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Water: The Greatest Global Challenge, DCU Dublin, 27 th November 2014 Fate, Effects and Management of Emerging Contaminants in River Catchments under Water Scarcity Dr. Damià Barceló IDAEA-CSIC, Barcelona, Spain and ICRA, Girona, Spain

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Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Fate, Effects and Management of Emerging Contaminants in River Catchments under Water Scarcity

Dr. Damià Barceló IDAEA-CSIC, Barcelona, Spain and ICRA, Girona, Spain

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Water and food security The challenge of feeding 9 billion

people • Will the World face a Perfect

Storm of problems by 2030? • Prof. John Beddington (Science,

2010): – Through 1963-2011 global meat

consumption increased from 72 to 297 Million Tonnes (meat–based diets)

– Water, Food and Energy problems are intimately connected

• In the agricultural sector, farmers do not want to use water per se… they just want to grow crops profitably.

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Water and food security The challenge of feeding 9 billion

people • China has destroyed 28,000 rivers in

1993-2013… equivalent to Mississippi river flow of 16.790 m3/s

• “It has become a truism that Water Scarcity will be an important issue worldwide in the 21st century. We need to change in water management and use” (The Big Thirst: The Secret life and Turbulent Future of Water, by Charles Fishman, 2011)

• From water scarcity to resource scarcity

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Drought in California

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

California governor declares drought emergency Posted on January 18, 2014

Currently 85 percent of California is experiencing a severe drought; this is very serious because without water the nations leading agricultural producer at $16 billion annually (including the world's largest almond crop at $3 billion, alone) is in dire straights. The drought is predicted to cost farmers at least $1 billion.

Drought in California

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014 6

Drought in California

International New York Times, 4th October 2014

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Effects on water availability and biodiversity

80% of human population under risk 72% of large rivers show high threat level

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Water scarcity world map

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Higher hydrological variability Higher frequency of extreme events (floods, droughts) Higher water temperature Higher nutrient concentrations Presence of inorganic pollutants Presence of emerging contaminants Higher temperatures facilitate introduction of new pathogens Higher Indirect Human Exposure (via food) to pathogens and chemicals from agriculture

Multiple stressors affect the response to scarcity

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Addressing these issues requires moving from stressors to receptors, and then to the implications for biodiversity and humans, so recommendations can be provided for management

Why GLOBAQUA/SCARCE

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

GLOBAQUA is a multipurpose project that aims to: Identify the prevalence, interaction and linkages between stressors in multiple stressor situations, and to assess their effects in the chemical and ecological status

Water scarcity as a central stressor Holistic approach, including water quality, biodiversity, and ecosystems

with the effects on socio-economical regional development Establish cause-effect relationships using experimental manipulation

and integrative modelling

Improve water management practice and policies by taking into consideration the influence of multiple stressors

Consider the WFD (2000/60/EC) and other related regulations Analysis of current policies and scenario analysis of alternative

management practices and policies

Project goals

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014 13

Extensive field work Adige Sava Ebro Evrotas Evaluation of different management scenarios Anglian Souss Massa

Geographic coverage of GLOBAQUA study sites

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Occurence

More than 50 organic chemicals and 5 - 8 metals detected in each sample Concentrations: metals>industrial organic>pesticides>pharmaceuticals>PFC

The most polluted basin- Llobregat (metals, industrial organics, pharmaceutical and perflourinated compounds) Júcar- metals and pesticides Ebro metals, industrial organics, pharmaceuticals and perflourinated compounds Guadalquivir- the least polluted (lower number of pharmaceuticals,high concentrations of alkylphenols and metals)

Corganic=7 µg/l (pharmaceuticals, industrial organics) Cmetals=83 µg/l

Corganic=4 µg/l (pesticides, industrial organics) Cmetals= 44 µg/l

wwtp

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Estimates of human sources in different locations in the

Llobregat basin

Osorio V et al.(2012).Science of the Total Environment 440: 3–13.

