emerging contaminants: risk and challenges for water
TRANSCRIPT
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Emerging Contaminants: Risk and Challenges for Water
Quality. A Reconnaissance Study In Iberian River BasinsSolutions using advanced treatment technologies in a Europe
Damià Barceló1,2, Paola Verlicchi3, Sara Rodriguez-Mozaz2 ,Pablo Gago-Ferrero1, Daniel Molins-Delgado1,
Silvia Diaz-Cruz1, Nicola Mastroianni1, Marianne Köck-Schulmeyer1, Cristina Postigo1, Bozo Zonja1, Miren
Lopez de Alda1, Jaume Aceña1 Sandra Perez1,Maja Kuzmanovic1, Antoni Ginebreda1 Gloria Caminal and
Teresa Vicent4Santi Esplugas5 and Yolanda Pico6
1IDAEA-CSIC, Department of Environmental Chemistry, Barcelona, Spain2ICRA - Catalan Institute for Water Research, Girona, Spain3University of Ferrara, Italy4Department of Chemical Engineering, UAB,Barcelona, Spain5Department of Chemical Engineering, UBarcelona, Spain6University of Valencia, Spain
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
• Britain faces a £30bn bill to clean
up rivers, streams and drinking
water supplies contaminated by
synthetic hormones from
contraceptive pills.
• More than 2.5 million women take
birth control pills in the UK.
• Ethinyl estradiol (EE2), the main
active ingredient is excreted and
washed into sewage systems and
rivers.
• EE2 can trigger a condition known
as intersex in freshwater fish, which
is thought be contributing to
significant drops in populations in
many species. • To achieve the EU proposed target of 0.035ppt for EE2
in water for a town of about 250,000 people, it would
cost about £6m to install granular activated carbon to
cut EE2 levels, with a further £600,000 being needed to
operate the system each year.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Introduction
Occurrence of polar pesticides, pharmaceuticals, illicit
drugs , personal care products and perfluoralkyl substances
Monitoring in the Iberian river basins: Ebro, llobregat, Jucar and
Guadalquivir
WWTP as a pathway for aquatic contamination
Transformation Products at the WWTP and in the river
Elimination and fate in advanced water treatment processes
Membrane bioreactors (MBR)
Fungal biodegradation- Ecofriendly treatment
Advanced oxidation processes: solar photocatalytic treatments
Nanofiltration, Reverse Osmosi, Hybrid Systems, Cyclodextrin
Polymer
Lessons learned at EU level
Outline
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Science (Smarter Pest Control, Special issue – 16/08/2013)http://www.sciencemag.org/site/special/pesticides/index.xhtml
Global pesticide sales by region
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Perfluoroalkyl substancesDue to PFASs properties are used in a lot of industrial applications
carpet, upholstery, paper, textiles, cookware, paint, polymers, lubricants, flame retardants, …
Hepatotoxic Immunotoxicity Disruptors of thyroid hormones
Thermally stable Resists degradation Hydrophobic and oleophobic Good surfactants, lubricants Non-flammable Chemically inert
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Main ingredients in PCPs
FAMILY COMPOUND
ANTIMICROBIALSAntibacterials and fungicide agents added to remove microorganisms and for their growth inhibition High lipophylicity/ Endocrine disrupting effects
Triclosan – Metiltriclosan– Triclocarban
MUSKSCompounds added to many products to provide fragance and to help to the absorption of the chemical products through the skinHigh lipophylicity/ Endocrine disrupting effects
NitromusksNitrogenous aromatic part
Musk ambrette– Musk xylene– Musk ketone
Polycyclic musksMore used that the nitrogenous.Quiral compounds; selective bioaccumulation of enantiomers
Galaxolide – Tonalide– Celestolide
INSECT REPELLANTSMedium-low lipophylicity
N,N-deethyl-m-toluamide(DEET) -1,4-dichlorbenzene (DCB)
PRESERVATIVES (PARABENS)Prevent bacteria from growing in water-based productsMedium-low lipophylicity/ Endocrine disrupting effects
Benzilparaben (BzP) – Butilparaben (BuP) – Etilparaben (EP) – Metilparaben (MEP) – Propilparaben (PP)
ORGANIC UV STABILIZERS (UV FILTERS) Absorb UV radiation. Prevent damage from sunlightDiverse lipophylicity/ Endocrine disrupting effects
Benzophenones, Ethylhexyl dimethyl PABA (OD-PABA) 4-methylbenzylidene camphor (4-MBC) –Octocrylene (OC)
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
• Due to widespread usage of PPCPs in everyday life and
their purpose is to produce specific biological effects on organisms, unwanted
environmental effects are to be expected.
