1

Elimination of emergingcontaminants (surfactants,

pharmaceuticals) by membranebioreactor (MBR) technology

Catalan Institution for Research and Advanced Studies, Barcelona, Spain

IIQAB-CSIC, Department of Environmental Chemistry, Barcelona, Spain

Mira Petrovic, Jelena Radjenovic, Damia Barcelo

Outline• Introduction on MBR

– types of membranes– types of bioreactors– advantages and disadvanteges

• Case study (I)– elimination of pharmacueticals in a laboratory scale MBR (vs CAS)

• Case study (II)– elimination of pharmacueticals in a pilot scale MBR (vs CAS)

• Case study (III) – elimination of surfactants in a laboratory scale MBR (vs CAS)

• Conclusions

2

Membrane bioreactors (MBRs) combine the use of biological processes andmembrane technology to treat wastewater.

Within one process unit, a high standard of treatment is achieved, replacing theconventional arrangement of aeration tank, settling tank and filtration that generally produces what is termed as a tertiary standard effluent.

Membrane bioreactors (MBRs)

MF/UFmembrane

permeate

Permeate tank

Areation

Denitrification

BIOREACTOR

Why MBR?

Technical aspects

• adsorption, improved physical sludge characteristics, with higher biomass concentration and more effective surface;

• biodegradation, cultivation of metabolic speciation, with high sludge age, low mass organic load favouring biological synthesis of broader substrate spectrum

• direct and complete separation through membrane with entire removal of all contaminants bound to colloids and particulate matter.

3

Submerged MBR

Submerged MBR with internal vacuum driven membrane filtration

External MBR

Side-stream MBR with external pressure driven membrane filtration

4

The configurations of MBR are based on either a planar or cylindrical geometry.

There are five principal membrane configurations currently employed in practice:

hollow fiber (HF)

spiral wound

plate-and-frame (i.e. flat sheet (FS))

pleated filter cartridge

tubular.

Types of MBR configurations

MicrofiltrationUltrafiltration

The pore size of themembrane is 0,4 µm (microfiltration)

A layer of proteins andcellular material in themembrane surface changethe porosity into ≃ 0,01 µm: Range of filtration change into ULTRAFILTRATION

The disinfection depends on the membrane pore size, MICROFILTRATION (elimination of bacteria and pathological organisms) ULTRAFILTRATION (total disinfection including virus elimination).

5

Types of membranes

Spiral wound membrane for NF/RO

Hollow fibre

for MF/UF

Send filtrationSend filtrationaa

MicrofiltrationMicrofiltration

UUltrafiltrationltrafiltration

NNanofiltrationanofiltration

RReverse Osmosiseverse Osmosis

0.0001 0.001 0.01 0.1 1 10 100µm

Plate & frame membrane

Membrane for nanofiltration

(NF) and reverse

osmosys (RO)

MEMBRANE PROCESSES

Configurations most frequently used in wastewater treatment are hollow fiber (HF) and flat sheet (FS) MBR

Hollow fiber membranes

Flat sheet membranes

6

ImmersibleOutside-In Membrane

Advantages of MBR• Sludge production is significantly reduced, compared to conventional CAS, as

longer sludge ages are achievable• Effluent quality is consistently high and generally independent of the influent

quality.• Good disinfection capability, with significant bacterial and viral reductions

achievable using UF and MF membranes.• Longer retention of nitrifying bacteria within the bioreactor results in greater

nitrification than in a conventional CAS. • Denitrification can be achieved by utilizing a second anoxic vessel.• Sludge age and hydraulic retention time are independent• Growing of specialized microorganisms

Disadvantages of MBR• Higher energy consumption (bigger oxygen consume)• Higher cost (membranes and maintenance) (the cost of MBR drop from 2001 to

2004 and is estimated to be from 0.8 $ m-3 to 0.5 $ m-3)• Higher initial investment

7

Case study (1): elimination of pharmaceuticals in wastewater treatment plant (WWTP) Rubí,

