Removal of Endocrine Disrupting Compounds from Urban Waste

Water using a novel process combining PAC (Powder Activated

Carbon) and ballasted clarification

➢ Actiflo® Carb

▪ Process descriptions

▪ Applications

▪ References

➢ Micropollutants within urban waste water

▪ A wide range of pollutants and concentration

▪ Typical performance data of biological waste water plants

➢ Micropollutants removal with Actiflo® Carb

▪ Process descriptions

▪ First References

▪ Perspectives using Frogbox®

2

Agenda

Actiflo® Carb

Proces description, usages and

references

o Ballasted clarification:o Short floculation time

o High clarification rate : 40 to 60 m/h (waste water)

o Benefits of recirculated PACo Constant availability of PAC for adsorption

o Continuous removal

1

2

3 4

5

67

1 = New PAC2 = PAC reactor3 = Coagulation4 = Flocculation 5 = Clarifier6 = Cycloning PAC removal7 = PAC recirculation

PAC under microscope

Process descriptive

• Natural Organic Matter

• Disinfection By Products

• Pesticides (atrazine, metaldehyde, DEA...)

Drinking water

• Endocrine Disruptors (hormones...)

• Drugs residues (antibiotic, anti-inflammatory, anti-epilectic...)

• Biocides

Waste water

Any pollutants with an affinity with PAC

Over 12 years of experiences

Applications

Corporate Municipal Marketing - September 2016 6

Parker WSD, CO, (38 MLD)

Indianapolis, IN, (91 MLD) Medias, Romania

(16 MLD)

Huntsman, China, (1 MLD)

Harpeth VUD, Nashville, TN,

(90 MLD)

Rexam Plastic, China,

(0.2 MLD)Guangzhou,LGInd.Park China,

(36 MLD)

Beash Dam, Saudi Arabia

(31 MLD) Rizal Prov. Gr. Manila Philippines (77 MLD)

Drinking Water (40 Ref / (total 1,138 MLD)Municipal Wastewater ( 5 Ref. / (total 446 MLD)Industrial Water & WW ( 6 Ref./ (total 76 MLD))

DSM NUTRITIONAL, F (2.5 MLD)

Tongxiang, China(66 MLD)

Fuyang, China(250 MLD)

Jiaxing, China(2x50 MLD)

Design & Build

Solutions

France30 Refs

(680 MLD)USA

4 Refs(236 MLD)

China12 Refs

(619 MLD)

A world wide extension

Actiflo® Carb – Drinking water plants in operation

Surface water with colour and Algae

TOC 3 to 6 mg/l & pesticides (50 to 75% removal)

µ Coagulation

Geosmin & MIB Tests Results

Geosmin (in) Geosmin (out)

MIB (in) MIB (out)

Ge

osm

in

(mg

/l)

MIB

(m

g/l

)

IN (ppb) Out (ppb)

Removal (%)

Atrazine 0.36 0.05 86

DEA 0.26 < LQ > 93

DEDIA 0.37 0.03 92

Isoproturone 0.40 < LQ > 98

Acetochlorine 0.77 < LQ > 94

Bentazone 0.37 0.04 89

Glyphosate 0.23 < LQ > 68

Acetochlorine 0.22 < LQ > 68

Actiflo® Carb – Moses Indianapolis

Actiflo® Carb

for pesticides removal

Pesticide Removal : testing under “live” conditions

10

o Dosing of pesticides in the raw water (reservoir) to simulate peaks of concentrations

o Target concentration in the raw water: 0.3 µg/L

Compounds Inlet T +1h

Outlet T + 1h

% removal Outlet T + 24h

% removal

[mg/L] [mg/L] [%] [mg/L] [%]

Atrazine 0.39 n.d. >95 n.d. >95

DEA 0.34 n.d. >94 n.d. >94

DEDIA 0.36 n.d. >94 n.d. >94

Isoproturon 0.66 n.d. >97 n.d. >97

Acetochlore 0.81 n.d. >97 0.24 70.4

Bentazone 0.27 n.d. >92 0.03 89.0

Glyphosate 0.35 n.d. >77 n.d. >77

AMPA 0.46 n.d. >82 n.d. >82

Eff. Removal > 77 to 97%n.d.: below detection level

Pesticides removal

Spiking program

• Pesticide spiking changed each day (up to 1.5 µg/L)• Metaldehyde, carbetamide, metazachlor and propyzamide

