ROS, helping prevent damage. Peroxide (peróxido, perossido, Peroxid neuter) Chemical compound containing two oxygen atoms, each of which is bonded to the other and to a radical or some element other than oxygen; e.g., in hydrogen peroxide (H2O2) the atoms are joined together in the chainlike structure H-O-O-H. Peroxides are unstable, releasing oxygen when heated, and are powerful oxidizing agents. Peroxides may be formed directly by the reaction of an element or compound with oxygen. The simplest stable peroxide is hydrogen peroxide. Superoxides, dioxygenyls, ozones and ozonides are considered separately

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SLIDE 26

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Advanced oxidation processes (abbreviation: AOPs), in a broad sense, are a set of chemical treatment procedures designed to remove organic (and sometimes inorganic) materials in water and waste water by oxidation through reactions with hydroxyl radicals (·OH).[1] In real-world applications of wastewater treatment, however, this term usually refers more specifically to a subset of such chemical processes that employ ozone (O3), hydrogen peroxide (H2O2) and/or UV light.[2] One such type of process is called in situ chemical oxidation AOPs rely on in-situ production of highly reactive hydroxyl radicals (·OH). These reactive species are the strongest oxidants that can be applied in water and can virtually oxidize any compound present in the water matrix, often at a diffusion controlled reaction

  • speed. Consequently, ·OH reacts unselectively once formed and contaminants will be

quickly and efficiently fragmented and converted into small inorganic molecules. Hydroxyl radicals are produced with the help of one or more primary oxidants (e.g.

  • zone, hydrogen peroxide, oxygen) and/or energy sources (e.g. ultraviolet light) or

catalysts (e.g. titanium dioxide). Precise, pre-programmed dosages, sequences and combinations of these reagents are applied in order to obtain a maximum •OH yield. In general, when applied in properly tuned conditions, AOPs can reduce the concentration

  • f contaminants from several-hundreds ppm to less than 5 ppb and therefore

significantly bring COD and TOC down, which earned it the credit of “water treatment processes of the 21st century

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SLIDE 27

27

Con

  • nsumption of PPCPs

Antib tibiotic: Amoxicil illi lin Thaila iland 5.4 .43 g/p /person/year Ger ermany 1.3 .39 g/p /per erson/year Analg lgesic or Pain in kille iller: Acetaminophen (p (paracetamol) l) Thaila iland 47g/p /person/yea ear Ger ermany 1.3 .39 g/p /per erson/year

WWTS: De Developin ing countrie ies

  • On

On-sit ite sanit itation systems (O (OSS) or

  • r De

Decentrali lized wastewater tr treatment system (DE (DEWATS) are com

  • mmonly used

ed.

  • Over

er 80% of

  • f dom
  • mestic

wastewater is is tr treated ed OOS in in Thaila iland

In Introduction

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