• Some of these adverse environmental effects of PPCPs are toxicity,
development of resistant pathogenic bacteria, genotoxicity and endocrine
disruption [1,2].
• Although many PPCPs do not exhibit acute toxicity, they can have a cumulative
effect on the metabolism of non-target organisms [3,4] and ecosystems as a
whole [5].• Bioconcentration/bioaccumulation in fish: pharmaceuticals sertraline and fluoxetine,
UV filters octocrylene (OC), benzophenone-3, 4-methylbenzilidene camphor (MBC)
and EHMC (methoxycinnamate).OC, 4MBC, OctylMC impact key ENDOCRINE and
STRESS GENES in Embryos and larave of Chironomus riparus
• The anti-inflammatory drug diclofenac accumulates in trout’s liver and causes renal
alterations-this was the cause of the hight mortality of vultures
[1] Sumpter et al. (1998) Toxicol. Lett., 337, 102-113, [2] Kummerer (2004) J. Antimicrob. Chemother., 54, 311,
[3] Brooks et al. (2005) Environ. Toxicol. Chem.,24, 464-469, [4] Fent K, Kunz PY, Zenker A, Rapp M (2010)
Marine Environ Res 69:54-56, [5] Oaks et al. (2004) Nature, 427, 630-633
Environmental effects
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Occurrence and effects of PPCPs , Pesticides, Illicit drugs
and PFAS in Iberian River basins
WWTP as apathway for aquatic contamination
Transformation Prodcuts (TPs) formed in WWTP and River
Removal options (MBR, Fungal Biod, AOP, MF-RO,
Cyclodextrin Polymer)
Case studiesMonitoring
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
•
Júcar: designated as a European Pilot
River Basin for the implementation of
the WFD, overextraction of
groundwater, water quality problems in
the medium and lower parts
Guadalquivir: ecological value of the Doñana National Park,
many inputs (natural and anthropogenic origin), navigable up as
far as Seville (serious environmental problem)
Llobregat: Heavily managed in
its lower course, Barcelona’s
major drinking water resources,
extensive urban and industrial
waste water discharges
Ebro: intensive agricultural
activity, largely regulated
(200 dams and channels),
decreasing of 30% of the
mean annual flow
Study approach
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
•9166 ng/L
JÚCAR
Juc1
1
2
3
4
Juc2
1
2
3
4
Juc4
1
2
3
4
Juc6
1
2
3
4
Juc7
1
2
3
4
GUADALQUIVIR
Gua1
1
2
3
4
Gua2
1
2
3
4
Gu
a3
1
2
3
4
Gua4
1
2
3
4
EBRO
Ebr1
1
2
3
4 Ebr2
1
2
3
4
Ebr3
1
2
3
4Ebr4
1
2
3
4
Ebr5
1
2
3
4
Organic compounds in waterLLOBREGAT
LLo3
1
2
3
4
LLo4
1
2
3
4
LLo5
1
2
3
4
LLo6
1
2
3
4
LLo7
1
2
3
4
LLo3
% Pesticides (Pest)
% Endocrine Disruptors (ED)
% Perfluorinted compounds (PFC)
% Pharmaceuticals (Pharm)
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Spatial distribution of pesticides in the Ebro River Basin 2010-2011
The most polluted sites are ZAD, SEG and Ebro Delta (EBRO7, EBRO8 and EBR9)
ZAD showed a concentration of diuron > 100 ng L−1 (150 ng/L) in 2010
SEG showed a concentration of imazalil > 100 ng L−1 (409.73 ng/L) and for the sum of all pesticides >500 ng L−1 in 2010