• Main conditions target for each week

12

Inlet Load, PAC dosing

Target: Test upper limits of Actiflo®Carb process

Actiflo® carb (most recent tests)

Trials in 2015 for Metaldehydes removal: North Mymms WTW with Affinity Water – DTP support of VWT (UK) for Metaldehyde (CH3CHO)4

Particularly challenging compound for traditional technologies eg GAC LogKow < 0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

15/4/15 9:10 16/4/15 9:20 16/4/15 14:00 16/4/15 16:00 17/4/15 11:00

Met

alde

hyde

con

cent

rati

on (µ

g/L)

Date

North Mymms phase II - Actiflo®Carb - Metaldehyde concentrationWeek 1

Raw Water Inlet Actiflo® Carb Outlet Actiflo® Carb

0.0090.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

28/4/15 13:10 28/4/15 14:45 29/4/15 15:15 30/4/15 12:15 30/4/15 14:00 1/5/15 12:00 10/5/15 13:10

Conc

entr

atio

n (µ

g/L)

Date

North Mymms phase II - Actiflo® Carb - Total Pesticide concentrationWeek 3

Raw water Inlet Actiflo® Carb Outlet Actiflo® Carb

0.031

2018 America’s Sales Meeting 7

Micropollutants in urban waste water

Pharma residuals during 2010 - 2011

15

N

FRANCE

Paris

Marne

Seine

STEP

Marne Aval

75 000 m3.j-1

STEP - Seine Amont

600 000 m3.j-1

STEP - Seine Centre

240 000 m3.j-1

STEP - Seine Aval

1 700 000 m3.j-1

10 km

STEP - Seine Grésillons

100 000 m3.j-1

Sites de prélèvement en Seine

Stations d’épuration du SIAAP

Déversoirs d’orages SIAAP

1

23

4

5

6

7

1

2

Oise

Pharma residuals during 2010 - 2011

16

Co

nce

ntr

atio

n m

édia

ne

(ng.

l-1)

Fréqu

ence d

e détectio

n (%

)

1

10

100

1000

Sufa

chlo

rpyr

idazi

ne

Sulfa

méra

zin

e

Sulfa

méth

oxa

zole

Ery

thro

myc

ine

Spiram

ycin

e R

oxith

rom

yci

ne

Trim

éth

oprim

e A

mpic

illin

e A

moxi

cilli

ne

Oxy

tétr

acy

clin

e C

hlo

rtétr

acyc

line

Tétr

acy

clin

e A

cid

e o

xolin

ique

Cip

rofloxa

cine

Norf

loxacin

e O

floxaci

ne

Para

ceta

mol

Acid

e acé

tyls

alic

yliq

ue

Acid

e s

alic

yliq

ue

Nefo

pam

Dic

lofe

nac

Ibupro

fène

2-h

ydro

xy

ibupro

fen

Kéto

pro

fène

Napro

xène

Carb

am

azépin

e P

rim

idone

Beza

fibra

te F

enofib

rate

Clo

fibra

te G

em

fibro

zil

Acebuto

lol

Méto

pro

lol

Pro

pra

nolo

l S

ota

lol

Bro

mazepam

Dia

zepam

Flu

oxetine

Acid

e d

iatr

izoïq

ue

Co

ncen

trati

on

(n

g/L

)

0

10

20

30

40

50

60

70

80

90

100

Occu

ren

ce (

%)

Max =1200 ng/L

Antibiotiques Analgésiques Anti-épileptiques Hypolipémiants Bétabloquants Antidépresseurs