Spain

- full scale CAS treatment,- laboratory scale MBR treatment

Influent type: municipal/hospital/industrial wastewater Equivalent inhabitants: 125 550Average daily flow: 1 125 m3/hMaximum daily flow: 1 800 m3/hHydraulic retention time: 14 hSolids retention time: 3 days

Treatment:1. Preliminary treatment (large solids

are removed)2. Primary treatment (physical process

of settling removes more solids)3. Secondary treatment (removes the

demand for oxygen using microbial action) consisting in pre-denitrification (anaerobic) and nitrification (aerobic)

Wastewater treatment plant (WWTP) Rubí

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

8

Volume: 2020--22 l22 lHydraulic retention time (HRT): 14 hSolids retention time (SRT): infinite.Nominal porosity: 0.4 µm (MF)Effective porosity: in the range of UFKubota flat sheet membranes (chlorinatedpoliethilen): 2 A4 embranes (A=0.3 m²), maximum capacity ~ 6 l/h.

Laboratory-scale membrane bioreactor (MBR) was operating in parallel to a conventional activated sludge (CAS) treatment. Their performance was monitored during a period of approximately two months, during which 28 integrated samples were analyzed.

Laboratory scale submerged plate-and-frame MBR

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

COMPARATION OF BASIC PARAMETERS

6-92535125Legislation

7.2717.8 (± 39.6)24 (± 37.4)80.7 (± 30.3)CAS

7.438.3 (± 42.4)7.1 (± 74.85)42.7 (± 23.3)MBR

pHNH4

+

(mg/l) (C.V.%)

TSS(mg/l)

(C.V.%)

COD, (mg/l)

(C.V.%)Effluent

9

MBR (72.2 ± 11.7 %)CAS WWTP (58.90 ± 23.8 %)

0

20

40

60

80

100

120

marzo abril mayo junio julio agosto

> 80 %El

imin

ació

n C

OD

(%)

COD

ANTI-HISTAMINICS

LIPID REGULATOR AND CHOLESTEROL LOWERING STATIN DRUGS

HYPOGLYCAEMIC AGENTS

DIURETICS

B-BLOCKERS

ANTIBIOTICS

ANTIEPILEPTIC DRUGS

PSYCHIATRIC DRUGS

ANTI-ULCER AGENTS

ANALGESICS AND ANTI-INFLAMMATORY DRUGS

FamotidineRanitidineLoratidine

Clofibric acidGemfibrozilBezafibratePravastatinMevastatin

Glibenclamide

Hydrochlorothiazide

AtenololSotalolMetoprololPropranolol

ErythromycinAzythromycinSulfamethoxazoleTrimethoprimOfloxacin

Carbamazepine

FlouxetineParoxetine

Lansoprazole

Ibuprofen IndomethacineKetoprofen AcetaminophenNaproxen Mefenamic acidDiclofenac Propyphenazone

To relieve allergy reactions

To lower fat (lipids) level

To treat type II diabetes

To treat excessive fluid accumulation

Antianginal antihypertensive

Antibacterial agents

To treat epileptic attacks

Antidepressants

To prevent and treat ulcers

To relief pain, inflammation and fever

Target compounds monitored

10

Compounds that were found in highest influent Compounds that were found in highest influent concentrations (µg/L) were:concentrations (µg/L) were:

analgesics and antianalgesics and anti--inflammatory drugs: ibuprofen, ketoprofen, inflammatory drugs: ibuprofen, ketoprofen, naproxen, diclofenac, indomethacin, acetaminophennaproxen, diclofenac, indomethacin, acetaminophen

lipid regulator and cholesterol lowering statin drugs: gemfiblipid regulator and cholesterol lowering statin drugs: gemfibrozil, bezafibrate rozil, bezafibrate

diuretics: hydrochlorothiazide diuretics: hydrochlorothiazide

Out of 31 pharmaceutical products included in the analytical method, 22 were detected in the wastewater entering WWTP Rubí.