Modeling of pharmaceuticals in river

networks

First order reaction rates for different compounds in different reaches clearly identified conservative compounds from those

suffering rapid degradation

Selected modeling developments during 2012

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

↑ hydrologic variability

Climate change:

•Glo

bal c

hang

e

Human activity:

Seasonality:

↓ natural hydrodynamics

Water quantity and quality is altered due to global change

↑Conductivity ↑Nutrients ↑Toxicants

(i.e. biofilms) Predicts ↑ extreme

hydrological situations

Nat

ural

co

ndit

ions

Drougths Floods

Epilithic biofilms

are subject to

river

characteristics

and respond very

quickly in front

stress conditions

Mediterranean rivers

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Castle Creek, Euroa, Victoria, Australia- Photograph by Nick Bond, Monash University

Complete dewatering of rivers- direct effects on organisms

MEDITERRANEAN rivers hydrology

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014 18

1. Between 30-60 % of global river network is temporary, that is, waterways that cease to flow at some points in space and time along their course are as abundant as permanently flowing waterways. Moreover, some large permanent rivers are shifting to temporary because of climate change and extraction of water.

2. Temporary waterways have a non negligible ecological and economical value, with unique aquatic and terrestrial diversities and crucial ecosystem services in semi-arid regions worldwide.

Acuña et al 2014 Science 343: 1080-1081

Why should we care about temporary waterways?

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Brasilian Fishes that survive in temporary pools

November 2014

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Indoor Experimental Streams Facility at the Catalan Institute of Water Research (ICRA)

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Pharmaceuticals exposure: mixture of 9 compounds (5000 ng/L) (similar to Llobregat River)

Flow Intermittency: water flow interrupted for one week in half of the channels

Carbamazepine Psychiatric drug 2% 124Sulfamethoxazole Antibiotic 14% 699Erythromycin Antibiotic 3% 169Metoprolol β-Blocker 37% 1845Atenolol β-Blocker 2% 117Ibuprofen Anti-inflammatory 8% 404Diclofenac Anti-inflammatory 7% 366Gemfibrozil Lipid regulator 3% 139Hydrochlorothiazide Diuretic 23% 1135

Nominal conc. (ng/L)

Treated channels% each

compound (*)Therapeutic family

Colonization period

Dry period

Return flow period

3 wk 1 wk 2 wk 6 wk

Experimental design Stress factors

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Intermittent Flow total biomass reduction≈ 17% algal biomass reduction≈ 87% increase in bacterial density at

2d-5d

Pharmaceuticals: total biomass reduction≈ 8% algal biomass reduction ≈ 20% non-effect on bacterial density

* p<0.05 (ANOVA 2 ways of repeated measures)

noP: no pharmaceuticals P: pharmaceuticals exposure

P x F (multi stress) no significant effects

Experimental design Biomass results

Intermittent Flow

0.2

0.3

0.4

0.5

0.6noPP

0

1050

60noPP

2d 5d 9d 11d

1e+11

2e+11

3e+11

4e+11

5e+11

6e+11

noPP

Flow (F)*

Flow (F)*

AFD

W (m

g / c

m2 )

0.2

0.3

0.4

0.5

0.6noPP

Continuous Flow

Chl

-a (µ

g · c

m- 2

)

0

10

20

30

40

50

60noPP

2d 5d 9d 11d

Bact

eria

(cel

ls ·

cm-2

)

1e+11

2e+11

3e+11

4e+11

5e+11

6e+11

noPP

Pharm (P)*

Pharm (P)*

Pharm (P)

P x F

P x F

P x F

Flow (F)

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Article on drugs

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Modelling of Pharmaceutical on a sewage-impacted Mediterranean river is feasible. First order reaction rate, conservative behaviour

Pharmaceutical compounds at environmental concentrations altered the algal biomass, the algal and bacterial community composition, and interfered in the metabolic processes (NPP and CR) of the biofilm