Produit de

contraste

Overview of some molecules across Paris

17

Flux (g.j-1) Campagne du 20 octobre 2011 (Q Austerlitz = 160 m3.s-1)dfhs

0

1000

2000

3000

4000

5000

6000

7000

8000

Sulfa

mét

hoxa

zole

Spira

micine

Acé

tam

inop

hène

- Par

acet

amol

2-h

ydro

xy ib

upro

fen

Két

opro

fen

Car

bam

azép

ine

Mét

ropr

olol

Sot

alol

Flu

x (

en

g/j

ou

r)

Choisy Bougival Triel

Gradient spatial marqué entre l’amont et l’aval de l’agglomération parisienne

dfhs

0

1000

2000

3000

4000

5000

6000

7000

8000

Sulfa

mét

hoxa

zole

Spira

micine

Acé

tam

inop

hène

- Par

acet

amol

2-h

ydro

xy ib

upro

fen

Két

opro

fen

Car

bam

azép

ine

Mét

ropr

olol

Sot

alol

Flu

x (

en

g/jo

ur)

Choisy Bougival Triel

The context: typical WwTW performances

18

Verschiedene Quellen (1996-2010) aus Beier, S. et al. 2010

20 à 40% removal

depending on molecules

Hospitals

Inlet

Outlet

Rivers

Drinking water

12 months operational study with SIAAP*

• Organisation & scientific plan

– To operate on a real plant

– 138 micropolluants analysed

WwTW Seine Aval (Achères) 6 million

Pop. eq. – removal C/N/P

Sand and

grease catcherScreening

Seine river

Sewer

Settling

Pré-treatment

Treated water

Primary treatment

Carbon biological treatment (activated sludge)

Phisico-chemical

lamellar settling

Activated sludge tank Secondary settling

Total nitrification

Air

Nitrogen biological treatment (bioflters)

Denitrification

Daily monitoring

TSS, DOC, BOD, DOC, TKN, NO3, NO2, Pt, P-

PO4, Colour , Turbidity, Abs. UV 254 nm

Pharmaceutical and Hormones

Antibiotiques (humains et vétérinaires),

analgésiques, bétabloquants, hypolipémiants,

antidépresseurs, antiépileptiques, diurétiques,

antifongiques, hormones

Other micropollutants

HAP, solvants chlorés, Alkylphénols,

herbicides/insecticides, acides perfluorés,

bisphénol A, Métaux

MEDICAMENTS HUMAINS MEDICAMENTS VETERINAIRES HORMONES DIVERS

Naphtalène Alachlore Metronidazole Florfenicol α oestradiol PFOA

Acénaphtylène Atrazine Trimethoprim Sulfanilamide β oestradiol PFOS

Acenaphtène Chlorfenvinphos Sulfamethoxazole Dicyclanile Estrone Bisphénol A

Fluorene Diuron Ofloxacine Sulfadiazine Estriol

Phenanthrene Isoproturon Ciprofloxacine Sulfathiazole Norethindrone

Anthracene Pentachlorophénol Roxithromycine Marbofloxacine Androstenedione

Fluoranthene Simazine Paracétamol Ampicilline Gestodène

Pyrène Trifluraline Kétoprofene Norfloxacin Testosterone

Benzo[a]anthracene HCH alpha Diclofenac Tétracycline Levonorgestrel

Chrysène HCH béta Ibuprofène Oxytetracycline Progesterone

Benzo[b]fluoranthène HCH gamma Naproxen Sulfabenzamide

Benzo[k]fluoranthène HCH delta Acide salicylique Danofloxacine

Benzo[a]pyrène Chlopyrifos Aténolol Enrofloxacine

Indeno[1,2,3-cd]pyrène Aldrine Propranolol Orbifloxacine

Dibenz[a,h]anthracène Isodrine Fenofibrate Difloxacin

Benzo[ghi]perylène Endosulfan alpha Bezafibrate Sulfadimethoxine

1,2,4-trichlorobenzène DDE pp Fluvoxamine Chlortetracycline

Hexachlorobutadiène Dieldrin Oxazepam Penicilline G

Hexachlorobenzène Endrin Lorazepam Tylosine Tartrate

BPA DDD pp Carbamazepine Erythromycine

Nonylphénol DDT op Furosemide Monensin

4-nonylphénol Endosulfan béta Econazole Narasin

Octylphénol DDT pp Sulfameter

Para-ter-octylphénol Sulfadimerazine

LISTE DCE

Micropolluants organiques

HAP Herbicides / insecticides Antibiotiques Bétabloquants Antidépresseurs / anxiolytiques Diurétique HormonesSolvants chlorés Alkylphénols Analgésiques Hypolipémians Antiépyleptique Antifongique Perfluorés

