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

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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

cmm@isep.ipp.pt

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

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”

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E

MERGING

P

OLLUTANTS

Drugs of abuse Personal care products

Fuel additives Pharmaceuticals

Surfactants

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SOURCES AND FATE IN THE ENVIRONMENT

Pharmaceuticals do not need to persist in the environment, since they are continuously introduced

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 Pharmaceuticals have been detected in the environment worldwide

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ANTIEPILEPTIC DRUGS DICLOFENAC CARBAMAZEPINE IBUPROFEN SULFAMETHOXAZOLE NAPROXEN ESTRONE 17-β-ESTRADIOL 17-α-ETHINYLESTRADIOL TRIMETROPIN ANALGESICS ANALGESICS ANTIBIOTICS ANALGESICS ESTROGENS ESTROGENS ESTROGENS ANTIBIOTICS

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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 Sertraline Fluoxetine Carbamazepine Norfluoxetine In te n si ty

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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

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P

RESENCE OF PHARMACEUTICALS IN

P

ORTUGUESE RIVERS

:

IBUPROFEN

 33 surface water samples (rivers, stream, estuaries)  15 positive samples for the presence of ibuprofen

0 100 200 300 400 500 600 700 800 Ibuprof e n c onc. (n g L -1 )

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

-AMINOPHENOL

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 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

P

RESENCE OF PHARMACEUTICALS IN

P

ORTUGUESE RIVERS

:

PARACETAMOL

,

PARACETAMOL

-GLUCURONIDE AND P

-

AMINOPHENOL

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 Con c . (μ g L -1)

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E

VALUATION OF THE PRESENCE OF PHARMACEUTICALS IN

P

ORTUGUESE 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

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Lolić et al., STOTEN 508 (2015) 240

T

EMPORAL DISTRIBUTION OF

AINE

S

/A

NALGESICS ALONG BATHING SEASON

2013

Highest concentrations detected in August and September

Increase of the population in the studied area during these months

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E

NVIRONMENTAL

R

ISK

A

SSESSMENT

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

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Cristina Delerue-Matos– 05/07/2016 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 1.00E+01 Ha za rd q u ot ie n t (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 H az ar d qu ot ie nt (H Q ) Título do Gráfico Acetaminophen Acetylsalicylic acid Diclofenac Ibuprofen Naproxen Ketoprofen

E

NVIRONMENTAL

R

ISK

A

SSESSMENT

-

SEAWATERS

Ha za rd q u ot ie n t (HQ )  Diclofenac

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Algae 1,00E-04 1,00E-03 1,00E-02 1,00E-01 1,00E+00 H az ar d qu ot ie nt (H Q ) Título do Gráfico Acetaminophen Acetylsalicylic acid Diclofenac Ibuprofen Naproxen Ketoprofen

E

NVIRONMENTAL

R

ISK

A

SSESSMENT

-

SEAWATERS

1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 Haz ar d q u otien t (H Q )

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C

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

University General Pediatric _Maternity

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

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C

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

 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

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I

MPACT 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

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

0 10 20 30 40 50 60 70 80 90 R e m o v a l e ff ic ie n c y ( % )

C

Removal efficiency of pharmaceuticals in the WWTP goes from not eliminated to >80%

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E

NVIRONMENTAL

R

ISK

A

SSESSMENT

– WWTP E

FFLUENTS

 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

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I

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

• _{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)

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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

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Pharmac

eutic

als

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  Sulfamethazine  Sulfadimethoxine  Sulfadiazine  Sulfapyridine  Ciprofloxacin  Enrofloxacin  Azithromycin  Clarithromycin SPE-UHPLC-MS/MS

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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

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Source Upstream WWTP1 Downstream WWTP1 Upstream WWTP2 Downstream WWTP2

An

tibioti

cs

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Carbamaz

epin

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 Concentration (ng/L) Upstream WWTP 1 0 50 100 150 200 250 300 Concentration (ng/L) Source of Lis River

