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