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Pontes e Parcerias nos Países de Língua Portuguesa

Coimbra, 5 de Julho de 2016

O problema dos poluentes emergentes e a sua presença em águas superficiais e águas residuais

CRISTINA DELERUE-MATOS [email protected]

www.requimte.pt | www.graq.isep.ipp.pt


Cristina Delerue-Matos– 05/07/2016

Emerging Pollutants

“Pollutants currently not included in routine monitoring

programmes at Union level but which could pose a significant

risk requiring regulation, depending upon their potential

ecotoxicological and toxicological effects and on their levels in

the aquatic environment”

Directive 2013/39/EU



EMERGING POLLUTANTS

Drugs of abuse Personal care products

Fuel additives

Pharmaceuticals

Surfactants

Disinfection

byproducts

Endocrine disruptors

Nanomaterials



SOURCES AND FATE IN THE ENVIRONMENT

Pharmaceuticals do not need to persist in the

environment, since they are continuously

introduced



Pharmaceuticals have been detected in the environment worldwide

Nowadays there are a few data of the presence of pharmaceuticals in developing countries



Number of pharmaceuticals found in drinking water worldwide.



ANTIEPILEPTIC DRUGS

DICLOFENAC

CARBAMAZEPINE

IBUPROFEN

SULFAMETHOXAZOLE

NAPROXEN

ESTRONE

17-β-ESTRADIOL

17-α-ETHINYLESTRADIOL

TRIMETROPIN

PARACETAMOL

ANALGESICS

ANALGESICS

ANTIBIOTICS

ANALGESICS

ESTROGENS

ESTROGENS

ESTROGENS

ANTIBIOTICS

ANALGESICS

Number of pharmaceuticals detected in surface water, ground water, tap water and/or drinking water



Sampling Sample

preparation Chromatographic

separation Detection Results

ANALYTICAL PROCEDURE

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 min

0

25000

50000

75000

100000

125000

150000

175000

200000

225000

250000

Diazepam-d5

Venlafaxine-d6

Fluoxetine-d5

Carbamazepine-d10

Trazodone

Paroxetine

Venlafaxine

Citalopram

SertralineFluoxetineCarbamazepine

Norfluoxetine

Inte

nsity



PHARMACEUTICALS DETECTED BY OUR GROUP REQUIMTE/LAQV-ISEP

PRESENCE OF PHARMACEUTICALS IN PORTUGUESE RIVERS: IBUPROFEN

PRESENCE OF PHARMACEUTICALS IN PORTUGUESE RIVERS: PARACETAMOL, PARACETAMOL-GLUCURONIDE AND P-AMINOPHENOL

EVALUATION OF THE PRESENCE OF PHARMACEUTICALS IN PORTUGUESE SEAWATERS

CONTRIBUTION OF HOSPITAL EFFLUENTS TO THE LOAD OF PHARMACEUTICALS INTO URBAN WASTEWATERS

IMPACT OF URBAN WASTEWATERS TO THE LOAD OF PHARMACEUTICALS INTO SURFACE WATERS



PRESENCE OF PHARMACEUTICALS IN PORTUGUESE RIVERS: IBUPROFEN 33 surface water samples (rivers, stream, estuaries)

15 positive samples for the presence of ibuprofen

0

100

200

300

400

500

600

700

800Ib

up

rofe

n c

on

c. (n

g L

-1)



7 Rivers of the North of Portugal

At least one compound detected in all the studied rivers

Metabolite and transformation product detected in higher concentrations than the parent compound


0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

Co

nc

. (μ

g L

-1)

Paracetamol Paracetamol-glucuronide p-Aminophenol



EVALUATION OF THE PRESENCE OF PHARMACEUTICALS IN PORTUGUESE SEAWATERS • 101 Seawater samples were collected in Atlantic Ocean

• 14 Beaches with different bathing water quality (excellent, good, sufficient)

• 5 Cities and surrounding area (Vila do Conde, Matosinhos, Porto, Vila Nova de Gaia, Espinho)