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

In some cases the removal efficiencies were very similar and hIn some cases the removal efficiencies were very similar and high for both igh for both treatments (e.g. ibuprofen, naproxen, acetaminophen, hydroctreatments (e.g. ibuprofen, naproxen, acetaminophen, hydrochlorothiazide, hlorothiazide, paroxetine). paroxetine).

Elimination of acetaminophen Elimination of hydrochlorothiazide

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

11

ELIMINATION OF PAROXETINE

0

20

40

60

80

100

120

April,2

5.

May,03

.

May,09

.

May,23

.

May,30

.

June

,06.

July,0

5.

July,1

2.

July,2

5.

Augus

t,09.

sampling days, 2006.

%

ELIMINATION IN MBRELIMINATION IN CAS

ELIMINATION OF GLIBENCLAMIDE

0102030405060708090

April,2

5.

May,03

.

May,09

.

May,23

.

May,30

.

June

,06.

July,0

5.

July,1

2.

July,2

5.

Augus

t,09.

sampling days, 2006.

%

ELIMINATION IN MBRELIMINATION IN CAS

ELIMINATION OF NAPROXEN

0

20

40

60

80

100

120

April,2

5.

May,03

.

May,09

.

May,23

.

May,30

.

June,0

6.

July,0

5.

July,1

2.

July,2

5.

Augus

t,09.

sampling days, 2006.

%

ELIMINATION IN MBRELIMINATION IN CAS

ELIMINATION OF IBUPROFEN

0

20

40

60

80

100

120

April,2

5.

May,03

.

May,09

.

May,23

.

May,30

.

June,0

6.

July,0

5.

July,1

2.

July,2

5.

Augus

t,09.

sampling days, 2006.

%

ELIMINATION IN MBRELIMINATION IN CAS

12

For most of the investigated compounds MBR treatment For most of the investigated compounds MBR treatment had better performance (removal rates>80%) and steadier had better performance (removal rates>80%) and steadier effluent concentrations than the conventional system (e.g. effluent concentrations than the conventional system (e.g. diclofenac, ketoprofen, gemfibrozil, bezafibrate, ranitidine, diclofenac, ketoprofen, gemfibrozil, bezafibrate, ranitidine, pravastatin, ofloxacin). pravastatin, ofloxacin).

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

Outlier

1.5 interquartile range

75% samples

Median

25% samples

1.5 interquartile range

ELIMINATION OF DICLOFENAC

0.0

20.0

40.0

60.0

80.0

100.0

120.0

April,2

5.

May,03

.

May,09

.

May,23

.

May,30

.

June,0

6.

July,0

5.

July,1

2.

July,2

5.

Augus

t,09.

sampling days, 2006.

%

ELIMINATION IN MBRELIMINATION IN CAS

ELIMINATION OF OFLOXACIN

0

20

40

60

80

100

120

April,2

5.

May,03

.

May,09

.

May,23

.

May,30

.

June,0

6.

July,0

5.

July,1

2.

July,2

5.

Augus

t,09.

sampling days, 2006.

%

ELIMINATION IN MBRELIMINATION IN CAS

13

The antiepileptic drug carbamazepine turned out to be the mosThe antiepileptic drug carbamazepine turned out to be the most persistentt persistentpharmaceutical as it passed both through MBR and CAS systempharmaceutical as it passed both through MBR and CAS systemuntransformed. untransformed.