Often found Seldom foundAlways

found

Micropollutants analysed

Box plot final effluent quality

SO4Cl F AOXSr Fe Mn Zn Ba Al

1

10

100

1000

10000

Co

ncen

trati

on

s (

un

ités l

og

)

Minimum/Maximum

Ni V Cu Co Sb Cr Pb Ag Cd0,001

0,01

0,1

1

10

Co

ncen

trati

on

s (

un

ités l

og

)

Résultats métaux

(4 campagnes – 2

configurations, 11 campagnes

en attente de résultats)

Faible variabilité des

concentrations et ordres de

grandeur conformes aux

suivis RSDE des usines du

SIAAP

mg/

L

µg/L

µg/L

0,1

1

10

100

1000

10000

0,1

1

10

100

1000

10000

Minimum/Maxi…

Box plot organic micropollutants

0,1

1

10

100

1000

10000

Co

nce

ntr

atio

ns

(un

ité

s lo

g)D

iclo

fen

ac

Ké

top

rofe

ne

Par

acé

tam

ol

Nap

roxe

n

Ibu

pro

fèn

e

Ofl

oxa

cin

e

Sulf

ame

tho

xazo

le

Trim

eth

op

rim

Cip

rofl

oxa

cin

e

Ro

xith

rom

ycin

e

Me

tro

nid

azo

le

Até

no

lol

Pro

pra

no

lol

Oxa

zep

am

Lora

zep

am

Car

bam

aze

pin

e

Be

zafi

bra

te

No

rflo

xaci

ne

Eryt

hro

myc

ine

Sulf

adia

zin

e

Estr

on

e

Bis

ph

én

ol A

PFO

S3

PFO

AP

ara

-ter-

octy

ph

én

ol

Diu

ron

Atr

azin

e

Analgésiques

Ab humains

Bêtabloquants

Anti-déprésseurs

Antiépileptiques

Hypolipémiants

Ab vétérinaires

Hormones

Bisphénol A

Perfluorés

DCE - herbicides

ng/l

Plus forte variabilité des concentrations

Actiflo® Carb

Micropollutants removal

o Avranches (France) – Pilot trials

o 18 months Actiflo Carb (2010 – 2012)

o PAC alone and combined with O3

o Industrial prototype – Cham (Lucerne, CH)

o 6 months trials in 2011 in cooperation with :

o Industrial unit 50 to 100 m3/h

o Industrial prototype – Milwaukee (USA)

o 4 months trials in 2011

o Industrial unit 50 to 100 m3/h

o Aachen (Germany) – Pilot trialso 6 months trials - RWTH Aachen

Over 10 pilot plants trials since 2010

0

20

40

60

80

100

120

Elim

inat

ion

%

Norit SAE Super PICA AFP23 CSC HPC HZ 1050

Average 55%Average 69% Average 69%

1. Analyses by Eawag (2011)

o CAP dose 10 ppm, CAP concentration in reactor 1 – 2 g/l

o Contact time 10 mn

Re

mo

val[

%]

Various PAC tested (Norit, Jacobi, Calgon, etc…)

➢ Actiflo® Carb : micropollutants removal

Micropollutants removal

26

Micropolluants

Abattement en %Sites et quantités de CAP

Aachen Achères Avranches Bruxelles Lucerne

10 ppm 20 ppm 30 ppm 5 ppm 10 ppm 15 ppm 20 ppm 20 ppm + O3 15-20 ppm 10 ppm

Atenolol / / / 38 47 67 90 92 / 76Metoprolol 88 91 95 / / / 69 76 82 85Propanolol / / / 75 88 95 / / 88 /