There is a gradient of concentration in the Ebre Delta from 2.32 ng L−1 to 109.24 ng L−1 and in 2011 from 1.11 ng L−1 to 30.54 ng L−1 from 2.32 ng L−1 to 109.24 ng L−1 and in 2011 from 1.11 ng L−1 to 30.54 ng L−1
Pesticides in sediments were less frequents
Out of the 42 pesticides analyzed in 2010 and 50 pesticides in 2011, 6 and 7 respectively, were detected at the concentrations over the MLODs
The concentrations detected ranged from 0.10 to 36.17 ng g−1 of dry weight (d.w)
Regarding the highest concentrations, in 2010 were for terbutryn (21.61 ng g−1) and chlorpyrifos (9.59 ng g−1) in points sampled ZAD and EBR-9 respectively. In 2011, chlorpyrifos (36.17 ng g−1 in EBR-1) and diclofenthion (28.82 ng g−1 in OCA) had the highest concentrations
Water Sediments
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Spatial distribution of PFAS in the Jucar River Basin 2010
Low PFASs concentration in Magro andCabriel (50 ng L−1 )
high cumulative concentrations weredetected the upper part (main contributionwas of PFBA), and close to the mouth (maincontribution PFOS and PFDA)
All water samples have PFASs
PFOA (53.3 % of the sample) showed higherfrequency than PFOS (40.0%)
Long-chain PFASs (C≥10) were less commonin water samples than short-chain ones(PFBA and PFPeA were present in 60% ofthe samples)
Mean PFCA values ranged from 0.04 ng L−1
(PFTrDA) up to 83.1 ng L−1 (PFBA)
Among PFSs only PFHpS and PFOS weredetected with mean values of 24.4 ng L−1 and28.2 ng L−1, respectively
The highest concentration found was644 ng L−1 of PFBA.
CAB1
CAB2
CAB3
CAB5
CAB4
JUC1
JUC2
JUC3
JUC4JUC5
MAG1
MAG2
JUC6
JUC8
JUC7
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Llobregat River basin 2010 Llobregat River 2010
Increasing downstream loads
Cumulative levels (ng/L) of drugs of abuse along the
Llobregat River basin and overall load (gr/day, 2010)
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Differences in DAs levels between sampling campaigns
• Based on the collected data, difference between 2011 and 2010 median predictions and its 95%
Confidence Interval were estimated with the Quantile Regression Models (Median Regression
Models)
• Overall, lower rivers’ flows were recorded in the second sampling campaign (2011)
Cocaine Methadone
Compared to 2010, in 2011 statistically significant ( = 0.05) higher median concentrations were predicted
for compounds:
• Lorazepam (Δ median 15.7 ng/L) and sum of benzodiazepines (Δ median 17.1 ng/L) in the Llobregat
River basin
• Cocaine (Δ median 2.7, 95%CI 1.4;4.0) in the Ebro basin,
• Cocaine (Δ median 2.4 ng/L), ephedrine (Δ median 12.06 ng/L), total DAs (Δ median 25.3 ng/L) and sum
of Amphetamine Like Compounds (ALCs) (Δ median 13.1 ng /L) in the Guadalquivir basin.On the other hand, statistically significant lower median concentrations were predicted for:
• METH in the Llobregat (Δ median -1.2 ng/L) and Jucar (Δ median -0.68 ng/L) basins
•sum of opiates/opioids (Δ median -2.6 ng/L) in the Llobregat basin.
