wastewater effluents as the principal emission source … · wastewater effluents as the principal...

Wastewater effluents as the principal emission source of pharmaceuticals to Iberian River

Basins (Spain)

Victoria Osorio, Aitor Larrañaga, Jaume Aceña, Sandra Pérez and Damià Barceló

5th SCARCE Final International Conference

Pharmaceuticals (PhACs): Why their study?Pharmaceuticals (PhACs): Why their study?Inherent bioactivity

Growing consume in human and veterinary medicine

(~4000 approved drugs worldwide)

Introduction Introduction

Source: OECD Health Data: Health expenditure and financing: OECD Health Statistics (database) (2012)

PhA

Cs

Expe

nditu

re p

er c

apita

PhACs PhACs : Entry into Aquatic System: Entry into Aquatic System

Animal excretion

Industrial or Direct flush

WWTPs ≠ treatmentsPhACs ≠ physico-chemical

properties

Wide range of removal rates

Human excretion

Detection of PhACs in WW effluents, surface waters, groundwater and drinking water.


Global Occurrence of PhACs in receiving surface watersGlobal Occurrence of PhACs in receiving surface waters

Data provided by Dr. Stephen Hughes (JBA consulting, NY, UK)Data provided by Dr. Stephen Hughes (JBA consulting, NY, UK)


PhACs: Environmental ConcernPhACs: Environmental ConcernContinuous entry into the environment: “pseudo-persistent”

Potential effects on aquatic systems:

NO ENVIRONMENTAL REGULATION DATADiclofenac, 17-beta-estradiol and 17-alpha-ethinylestradiol included in the EU Comision first watch list of

substances to gather monitoring data and to address the risk posed by those substances.

antibiotics resistance (A.S.Valenzuela et al. 2009)

antibiotics and antiinflammatories cause significant structural and

functional changes in microbial attached communities of bioflims

(Proia et al. 2013; Lawrence et al. 2012)

LOEC of diclofenac in fish in the range of WW effluent

concentrations (Schwaiger et al. 2004; Triebskorn et al. 2004)


DIRECTIVE 2013/39/EU OF THE EUROPEAN PARLIAMENT AND OF THE COUNCILof 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy.

Guadalquivir

Case study II: the Guadalquivir River and its tributaries Borosa, Guadiana menor, Magaña, Guadalbullón, Yeguas, Cacín, Genil, Bembézar, Corbones, Guadaira and Guadiamar (24 sampling sites)

The Iberian River BasinsThe Iberian River BasinsLlobregat

Case study I: lower section of the river (2 sampling points)

Case study II: the Llobregat River and its tributaries Cardener and Anoia (14 sampling sites)

Case study II: the Ebro River and its tributaries Arga, Gállego, Martín, Cinca, Ésera, Ribera Salada, Segre, Matarranya and Algars (24 sampling sites)

EbroJúcar

Case study II: the Júcar River and its tributaries Cabriel and Magro (14 sampling sites)

SCARCE ProjectSCARCE Project

WWTPs characteristicsWWTPs characteristicsSCARCE ProjectSCARCE Project

Basin WWTPEquivalent

people Flow

(m3 day-1)Treatments

% BOD5

(Inf/Eff)% SS

(Inf/Eff)

EBRO

Pamplona 776190 86141 (2011) Secondary n 94 96Logroño 466560 51387 (2011) Secondary n 96 96Tudela 46237 18573 (2010) Secondary 95 92

Zaragoza 1200000 259200 (2011) Secondary n 92 -Lleida 186000 59706 (2009) Secondary n 95 95Tortosa 46847 6670 (2011) Secondary 98 97

GUADALQUIVIR

Cordoba 522000 108000 (design) Secondary 95 94

Loja 30480 - Secondary - -Moron de la

Frontera30000 90000 (design) Secondary 96 -

Copero (Sevilla) 1487500 135000 (2010) Secondary n 36 63

Ranilla (Sevilla) 555000 90000 (design) Tertiary 93 91

LLOBREGAT

Manresa 196167 53500 (design) Secondary n 95 92

Igualada 285666 20000 (design) Secondary 95 90

Abrera 80000 23000 (design) Secondary n 98 98

JUCARCuenca 80000 15000 (2012) Secondary - -Alzira 232656 33584 (2012) Tertiary 95 98

Target CompoundsTarget Compounds

• Lipid regulators & cholesterol lowering statin drugs

•Antibiotics:

SulfamethoxazoleSulfamethoxazole

• Analgesics and anti-inflamatories

DiclofenacDiclofenac

• Psychiatric drugs •β-Blocking agents

AtenololAtenolol

79 Pharmaceuticals - 17 Therapeutic Groups

ExperimentalExperimental

EnalaprilEnalaprilBezafibrateBezafibrate

LorazepamLorazepam

• Antihypertensives

UPLCUPLC--ESIESI--QLITQLIT--MS MS

Gros M, RodrGros M, Rodrííguezguez--Mozaz S, BarcelMozaz S, Barcelóó D (2012) D (2012) Journal of Chromatography A, 1248104Journal of Chromatography A, 1248104–– 121121..