Flow intermittency caused similar effects on algae, bacteria and metabolic processes, but intensities were higher

When biofilms are faced to flow intermittency and pharmaceuticals: Algae were more affected and showed cumulative

effects Bacteria increased their resistance Field-derived BAFs>1000 were determined for selected

Pharmaceuticals and EDCs Selected Pharmaceuticals alter fish behavior

Conclusions 1

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

RIVER COMMON NAME Size

LLO3 Common carp 1 (B)

Ebro barbel 2 (B,S)

Punkim seed sunfish 1 (B)

LLO4 Common carp 1 (B) Ebro barbel 2 (B,S)

LLO5 Common carp 1 (B)

LLO6 Common carp 1 (B) Ebro barbel 2 (B, S)

LLO7 Common carp 1 (B)

RIVER COMMON NAME Size GUA 1 Andalusian barbel 1 (B)

GUA2 Andalusian barbel 1 (B)

GUA 3 Andalusian barbel 1 (B)

Common carp 1 (B) GUA 4 Andalusian barbel 1 (B) GUA 5 Andalusian barbel 1 (B)

RIVER COMMON NAME Size OCA Ebro barbel 2 (B, S)

EBR2 Ebro barbel 2 (B, S)

Common Carp 1 (B)

EBR3 Ebro barbel 2 (B, S) Common Carp 1 (B)

EBR4 Ebro barbel 2 (B, S) Common Carp 1 (B) European catfish 1 (B)

EBR5 Ebro barbel 2 (B, S) Common Carp 1 (B) European catfish 1 (B)

Pumpkinseed sunfish : Lepomis gibbosus Ebro barbel: Barbus graellsii

Common carp: Cyprinus carpio

Andalusian barbel: Luciobarbus sclateri

European catfish: Silurus glanis

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Intro

duct

ion

• Exp

erim

enta

l • R

esul

ts a

nd d

iscu

ssio

n • C

oncl

usio

ns

0

200

400

600

800

1000

1200

1400

1600

Commoncarp

EbreBarbel

Commoncarp

EbreBarbel

Commoncarp

EbreBarbel

Eurpeancatfish

Commoncarp

EbreBarbel

Eurpeancatfish

EbreBarbel

EBR2 EBR3 EBR4 EBR5 OCA

Conc

entr

atio

n (n

g/g

d.w

)

EDCs Emerging halogenated flame retardants Pesticides PFCs Pharmaceuticals UV filters

EBRO RIVER

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Membrane technology Membrane bioreactors (MBR) Nanofiltration/ultrafiltration Reverse osmosis Eco-friendly- technologies: Fungal Biodegradation

Advanced oxidation or reduction technologies (mainly catalytic or

photocatalytic) Advanced bioactive technologies (aerobic or anaerobic)

New solutions such as electrolysis/electro-dialysis, electromagnetic

treatment, pulsed UV or arc discharge, ultra-sound, cold plasma, and new type of permeable reactive barriers.

Advanced treatment options

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

1-naproxen 2-ketoprofen 3-ibuprofen 4-diclofenac 5-indomethacin 6-acetaminophen 7-mefenamic acid 8-propyphenazone 9-ranitidine 10- loratidine 11-carbamazepine 12- ofloxacin 13- sulfamethoxazole 14- erythromycine 15- atenolol 16- metoprolol 17- hydrochlorothiazide 18- glibenclamide 19- gemfibrozil 20- bezafibrate 21- famotidine 22- pravastatin 23-sotalol 24-propranolol 25-trimethoprim

0

0

20

40

60

80

100

10

30

50

70

90

CAS elimination, %

MBR

elim

inat

ion,

%

2

10-70% >70% <10%

20 40 60 80 100 10 30 50 70 90

1

3

4

6

5 7

8

9

10

11

14

17

12

13

15

16

18

19

20

21

22

23

24

25

Comparison of CAS and pilot-scale MBR performances

Radjenović et al. Wat. Res. 43 (2009), 831-841

Fate, removal and distribution of PhACs in wastewater treatment (MBR vs. CAS)

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Hospital batch bioreactor Non-Sterile treatment Antibiotics (53 compounds)

Cruz-Morato et al., STOTEN, submitted

Target analysis: Study of the removal of pharmaceutical compounds from hospital wastewater treated with fungi

Trametes Versicolor

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Wastewater as a o source of reusable water o source of contamination.