Clarithromycine 37 70 63 / / / / / 79 76Sulfamethoxazole 28 68 74 28 39 39 77 88 69 45

trimethoprim / / / 68 72 80 / / 79 95Diclofenac 57 89 91 38 45 60 82 97 71 65Bezafibrate / / / 20 15 30 / / 31 78

Carbamazepine 83 94 96 40 60 72 98 99 82 76

0,1

1

10

100

1000

10000

• Inlet quality : Pharma residues and hormones

0,1

Co

nce

ntr

ati

on

s n

g.l

-1

Analgésiques Antibiotiques

1

10

100

1 000

10 000

Analysis results over 24 campaigns of sampling

0

20

40

60

80

100Analgésiques Antibiotiques

Ab

att

em

en

ts (

%)

0

20

40

60

80

100

Average removal over 33 molecules :

> 70% for 5 molecules, [40 – 70%] for 11 molécules and < 40% for 9 molécules

Median removal

Synthesis over 6 molecules (cumulative concentration)

0

10

20

30

40

50

60

70

80

90

100

60-5-0 XX-10-0 40-15-0

ab

att

em

en

t m

oyen

(%

)

Vs PAC dose rate

Molecules of

reference

Diclofenac

Ibuprofene

Sulfamethoxazole

Atenolol

Propanolol

Carbamazepine

Mass removal

Actiflo® Carb

“hard” COD removal

Municipal wastewater

China Zhejiang Fuyang TertiaryActiflo Carb operation as needed to reduce refractory COD from nearby

paper mill

Industrial wastewater

ChinaShandon

gHuntsman, Qingdao HPI / CPI

Tertiary; removal of refractory COD from WW with dye chemicals used

in textile industry; very high COD up to > 900 mg/l

Industrial wastewater France

haut-rhin

DSM NutritionalProducts France, Village-

Neuf (close to Basel, Switzerland)

PharmaTertiary treatment after AS for TSS &

refractory TOC/COD removal; and pharma micropoll removal

Industrial wastewater

Italy SICRaffineria di Milazzo,

Milazzo (Sicily)HPI / CPI

Secondary clarification of MBBR effluent with Actiflo Carb; removal of refractory COD up to 200 mg/l;

reuse for fire protection water system

Actiflo® Carb for industrial effluents (« Hard COD »)

DSM references : Mulhouse, France

Date Débit alim Vitesse MES alim COT alimDosagepolymère

Dosage FeCl3

Dosage CAP

Type CAP pH rejet MES rejet COT rejet

m3/h m/h mg/l mg/l mg/l mg/l g/l upH mg/l mg/l

21/04/2015 60 30 500 40 0,7 100 _ _ 7,0 7

22/04/2015 35 12 240 30 0,7 100 _ _ 7,4 9

22/05/2015 65 32 65 140 1,5 250 1 HCAP2 6,9 19 15

08/06/2015 65 32 30 1,5 250 1 HCAP2 6,5 21

09/06/2015 65 32 15 1,5 350 1 HCAP2 6,4 25

22/06/2015 70 35 250 140 1,5 350 1 CPL 6,9 14 25

23/06/2015 70 35 140 150 1,5 350 1 CPL 6,8 13 30

29/06/2015 70 35 120 200 1,5 550 1,7 CPL 6,3 12 25

Taux de sable réglé à 7-10 g/L

Synthèse des essais de mise en route

DSM : results (Commissioning)

Messages to take home

➢ TOC & Colour Removal

▪ TOC < 2 ppm

▪ When used in combination with upstream clarification UVT > 90 / 92%

➢ Taste & Odour Removal

➢ Pesticides Removal

➢ Algal Toxins removal

➢ THM Removal when using Actiflo Carb; Filtraflo Carb or Opacarb MF

▪ THMs are formed by the reaction of free chlorine with natural organic matter (NOM), man-made organic

matter or bromide

▪ The NOM responsible for THMs consists of humic and fulvic acids produced by decaying organic matter

▪ Chloroform is typically found at higher concentrations in potable water than any other THM.

▪ THM5 < 100 ppb and generally below 50 ppb

These processes deliver :

35

Many thanks for your attention

We welcome your questions

36