Elimination of carbamazepine

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

Elimination of atenolol

Compound Elimination in Elimination inMBR, %a CAS,%b

Analgesics and anti-inflammatory drugs Naproxen 99.3 (1.52) * 85.1 (11.4)Ketoprofen 91.9 (6.55) 51.5 (22.9)Ibuprofen 99.8 (0.386) 82.5 (15.8)Diclofenac 87.4 (14.1) 50.1 (20.1)Indomethacin 46.6 (23.2) 23.4 (22.3)Acetaminophen 99.6 (0.299) 98.4 (1.72)Mefenamic acid 74.8 (20.1) 29.4 (32.3)Propyphenazone 64.6 (13.3) 42.7 (19.0)Anti-ulcer agentsRanitidine 95.0 (3.74) 42.2 (47.0)Psychiatric drugsParoxetine 89.7 (6.69) 90.6 (4.74)Antiepileptic drugsCarbamazepine no elimination** no eliminationAntibioticsOfloxacin 94.0 (6.51) 23.8 (23.5)Sulfamethoxazole 60.5 (33.9) 55.6 (35.4)Erythromycin 67.3 (16.1) 23.8 (29.2)Β-blockersAtenolol 65.5 (36.2) no eliminationMetoprolol 58.7 (72.8) no eliminationDiureticsHydrochlorothiazide 66.3 (7.79) 76.3 (6.85)Hypoglycemic agentsGlibenclamide 47.3 (20.1) 44.5 (19.1)Lipid regulator and cholesterol lowering statin drugsGemfibrozil 89.6 (23.3) 38.8 (16.9)Bezafibrate 95.8 (8.66) 48.4 (33.8)Clofibric acid 71.8 (30.9) 27.7 (46.9)Pravastatin 90.8 (13.2) 61.8 (23.6)

*values are presented as average with relative standard deviation (%) in brackets, for aN=10 and bN=8 samples.**as “no elimination” were considered all cases with elimination efficiency less than 10%.

J. Radjenovic et al. Anal. Bioanal. Chem. 387 (4), pp 1365-1377

14

1-naproxen, 2-ketoprofen, 3-ibuprofen, 4-diclofenac, 5-indomethacin, 6-acetaminophen, 7-mefenamic acid, 8-propyphenazone, 9-ranitidine, 10- paroxetine, 11-carbamazepine, 12- ofloxacin, 13- sulfamethoxazole, 14- erythromycin, 15- atenolol, 16- metoprolol,17- hydrochlorothiazide, 18- glibenclamide, 19- gemfibrozil, 20- bezafibrate, 21- clofibric acid,22- pravastatin

0

20

40

60

80

100

0 20 40 60 80 100

10

30

50

70

90

CAS elimination, %

MB

R e

limin

atio

n, %

101

2

3

4

5

6

7

8

9

11

12

13

1415

16

17

18

19

20

21

22

10-60% >60%<10%

Comparison of CAS and MBR performances – elimination of pharmaceutical residues

Case study (2): elimination of pharmaceuticals in wastewater

treatment plant (WWTP) Terrassa, Spain

- full scale CAS treatment,- two pilot scale MBR treatments

15

Influent type: industrial (mostly pharmaceutical and textile industry)/ municipal wastewaterEquivalent inhabitants: 277 000Average daily flow: 2 000 m3/hMaximum daily flow: 2 500 m3/hHydraulic retention time: 11.5 hSolids retention time: 12 daysTreatment:

1. Preliminary treatment2. Primary treatment3. Secondary treatment (pre-denitrification

and nitrification).

Wastewater treatment plant (WWTP) Terrassa

Two pilot-scale membrane bioreactors are operating in parallel to a conventional activated sludge proces.

3.64.69Volume (m3 )

infiniteinfiniteSRT

7.210-20HRT (h)

1710-20Flow (L m-2 h-1)

0.05 (UF)0.4 (MF)Nominal porosity(µm)

3040Membranesurface active area (m2 )

Hollow fibrePlate-and-frameMembrane type

Externalmembranemodule

Externalmembranemodule

Configuration

KOCHKUBOTAMBR

Pilot scale MBRs with external membrane module:plate-and-frame vs. hollow-fibre membranes

16

NPRX: Naproxen, Influent conc. range= 3.9-5 µg/ L.IBP: Ibuprofen, Influent conc. range= 51-57 µg/ L.ACTP: Acetaminophen, Influent conc. range= 35-36 µg/ L.CAF: Caffeine, Influent conc. range= 3.5-5.9 µg/ L.SMX: Sulfamethoxazole, Influent conc. range= 1.4-1.6 µg/ L.