With the exception of the Guadalquivir basin, not clear relationship between
the concentrations of DAs and the hydrological conditions of the river basinsMastroianni N et al. HAZMAT, 2016, Pages 134–142,
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
BP3 BP1 4HB 4DHB EHMC 4MBC OC
%
Mean concentrations of the UV Filters detected in surface waters (ng/L)
Frequency of detection
Occurrence of UV Filters in surface water
499
(n=14)
(n=24)(n=24)
(n=15)
0
20
40
60
80
100
120
140
160
180
200
BP3 BP1 4HB 4DHB EHMC 4MBC OC
Co
nc
. (n
g/g
)
Concentration ranges (ng/L)
1498
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
WWTP as a pathway for aquatic contamination
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
0-25%
< 0%
Azinphos-ethylBuprofezin Carbendazim Carbofuran Chlorfenvinphos Diazinon Deethylatrazine Deisopropylatrazine Dichlofenthion Diuron Fenthion-sulfoxide Hexythiazox Imazalil ImidaclopridIsoproturon MethiocarbOmethoatePropazine Pyriproxyfen Tebuconazole Terbuthylazine Terbuthylazine-2-hydroxyl Terbuthylazine-deethyl Terbutryn Thiabendazole
Acetochlor Atrazine Chlorpyriphos Dimethoate Fenthion Sulfone Metolachlor Prochloraz Simazine Terbumeton
Molinate
Ethion Fenoxon Sulfoxide Propanil Terbumeton-deethyl
10%
64%
3%
23%
Average removal efficiency of pesticides in the WWTPs
PESTICIDES IN WWTPs
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
No elimination
•Macrolide
antibiotics
•Carbamazepine
•Benzodiazepines
•Serotonin reuptake
inhibitors
Sulfadiazine
SulfamethoxazNorfloxacin
Ofloxacin
CiprofloxacinTetracycline
EnalaprilSalbutamol
FamotidineRanitidine
CimetidineGlibenclamide
Nadolol
AtenololBezafibrate
GemfibrozilAtorvastatin
PropyphenazoKetoprofen
NaproxenIbuprofen
Diclofenac
AcetaminophenSalicylic acid
Furosemide
0 20 40 60 80 100% elimination
Good elimination
Occurrence of 73 pharmaceuticals in the Ebro River
basin - STP removal
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Average removal of each analyte in the various WWTPs
Overall removal of drugs of abuse and metabolites in each WWTP
Some compounds e.g. MA, MDMA,
opioids and benzodiazepines present
occasionally higher levels in
effluents than in influents.
Removal efficiency: cocainics (95%)
> cannabinoids (79%) > amphetamine
like compounds (58%) >
opioids/opiates (38%) >
benzodiazepines (15%).
Between 66% and 91 %.
Removal of drugs of abuse and metabolites in WWTPs
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
WWTP
Benzylparaben
(ng/L)
Butylparaben
(ng/L)
Propylparaben
(ng/L)
Methylparaben
(ng/L)
Influent Effluent Influent Effluent Influent Effluent Influen
t
Effluent
Lleida < LOQ < LOQ 96 < LOQ 5010 < LOQ 2466 < LOQ
Reus < LOQ < LOQ 7.05 < LOQ 1371 < LOQ < LOQ < LOQ
Tarragona < LOQ < LOQ < LOQ < LOQ 459 5.56 < LOQ < LOQ
Vilafranca Penedès < LOQ < LOQ < LOQ < LOQ 76.8 < LOQ < LOQ < LOQ
Vila-Seca/Salou < LOQ < LOQ 39.3 < LOQ 858 83.6 714 137
La Llagosta < LOQ < LOQ < LOQ < LOQ 414 < LOQ 75.6 < LOQ
Sabadell/Riu Sec < LOQ < LOQ 65.7 < LOQ 1695 2.58 < LOQ < LOQ
Terrassa na1 < LOQ na1 < LOQ na1 < LOQ na1 < LOQ
Girona < LOQ < LOQ 16.35 < LOQ 1005 < LOQ 41.1 < LOQ
Mataró < LOQ < LOQ < LOQ < LOQ 696 < LOQ 801 < LOQ
Montornés del Vallès < LOQ < LOQ < LOQ < LOQ 47.4 < LOQ < LOQ < LOQ
Vic < LOQ < LOQ < LOQ < LOQ 225.3 < LOQ < LOQ < LOQ
Gavà/Viladecans < LOQ < LOQ 1.602 < LOQ 855 < LOQ < LOQ < LOQ
Montcada < LOQ < LOQ 105 < LOQ 1494 < LOQ < LOQ < LOQ
El Prat de Llobregat < LOQ < LOQ 360 < LOQ 5700 < LOQ 2211 < LOQ
Rubí < LOQ < LOQ < LOQ < LOQ 156.6 < LOQ < LOQ < LOQ
St Feliu de Llobregat < LOQ < LOQ < LOQ < LOQ 363 < LOQ < LOQ < LOQ
Besòs (Fòrum) < LOQ < LOQ 11.46 < LOQ 648 < LOQ < LOQ < LOQ
Granollers < LOQ < LOQ < LOQ < LOQ 204.9 < LOQ < LOQ < LOQ
Manresa nd2 < LOQ 71.1 < LOQ 2475 < LOQ 2220 < LOQ< LOQ: below the limit of quantification