• Analyzed by SPE-UHPLC-MS/MS



Lolić et al., STOTEN 508 (2015) 240

TEMPORAL DISTRIBUTION OF AINES/ANALGESICS ALONG BATHING SEASON 2013

Highest concentrations detected in

August and September

Increase of the population in the

studied area during these months



ENVIRONMENTAL RISK ASSESSMENT

Environmental Risk

Assessment

Based on Hazard Quotient (HQ) using 3 trophic

levels (algae, daphnids and fish)

“Worst case scenario” approach

HQ = MEC/PNEC

MEC – Measured Environmental Concentration

PNEC – Predicted No-effect Concentration

• Potential environmental risk HQ ≥ 1

• No risk is expected HQ < 1



1.00E-05

1.00E-04

1.00E-03

1.00E-02

1.00E-01

1.00E+00

1.00E+01

Haz

ard

qu

oti

ent

(HQ

)

Fish

Daphnid

1.00E-05

1.00E-04

1.00E-03

1.00E-02

1.00E-01

1.00E+00

1,00E-05

1,00E-04

1,00E-03

1,00E-02

1,00E-01

1,00E+00

Haz

ard

qu

oti

en

t (H

Q)

Título do Gráfico

Acetaminophen

Acetylsalicylic acid

Diclofenac

Ibuprofen

Naproxen

Ketoprofen

ENVIRONMENTAL RISK ASSESSMENT - SEAWATERS

Haz

ard

qu

oti

ent

(HQ

)

Diclofenac



Algae

1,00E-05

1,00E-04

1,00E-03

1,00E-02

1,00E-01

1,00E+00

Haz

ard

qu

oti

en

t (H

Q)

Título do Gráfico

Acetaminophen

Acetylsalicylic acid

Diclofenac

Ibuprofen

Naproxen

Ketoprofen

ENVIRONMENTAL RISK ASSESSMENT - SEAWATERS

1.00E-05

1.00E-04

1.00E-03

1.00E-02

1.00E-01

1.00E+00

Haz

ard

qu

oti

en

t (H

Q)

Acetaminophen Acetylsalicylic acid Diclofenac Ibuprofen Naproxen Ketoprofen




Santos et al., STOTEN 461-462 (2013) 302

University General Pediatric Maternity

WWTP

Number of beds

1456 350 110 96

The case study of Coimbra (Portugal)

78 pharmaceuticals

20 therapeutic

classes

SPE-UHPLC-MS/MS

Sampling period:

February-May 2011





Contamination pattern (relative concentration (%) for each therapeutic class)

0 20 40 60 80 100

Maternity

Pediatric hospital

General hospital

University hospital

Relative percentage (%)

X-ray contrast agent (iopromide)

Analgesics/anti-inflammatories

Antibiotics

Diuretics

Antihypertensives

Psychiatric drugs

β-Blockers

Oral antidiabetic (metformin)

Others



IMPACT OF HOSPITAL EFFLUENTS INTO URBAN WASTEWATERS

Higher impact of hospital effluents

Analgesics Antibiotics

NSAIDs

University hospital

General hospital

Pediatric hospital

Maternity hospital

Urban input


Psychiatric drugs




0

10

20

30

40

50

60

70

80

90

Re

mo

va

l e

ffic

ien

cy (

%)


Removal efficiency of pharmaceuticals in the WWTP goes

from not eliminated to >80%



ENVIRONMENTAL RISK ASSESSMENT – WWTP EFFLUENTS

Pharmaceuticals that have a potential environmental risk (HQ > 1)

Pharmaceutical HQ algae

Sulfamethoxazole 62.6

Ciprofloxacin 279

Ofloxacin 22.9

Azithromycin 15.6

Clarithromycin 3.34

Setraline 1.20


The level of pharmaceuticals found

in WWTP effluents showed a more

pronounced potential risk for algae

• Antibiotics are among pharmaceuticals that

have a high potential environmental risk




• The impact of WWTP effluents was evaluated using Lis river as a case study • Sampling points were selected through the river • WWTPs that discharge their effluent into the river were also monitored

9 Sampling points:

Source of Lis River

Upstream WWTP of Olhalvas

Downstream WWTP of Olhalvas

WWTP of Olhalvas (influent and effluent)

Upstream WWTP Norte

Downstream WWTP Norte

WWTP Norte (influent and effluent)

Sampling period: August 2013-June2014



WWTP 1 WWTP 2

• Designed for 49,315 p.e.