Elimination of target compounds in CAS and two pilot-plant MBRs in WWTP Terrassa

Pharmaceuticals with elimination during conventional treatment > 80%

0

20

40

60

80

100

120

NPRX IBP ACTP CAF SMXCompound

Elim

inat

ion,

%

Elimination in CAS

Elimination in KOCH MBR

Elimination in KUBOTA MBR

Pharmaceuticals with elimination during conventional treatment < 80 %

-20

0

20

40

60

80

100

120

ATL OFL INDM HCTZ GLBC

Compound

Elim

inat

ion,

%

Elimination in CAS

Elimination in KOCH MBR

Elimination in KUBOTA MBR

ATL: Atenolol, Influent conc. range=1.2-1.6 µg/ L.OFL: Ofloxacin, Influent conc. range= 2.1-3.0 µg/ L.INDM: Indomethacin, Influent conc. range= 42-98 ng/ L.HCTZ: Hydrochlorothiazide, Influent conc. range= 2.9-5.0 µg/ L.GLBC: Glibenclamide, Influent conc. range= 130-295 ng/ L.

Elimination of target compounds in CAS and two pilot-plant MBRs in WWTP Terrassa

17

Conclusions (I):Several pharmaceuticals (e.g. ibuprofen, naproxen, acetaminophen, ketoprofen, diclofenac, bezafibrate, gemfibrozil, ranitidine, ofloxacin, hydrochlorothiazide and paroxetine) with high attenuation rates can be expected to be completely removed from wastewater during membrane treatments by sorption, degradation or combination of both.

Some substances were not removed neither in MBR nor in CAS process (e.g. carbamazepine).

Performances of two types of MBR configuration, plate-and-frame and hollow fiber, were very similar for most of the pharmaceutical residues detected. Only for indomethacine and glibenclamide significantly higher reduction was noted for KOCH hollow fiber MBR.

Range of variation of removal rates of MBR system was small for most of the compounds, while in the conventional treatment stronger fluctuations were observed and it turned out to be a lot more sensitive to changes in operational parameters (temperature, flow rate, etc).

Further studies on the occurrence and fate of selected compounds in pilot-scale membrane bioreactors will be conducted, which will provide additional information on the behavior of these compounds during advanced membrane wastewater treatments.

Example: Non ionic surfactants

Alkylphenol ethoxylates

OOH

C9H19

n

n=1-20

Nonylphenol ethoxylates(NPEOs)

- Non-ionic surfactantsindustrial formulation (textile, tannery, pulp and paper industries)

- Pesticides adjuvants- Paint ingredients- Wetting agents

• Global production is well over 500.000 tons • Use restricted in many countries• Throughout northern Europe (Scandinavian countries, England, Germany) a

voluntary ban on NPEO use in household cleaning products began in 1995, and restrictions on industrial cleaning applications in 2000

• Spain – use in industrial formulations not restricted

18

Main concern: Poor ultimate biodegradability

Reproductive toxicity of some degradation products

Breakdown pathway of NPEOs

Increasing toxicity

Increasing bioconcentration

Increasing persistence

C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OH

C9H19 O CH2CH2O H9

C9H19C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

C9H19C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OHC9H19C9H19 OH

Breakdown pathway of NPEOs

Increasing toxicity

Increasing bioconcentration

Increasing persistence

C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OH

C9H19 O CH2CH2O H9

C9H19C9H19 O CH2CH2O H9

C9H19 O CH2CH2O H8

C9H19C9H19 O CH2CH2O H8

C9H19 O CH2CH2O CH2COOH8

C9H19C9H19 O CH2CH2O CH2COOH8

NP2EO

NP8EO

NP9EO

NP2EC

NP9EC

NP1EO

NPNP1EC

C9H19 OHC9H19C9H19 OH

Increasingpolarity

Breakdown during sewage treatment (AST)(according Ahel, Wat. Res. 1995)Ultimate biodegradation of NPEOs <40%