1na: not applicable (influent sample lacks)2nd: not detected
Occurrence of preservatives in wastewater
Propylparaben, the most ubiquitous (100% frequency of detection)
High elimination rates: ~ 100% (propylparaben 90-100 range and methylparaben 81-100 range)
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
• Individual parabens contribution in effluents
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
LLEIDA
REUS
TARRAGONA
VILAFRANCA DEL PENEDÈS
VILA-SECA/SALOU
LA LLAGOSTA
SABADELL/RIU SEC
TERRASSA
GIRONA
MATARÓ
MONTORNÉS DEL VALLES
VIC
GAVÀ/VILADECANS
MONTCADA
EL PRAT DE LLOBREGAT
RUBÍ
ST FELIU DE LLOBREGAT
BESÒS (Fòrum)
GRANOLLERS
MANRESA
Butylparaben
Propylparaben
Methylparaben
Occurrence of preservatives in wastewater
Accumulated loads (ng/L)
WW
TP
s
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Occurrence of preservatives in wastewater
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Perfluoroalkyl Substances (PFASs)Area of study Ebro Delta river
(Catalonia, Spain) WWTP IN
and OUT
Emissary
Irrigation
channels
Beach
Open sea
Estuary
Ebro river
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Water samples – First campaign
Results
• The most frequent: PFOA
• The highest concentration: PFPeA
• The most polluted sample: WWTP IN
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Risk Assessment and Pollutant Prioritization
III Jornada Agua y Sostenibilidad, Murcia, 15th December 201632Methods
For any compound i
Risk Assessment Methods
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Paraben EC50 (mg/L) HQ
D.
magna
P.
promelas
T.
Therm.
V.
fisheri
P.
leiogn.
O.
latip.
D.
magna
P.
promelas
T.
Therm.
V.
fisheri
P.
Leiogn.
O.
latipes
Butyl 5.3 7.3 7.3 2.8 4.3 3.1 < 0.5 < 0.5 < 0.5 0.58 Gavà < 0.5 < 0.5
Propyl 12.3 9.7 12.6 2.6 2.5 4.9 0.5 El Prat 0.55 Lleida
0.62 El Prat
2.04 Lleida
0.69 Sabadell
3.32 El Prat
1.01 Manresa
< 0.5 1.08 Lleida
1.23 El Prat
0.54 Manresa
Methyl 24.6 - 58 10 35 63 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5
BP4 50 - - - - - 0.01-004
0.01-0.02 (E)
- - - - -
Influent – Acute
Influents Effluents
Compound Concentration range (ng/L) Concentration range (ng/L)
Methylparaben < LOQ - 2466 < LOQ - 137
Propylparaben 47.4 - 5700 < LOQ – 83.6
Butylparaben < LOQ - 1603 < LOQ
Benzylparaben nd - < LOQ (0.00101) < LOQ (0.00101)
Summary of observed concentrations
ECOLOGICAL RISK ASSESSMENT
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
∑TU per site
Pharmaceuticals
Pesticides
Industrial
PFAS
TU i
TU Algae
Pesticides are the main
contributors to toxic risk for
algae (shown here), Daphnia
and fish.
Risk (Algae)
III Jornada Agua y Sostenibilidad, Murcia, 15th December 201635
CompoundLlobregat Ebro Júcar Guadalquivir
Algae Daphnia Fish Algae Daphnia Fish Algae Daphnia Fish Algae Daphnia Fish
Sertraline X X X X
Arsenic X X X X X
Cobalt X X X X X X X X
Triclosan X X X X
Parathion-Ethyl X X
Caffeine X X X X
Terbutrine X X
Isoproturon X X
Losartan X X X
Imazalil X X X X X
Tolytriazol X X X X
Simazine X X X
Atrazine X X X
Azinphos Ethyl X X X
Malathion X X X X X X X
Azinphos Methyl X X
Thiabendazole X
Methiocarb X X X
Venlafaxine X X X X
Gemfibrozil X X
Pyriproxyphen X X
RI higher than 0, lower than 12,5 %. In low TU at many sites in rivers
(pharmaceuticals and metals) or in high TU at few sites(pescides).
• Pesticides • Industrial
compounds
• Pharmaceuticals• Personal Care
• Metals Underline: WFD SP
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
hqHQsample
Additive model
PNEC
MECHQcompound
MEC: measured
environmental concentration
PNEC: predicted non effect
concentration
• For each compound, PNEC was derived from the lowest EC50 (algae, daphnids and fish) value divided by an uncertainty factor
(AF) of 1000.