• Secondary treatment by activated

sludge

• Average capacity: 6250 m3/day

• Designed for 248,685 p.e.

• Secondary treatment by activated

sludge

• Tertiary treament by UV during

bathing season

• Average capacity: 37,997 m3/day

Source: Paíga et al, in preparation



Ph

arm

ace

uti

cals

Anti-inflammatories/Analgesic

Psychiatric drugs

Antibiotics

Acetaminophen

Naproxen Ketoprofen

Nimesulide Ibuprofen Hydroxyibuprofen Carboxyibuprofen

Diclofenac

Acetylsalicylic acid Salicylic acid

Norfluoxetine Fluoxetine

Citalopram Venlafaxine

Carbamazepine

Paroxetine

Diazepam 10, 11-Epoxicarbamazepine

Sertraline

Trazodone

Trimethoprim

Ofloxacin

Sulfamethoxazole

Sulfamethazine

Sulfamethoxypiridazine

Sulfadimethoxine

Sulfadiazine

Sulfapyridine

Ciprofloxacin

Enrofloxacin

Azithromycin

Clarithromycin

SPE-UHPLC-MS/MS


Cristina Delerue-Matos– 05/07/2016 Source: Paíga et al, submitted

0 10 20 30 40 50 60 70 80 90 100

Azithromycin

Clarithromycin

Ciprofloxacin

Trimethoprim

Sulfamethazine

Sulfamethoxazole

Sulfapyridine

Sulfadiazine

Diazepam

10,11-Epoxycarbamazepine

Carbamazepine

Venlafaxine

Trazodone

Citalopram

Paroxetine

Sertraline

Norfluoxetine

Fluoxetine

Salicylic acid

Diclofenac

Ketoprofen

Acetaminophen

Naproxen

Hydroxyibuprofen

Carboxyibuprofen

Ibuprofen

Frequency of detection (%)

WWTP influent WWTP effluent River

NSAIDs/Analgesics

Psychiatric drugs

Antibiotics



Source

Upstream WWTP1

Downstream WWTP1

Upstream WWTP2

Downstream WWTP2

An

tib

ioti

cs



Car

bam

aze

pin

e

0

50

100

150

200

250

300

Concentration (ng/L)

Downstream WWTP 2

0

50

100

150

200

250

300

Concentration (ng/L) Upstream WWTP 2

0

50

100

150

200

250

300

Concentration (ng/L) Downstream WWTP 1

0

50

100

150

200

250

300


Upstream WWTP 1

0

50

100

150

200

250

300


Source of Lis River



1E+00

1E+01

1E+02

1E+03

1E+04

1E+05

1E+06

Load (

mg/d

/1000 in

habitants

)

Antibiotics (WWTP 1) Antibiotics (WWTP 2)

Psychiatric drugs (WWTP 1) Psychiatric drugs (WWTP 2)

NSAIDs/analgesics (WWTP 1) NSAIDs/analgesics (WWTP 2)

1E+00

1E+01

1E+02

1E+03

1E+04

Load (

mg/d

/1000 in

habitants

)




1E+00

1E+01

1E+02

1E+03

1E+04

1E+05

1E+06

Load (

mg/d

/1000 in

habitants

)






0 20 40 60 80 100

nov/13

dez/13

jan/14

fev/14

mar/14

abr/14

mai/14

jun/14

jul/14

Removal efficiency (%)

WWTP 2

WWTP 1

WWTP 2 shows a higher removal efficiency of antibiotics than WWTP 1

An

tib

ioti

cs



1E-05

1E-04

1E-03

1E-02

1E-01

1E+00

Cipr

oflo

xaci

n

Sulfa

met

hazi

ne

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Azi

thro

myc

in

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Cita

lopr

am

Paro

xetin

e

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

1E-05

1E-04

1E-03

1E-02

1E-01

1E+00

1E+01

Cip

rofl

oxa

cin

Su

lfa

me

tha

zin

e

Su

lfa

me

tho

xazo

le

Cla

rith

rom

yci

n

Ca

rbam

aze

pin

e

Flu

oxe

tin

e

Ser

tra

line

Ace

tam

ino

ph

en

Ibu

pro

fen

Ke

top

rofe

n

Sal

icyl

ic a

cid

Nap

rox

en

Dic

lofe

na

c

Ha

za

rd q

uo

tie

nt

(HQ

)