40-45% ends up in secondary effluent

20 % in sludge

Primary Effluents

68%

20%

5%7%

NPnEONP1EO+NP2EO

NP1EC+NP2ECNP

20%

25%47%

8%

Secondary Effluents Digested Sludge

5%

95%

19

Concentration levels in WWTP effluents

No datalevels of 10-40 µg/LCAPEC

<LOD-825<LOD-33

up to 225*NP

<LOD-651-115

up to 1120*NPEC

10-2400<LOD-60

up to 330*NPEO

Sludge (mg/kg)Secondary effluent (µg/L)Compound

* WWTP receiving industrial WW

Source: Knepper, Barcelo, de Voogt (Eds) Analysis and fate of surfactants in the aquatic environment, Elsevier 2003

The relative estrogenic potency (relative to 17b-estradiol) in-vitro(according Jobling and Sumpter, Aquatic. Toxicol. 1993)NP 9.0 x 10-6OP 3.7 x 10-5NP1EC 6.3 x 10-6NP2EO 6.0 x 10-6NP10EO 2.0 x 10-7

Biologically active concentrations: as low as 1-20 µg/L

Case study (3): elimination of surfactants in wastewater

treatment plant (WWTP) Rubí, Spain

- full scale CAS treatment,- laboratory scale MBR treatment

20

BOXPLOT

outliers

1.5 interq. range

75% samples

Median

25% samples1.5 interq. range

Effluent MBR

NP(3-15)EO

Influent CAS Effluent CAS0

50

100

150

200

250

300

350

400

450

Con

cent

ratio

n(p

pb)

0

50

100

150

200

250

300

350

400

450

Con

cent

ratio

n(p

pb)

NP(3-15)EO

NP(3-15)EO

0.00

50.00

100.00

150.00

200.00

250.00

300.00

350.00

400.00

450.00

500.00

1 2 3 4 5 6 7 11 18 22 23 24 25 26 27 28

time (day of the experiment)

conc

entr

atio

n (µ

g/L)

CAS influentCAS effluentMBR effluent

Long ethoxy chain NPEO

NP1EO

0.00

20.00

40.00

60.00

80.00

100.00

120.00

140.00

160.00

1 2 3 4 5 6 7 11 18 22 23 24 25 26 27 28

time (day of the experiment)

conc

entr

atio

n (µ

g/L)

CAS influentCAS effluentMBR effluent

NP2EO

0.00

20.00

40.00

60.00

80.00

100.00

120.00

140.00

1 2 3 4 5 6 7 11 18 22 23 24 25 26 27 28

time (day of the experiment)

conc

entr

atio

n (µ

g/L)

CAS influentCAS effluentMBR effluent

Effluent MBR0

50

100

Con

cent

ratio

n(p

pb)

NP1EO

Influent CAS Effluent CAS

150 NP1EO

Effluent MBR0

20

40

60

80

100

120

Con

cent

ratio

n(p

pb)

NP2EO

Influent CAS Effluent CAS0

NP2EO

Short ethoxy chain NPEO

21

NP1EC

0.00

5.00

10.00

15.00

20.00

25.00

1 2 3 4 5 6 7 11 18 22 23 24 25 26 27 28

time (day of the experiment)

conc

entr

atio

n (µ

g/L)

CAS influentCAS effluentMBR effluent

NP2EC

0.0020.0040.0060.0080.00

100.00120.00140.00160.00180.00200.00

1 2 3 4 5 6 7 11 18 22 23 24 25 26 27 28

time (day of the experiment)

conc

entr

atio

n (µ

g/L)