Challenge: eliminate pathogens and micro-pollutants for Water Reuse:

o urban, agri-cultural, industrial, recreational, and environmental applications

Tertiary treatment to produce better quality treated water: oxidation, activated carbon adsorption, membranes nanofil-tration (NF) and reverse osmosis (RO)

o RO: Very effective for more exigent purposes. o Microfiltration (MF) pretreatment necessary for turbidity reduction, etc. to prevent fouling of RO membrane

Tertiary treatment for Water Reuse

OBJECTIVE: Evaluation of a tertiary system based on MF–RO to treat the effluents form the Torroella de Montgrí WWTP (NE Spain)

Removal efficiency regarding pharmaceuticals and pesticides

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014 32

0

20

40

60

80

100Antibiotics

Analgesics and anti-inflammatories

β-blockers

Histamine

Lipid regulators

Psychiatric drugs

WWTPUV treatmentWWTP+ MFWWTP+ MF + RO

Rodriguez-Mozaz et al. Journal of Hazardous Materials “In press”

Removal efficiency of WWTP vs tertiary treatments

PHARMACEUTICALS Different removal depending on the therapeutic

group (different chemical group too)

Psychiatric drugs recalcitrant only removed with RO as final 3rd treatment

Lipid regulators easily removed during WWTP

Most of drugs Slightly better removal with uv or MF

99% removal for all drugs only with the WWTP-MF-RO system

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

blaTEM ermB qnrS

sulI tetW Total0

2

4

6

8

10

0

2

4

6

8

10- 10

- 8

- 6

- 4

- 2

0

- 10

- 8

- 6

- 4

- 2

0

Abso

lute

conc

entra

tion

Log

(ARG

cop

ies

/ ml)

Rela

tive

conc

entra

tion

Log

(ARG

cop

ies

/ 16S

rRNA

copi

es)

Absolute (bars) and relative (diamonds) concentrations of ARGs in the different water samples

ARGs in water samples

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Antibiotic Resistance Genes (ARG)

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

Solutions

The Need of More Information on Pharmaceutical residues in the Environment Residues in sediments, biota, links with ecological status,

hydrogeological regime and biodiversity

Advanced and Low Cost (if possible) Waste Water Treatment Options MBR, White rot fungi (WRF) and AOPs Dedicated treatment for hospital effluents-PPCPs and ARG EU and Swiss Strategy- advanced treatment processes

The Low-Dose Prescribing Concept and the implications of the Pharmaceutical Industry Avoid collateral impacts of non-optimized prescribing, lower-optimized dose, waste avoidance

Pharmaceutical industry work in line of saving lives means “all lives”

Water: The Greatest Global Challenge, DCU Dublin, 27th November 2014

ACKNOWLEDGEMENTS Acknowledgements

EU FP7 project Globaqua (Managing the effects of multiple stressors on aquatic ecosystems under water scarcity. Grant agreement No.: 603629-ENV-2013-6.2.1)

IDAEA-CSIC team ICRA team

Ministerio de Economia y Competitividad SCARCE (EVALUACIÓN Y PREDICCIÓN DE LOS EFECTOS DEL CAMBIO GLOBAL EN LA CANTIDAD Y LA CALIDAD DEL AGUA EN RÍOS IBÉRICOS) Consolider-Ingenio 2010 CSD2009-00065