1E-04

1E-03

1E-02

1E-01

1E+00

1E+01

1E+02

Cipr

oflo

xaci

n

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Azi

thro

myc

in

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Cita

lopr

am

Paro

xetin

e

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

ENVIRONMENTAL RISK ASSESSMENT – LIS RIVER

Ibuprofen

Ciprofloxacin Sulfamethozazole Clarithromycin Azithromycin



ENVIRONMENTAL RISK ASSESSMENT WWTP EFFLUENTS

1E-05

1E-04

1E-03

1E-02

1E-01

1E+00

1E+01

Cipr

oflo

xaci

n

Trim

eth

opri

m

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Dia

zep

am

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

1E-07

1E-06

1E-05

1E-04

1E-03

1E-02

1E-01

1E+00

1E+01

Trim

eth

opri

m

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Dia

zepa

m

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

WW

TP

2

WW

TP

1

Ibuprofen Diclofenac



1E-04

1E-03

1E-02

1E-01

1E+00

1E+01

Cipr

oflo

xaci

n

Trim

eth

opri

m

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Azi

thro

myc

in

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Cita

lopr

am

Dia

zep

am

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

WW

TP

1

1E-07

1E-06

1E-05

1E-04

1E-03

1E-02

1E-01

1E+00

1E+01

Trim

eth

opri

m

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Azi

thro

myc

in

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Cita

lopr

am

Paro

xetin

e

Dia

zep

am

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

WW

TP

2


Acetaminophen



1E-03

1E-02

1E-01

1E+00

1E+01

1E+02

Cipr

oflo

xaci

n

Trim

eth

opri

m

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Azi

thro

myc

in

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Cita

lopr

am

Dia

zep

am

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

WW

TP

1

1E-03

1E-02

1E-01

1E+00

1E+01

Trim

eth

opri

m

Sulfa

met

hoxa

zole

Clar

ithr

om

ycin

Azi

thro

myc

in

Carb

amaz

epin

e

Flu

oxet

ine

Sert

ralin

e

Cita

lopr

am

Paro

xetin

e

Dia

zep

am

Ace

tam

ino

phen

Ibu

prof

en

Keto

prof

en

Salic

ylic

aci

d

Nap

roxe

n

Dic

lofe

nac

Ha

za

rd q

uo

tie

nt

(HQ

)

WW

TP

2


Ciprofloxacin Sulfamethozazole Clarithromycin Azithromycin Fluoxetine

Sulfamethoxazole Fluoxetine



The presence of different therapeutic classes was quantified in portuguese surface waters (rivers, stream, estuaries, seawaters)

Wastewaters are an important source of entrance of pharmaceuticals into the environment

The contribution of hospital effluents to the load of pharmaceuticals to urban wastewaters varies among therapeutic classes and from hospital to hospital

More monitoring studies should be made in order to better understand the level of environmental pollution

Green pharmacy approach is a challenge in nowadays

New remediation technologies and solutions have to be found

CO

NC

LUSI

ON

S:



ACKNOWLEDGEMENTS • Lúcia Helena Moreira Lírio Matias dos Santos • Paula Celeste Batista Paíga

This work received financial support from the European Regional Development Fund (ERDF) through

the COMPETE - Operational Competitiveness Programme and national funds through FCT, under

UID/QUI/50006/2013 and project UTAP-ICDT/CTM-NAN/0025/2014. The authors wish to acknowledge

to the Agência Portuguesa do Ambiente (APA) for providing the seawater samples.

Muito Obrigada/o pela Vossa Atenção/ Thank you for your attention

http://www.graq.isep.ipp.pt

http://www.graq.isep.ipp.pt/

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