Analytical MethodAnalytical Method

SEWAGE &

SURFACEWATER

SAMPLESfiltration to 0.45 µm Spiked with deuterated

standards

SPE Off-line

Oasis HLB500 ml sample8 ml MeOH elution

Sample preSample pre--treatment:treatment:

Sample analysis:Sample analysis:

ExperimentalExperimental

ResultsResultsPhACs in Waste Water Treatment PlantsPhACs in Waste Water Treatment Plants

Defined Daily Dose of PhACs in SpainDefined Daily Dose of PhACs in SpainDiscussion Discussion

Data extracted from the Spanish Health National System Annual ReData extracted from the Spanish Health National System Annual Report 2011port 2011

0

200

400

600

800

1000

1200

1400

1600

1800

2000D

DD

(mill

ions

of c

onta

iner

s)

Therapeutic groups & individual compounds

AHT

ELR

IPF

LIR

SVT

MFM

PDT

LZM

ATV

ADB

ALS

AMP

MTL

ANT

AUR

OPZ

ALC

Antiulcerants

Analgesics & Antiinflammatories

Lipid Regulators & cholesterol lowering statin drugs

AntidiabeticsPsychiatric drugs

Antihypertensives

ResultsResultsPhACs in receiving surface watersPhACs in receiving surface waters

ANO 1 ANO 2 LLO 4 LLO 5 CAR 3 CAR 4 EBR 3 EBR 4 EBR 5 EBR 6 EBR 7 EBR 8

250

2250

750


JUC 2 JUC 3 JUC 6 JUC 7 GEN 2 GEN 1 CAC GUA 3 GUA 4

50

250200

Occurrence of PhACs in receiving surface waters Occurrence of PhACs in receiving surface waters (former studies)(former studies)

Discussion Discussion

Psychiatric drugs


Lipid regulators & cholesterol lowering statin drugs

Histamine H1 & H2 receptor antagonistsAntibiotics

β-Blocking agents

Gros et al., 2007 Environ. Toxicol. Chem. 26



AntibioticsAntibiotics

Psychiatric drugs Histamine H1 & H2

receptor antagonists

LLO 4

Con

cent

ratio

n ng

L-1


WWTP ABR

WWTP MAN

WWTP IGU

WWTP LOG WWTP ZAR

WWTP TORWWTP TUD

DiscussionDiscussionPhACs in receiving surface watersPhACs in receiving surface waters

WWTP ALZ

WWTP CUE

WWTP ECI

WWTP CORWWTP LOJ

DiscussionDiscussionVariation of pharmaceutical concentrations in WWVariation of pharmaceutical concentrations in WW

Gros et al., 2010Environment International 36 15–26

CarbamazepineGlibenclamide

CodeineEnalapril

DiscussionDiscussionVariation of pharmaceutical concentrations in WWVariation of pharmaceutical concentrations in WW

log10(Effluent/Influent)

-3 -2 -1 0 1 2 3

Analgesic/anti-inflamatories

ators and cholesterol lowering statin drugs

Others

Antihypertensives

Diuretics

Beta-Blocking agents

Histamine H1 and H2 recetors antagonists

Psychiatric drugs

Antihelmintics

Antibiotics

Diluted Concentrated



Others

Antihypertensives

Diuretics

β-Blocking agents

Histamine H1 & H2 receptor antagonists

Psychiatric drugs

Antihelmintics

Antibiotics

Dilution Concentration

Gros et al., 2010Environment International 36 15–26

β-Blocking agents


Lipid regulators

Cholest. lowering statin drugs

Diuretics

Antibiotics (macrolides)

DiscussionDiscussionWW effluent loads of PhACs into SWWW effluent loads of PhACs into SW

LOA

D=

Flow

x C

once

ntra

tion

Llobregat Ebro Júcar Guadalquivir

PhACs were detected in the µgL-1 range in WW and ngL-1 range in SW

The more consumed PhAcs: Analgesics and Antiinflamatories, Antibiotics and

Lipid regulators and cholesterol lowering statin drugs are the more ubiquous and

concentrated in WW and SW.

The variation of PhACs levels after the WW treatment revealed that the WWTPs

studied are unable to remove a wide range of PhACs.

The increase of loads of PhACs in WW effluent receiving SW pointed out

WWTPs as the main emission source of PhACs into Iberian River basins.

ConclusionsConclusionsConclusionsConclusions

Evaluation of potential ecotoxicological risk of PhACs on aquatic

organisms:

• Determination of Hazard Quotients (HQAlgae, HQDaphnid, HQFish)

Toxicity vs levels variation success in WWTP:

• Prioritization of PhACs depending on their concentration/dilution in the WWTP

and their ecotoxicological effect treshold values.

• Detection of sensitive locations of the river basin and seasons of the year

where and when there is a special ecotoxicological risk.

Future WorkFuture WorkConclusionsConclusions

Thanks for your attention

This work has been supported by the Spanish Ministry of Science This work has been supported by the Spanish Ministry of Science and Innovation through the Consoliderand Innovation through the Consolider--Ingenio 2010 project Ingenio 2010 project SCARCE (CSD2009SCARCE (CSD2009--00065) and reflects the author00065) and reflects the author’’s view.s view.

AcknowlegdmentsAcknowlegdments

Occurrence of PhACs in receiving surface waters Occurrence of PhACs in receiving surface waters (former studies)(former studies)

Discussion Discussion

Psychiatric drugs



Histamine H1 & H2 receptor antagonistsAntibiotics

β-Blocking agents

Gros et al., 2007 Environ. Toxicol. Chem. 26

Analgesics & Antiinflammatories Lipid regulators &

cholesterol lowering statin drugs

AntibioticsAntibiotics

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