CAS influentCAS effluentMBR effluent

Effluent MBR

NP1EC

Influent CAS Effluent CAS Effluent MBR0

5

10

15

20

Con

cent

ratio

n(p

pb)

0

5

10

15

20

Con

cent

ratio

n(p

pb)

NP1EC

Effluent MBR

NP2EC

Influent CAS i Effluent CAS i Effluent MBR

0

20

40

60

80

100

120

140

160

180

Con

cent

ratio

n(p

pb)

0

20

40

60

80

100

120

140

160

180

Con

cent

ratio

n(p

pb)

NP2EC

Nonylphenoxy carboxylates

NP

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

1 2 3 4 5 6 7 11 18 22 23 24 25 26 27 28

time (day of the experiment)

conc

entr

atio

n (µ

g/L)

CAS influentCAS effluentMBR effluent

Effluent MBR

0

10

20

30

40

50

60

Con

cent

ratio

n(p

pb)

NP

Influent CAS Effluent CAS

0

10

20

30

40

50

60

Con

cent

ratio

n(p

pb)

NP

Nonylphenol

22

Effluent MBR

19%

15%

16%

19%

8%

Effluent CAS Rubí0

200

400

600

800

1000

1200

1400

1600

1800

2000

Con

cent

ratio

n(n

mol

/L)

Effluent MBR

19%

15%

19%

8%NP1EONP2EONP(3-15)EONP1ECNP2ECNP

NP1EONP2EONP(3-15)EONP1ECNP2ECNP

Effluent CAS Rubí

23%18%

10%

43%

2%

14%

13%19%

10%

10%

6%

54%

1%19%

15%

23%

16%

19%

8%23%18%

10%

43%

2%

14%

13%19%

10%

10%

6%

54%

1%19%

15%

23%

16%

19%

8%

Influent CAS Effluent CAS Effluent MBR

0

200

400

600

800

1000

1200

1400

1600

1800

2000

Con

cent

ratio

n(n

mol

/L)

Total nonylphenolic compounds

LAS and CDEA

Influent CAS Rubi Effluent CAS Rubi Effluent MBR

0

100

200

300

400

500

600

700

800

900

Con

cent

ratio

n (p

pb)

LAS

Influent CAS Rubi Effluent CAS Rubi Effluent MBR

0

100

200

300

400

500

600

700

800

900

Con

cent

ratio

n (p

pb)

LAS

Influent CAS Rubi Effluent CAS Rubi Effluent MBR

0

100

200

300

400

500

600

700

800

900

Con

cent

ratio

n (p

pb)

LAS

Influent CAS Rubi Effluent CAS Rubi Effluent MBR

0

20

40

60

80

100

120

140

160

180

Con

cent

ratio

n (p

pb)

CDEA

Influent CAS Rubi Effluent CAS Rubi Effluent MBR

0

20

40

60

80

100

120

140

160

180

Con

cent

ratio

n (p

pb)

CDEA

Influent CAS Rubi Effluent CAS Rubi Effluent MBR

0

20

40

60

80

100

120

140

160

180

Con

cent

ratio

n (p

pb)

CDEA

23

Conclusions (II)

• MBR treatment retained and degraded alkyphenoliccompounds with an overall efficiency of 94%, which represented a significant improvement in comparison to the CAS treatment where only 54% of the total nonylphenoliccompounds were removed.

• MBR is very efficient in removal of acidic metabolites(NP1EC and NP2EC) which are the most abundant biodegradation products formed in CAS.

Acknowledgements

This work has been supported by:

EU project EMCO (INCO CT 2004-509188) (Reduction of environmental risks, posed by Emerging Contaminants, through advanced treatment of municipal and industrial wastes)

EU project AquaTerra ( GOCE-CT-505428) Integrated modelling of the river-sediment-soil-groundwater system; Advanced tools for the management of catchment areas and river basins in the context of global change

Spanish Ministerio de Ciencia y TecnologiaProject CTM2004-06255-CO3-01