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1E+00 1E+01 1E+02 1E+03 1E+04 1E+05 1E+06 L o a d ( m g /d /1 0 0 0 in h a b it a n ts ) 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 L o a d ( m g /d /1 0 0 0 in h a b it a n ts ) 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 1E+05 1E+06 L o a d ( m g /d /1 0 0 0 in h a b it a n ts ) Antibiotics (WWTP 1) Antibiotics (WWTP 2)

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

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Source: Paíga et al, submitted

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

tibio

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1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 Ci pr of lo xa ci n Su lfa m eth az in e Su lfa m eth ox az ol e Cl ar ith ro m yc in A zi th ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e Ci ta lo pr am Pa ro xeti n e A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q ) 1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 C ip ro fl o xa ci n S u lf a m eth a zi n e S u lf a m eth o xa zo le C la ri th ro m y ci n C a rb am a zep in e F lu o xeti n e S er tr a lin e A ceta m in o p h en Ib u p ro fen K eto p ro fen S al ic yl ic a ci d N ap ro x en D ic lo fen a c H a z a rd q u o ti e n t (H Q ) 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 Ci pr of lo xa ci n Su lfa m eth ox az ol e Cl ar ith ro m yc in A zi th ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e Ci ta lo pr am Pa ro xeti n e A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q )

E

NVIRONMENTAL

R

ISK

A

SSESSMENT

– L

IS RIVER

 Ibuprofen

 Ciprofloxacin

 Sulfamethozazole  Clarithromycin  Azithromycin

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E

NVIRONMENTAL

R

ISK

A

SSESSMENT

WWTP

EFFLUENTS 1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 Ci pr of lo xa ci n Tr im eth op ri m Su lfa m eth ox az ol e Cl ar ith ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e D ia zep am A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q ) 1E-07 1E-06 1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 Tr im eth op ri m Su lfa m eth ox az ol e Cl ar ith ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e D ia zep am A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q ) WW TP 2 WW TP 1  Ibuprofen  Diclofenac

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1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 Ci pr of lo xa ci n Tr im eth op ri m Su lfa m eth ox az ol e Cl ar ith ro m yc in A zi th ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e Ci ta lo pr am D ia zep am A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q ) WW TP 1 1E-05 1E-04 1E-03 1E-02 1E-01 1E+00 1E+01 Tr im eth op ri m Su lfa m eth ox az ol e Cl ar ith ro m yc in A zi th ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e Ci ta lo pr am Pa ro xeti n e D ia zep am A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac z a rd q u o ti e n t (H Q ) WW TP 2

E

NVIRONMENTAL

R

ISK

A

SSESSMENT

WWTP

EFFLUENTS

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Cristina Delerue-Matos– 05/07/2016 1E-03 1E-02 1E-01 1E+00 1E+01 1E+02 Ci pr of lo xa ci n Tr im eth op ri m Su lfa m eth ox az ol e Cl ar ith ro m yc in A zi th ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e Ci ta lo pr am D ia zep am A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q ) WW TP 1 1E-03 1E-02 1E-01 1E+00 1E+01 Tr im eth op ri m Su lfa m eth ox az ol e Cl ar ith ro m yc in A zi th ro m yc in Ca rb am az ep in e Fl u ox eti ne Se rtr al in e Ci ta lo pr am Pa ro xeti n e D ia zep am A ceta m in o ph en Ib u pr of en Keto pr of en Sa lic yl ic a ci d N ap ro xe n D ic lo fen ac H a z a rd q u o ti e n t (H Q ) WW TP 2

E

NVIRONMENTAL

R

ISK

A

SSESSMENT

WWTP

EFFLUENTS  Ciprofloxacin  Sulfamethozazole  Clarithromycin  Azithromycin  Fluoxetine  Sulfamethoxazole  Fluoxetine

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 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

C

ONCL

USIONS

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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.

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