• When no experimental values were available from the literature, EC50 were estimated by ECOSAR program (v 1.11)
• Only 2 samples (ZAD and GUA A) collected in the Ebro and Guadalquivir River basins, respectively, exhibited cumulative HQ>1
• The highest toxicity risk is associated to the presence of EDDP, followed by methadone, lorazepam and esctasy.
Cumulative hazard quotients (HQs): Ecotoxicological risk
Mastroianni N, Bleda MJ, López de Alda M, Barceló D. Journal of Hazardous Materials, Volume 316, 5 October 2016, Pages 134–142,
doi:10.1016/j.jhazmat.2016.05.025.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
”Non priority”
WFD priority
compounds
excluded
Risk of chronic
effects at 98% of the
sites
Acute risk 15% of
the sites
All the measured
compounds
Chronic risk at all
sites
Acute risk at 42% of
the sites
Emerging
contaminants
WFD priority
compounds and
banned pesticides
excluded
Risk of chronic effects
at 30% of the sites
No acute risk
Spatial risk assessment-legislation
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
0
50
100
150
200
250
300
350
400
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84
ng
/L
Xúquer River basin
Llobregat River basin
Ebro River basin
Barcelona area Valencia city
Guadalquivir River basin
Hessen Federal district
Tap water
PFASs in River and Drinking Waters of Spain
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Main objective To assess 16 PFASs in 96 drinking waters
(38 bottled waters and 58 samples of tap water) from Brazil, France and Spain.
The total daily intake and the risk index (RI) of 16 PFASs through drinking water
in Brazil, France and Spain have been estimated.
Perfluoroalkyl substancesPFASs in the water cycle in Europe and Brazil
TG. Schwanz, et al. (2012). STOTEN
Bottled water Tap water
Main compounds in bottled water:
In France: PFHxA and PFNA
In Spain: PFNA, PFOA and PFHxA
In Brazil: PFOA, PFOS and PFHxA
Main compounds in tap water:
In all countries: PFOS and PFNA
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
0
1
2
3
males femalesmales femalesmales femalesmales females
Children(6-11)years
Adolescents(12-19)years
Adults(20-60)years
Seniors(>60)years
ng/kgb.w
.day
BRAZIL
Beverage
Bo led
Tap
0
1
2
3
males femalesmales femalesmales femalesmales females
Children(6-11)years
Adolescents(12-19)years
Adults(20-60)years
Seniors(>60)years
ng/kgb.w
.day
SPAIN
Beverage
Bo led
Tap
0
1
2
3
males femalesmales femalesmales femalesmales females
Childrens(6-11)years
Adolescents(12-19years)
Adults(20-60years)
Seniors(>60years)
ng/Kg.b.w
.day
FRANCE
Beverage
Bo led
Tap
Results of total daily intake in different
countries and gender/age groups
The values of total dietary intake were as follow:
Brazil>France>Spain.
The contribution of tap water was higher that bottled
mineral water in Spain and Brazil, but not in France.
In France major contribution to PFAS through
hydration was tap water or other beverages.
In Brazil the influence of PFASs through other
beverages was the highest contribution.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Short term
exposure
In January 2009 the USEPA set short-term exposure scenario (acute toxicity) for
PFOS (200 ng/L). However, there is no available data regarding the continuous
exposure (chronic exposure).
The majority of the samples may not pose an immediate health risk to consumers,
with exception of 6 of the samples from the same village which concentrations of
PFOS exceeded the PHA level.
Long term
exposure
It should be considered the long time exposure (especially relevant for drinking
water).
Long-life exposure values ~10 times inferior than those for short-time exposure,
then 16 samples presented higher concentrations for PFOS (<20 ng/L).
The total sum of compounds should be considered but there is no available
information about this exposure.
Llorca, M. et al. (2012). STOTEN, 431(0): 139-150.
PFASs in Water . Exposure data
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Conclusions
Pesticides, PPCPs and illicit drugs are present at measurable
levels in surface river waters → high use of these substances and incomplete
elimination in WWTPs ( 50 % of pesticides poor or no removal)
Sometimes higher levels in Effluents as compared to Influents (i.e. sampling
variations not considering SRT, HRT, sludge, 24 composite samples) and
Pesticide Conjugates (desorption from particulate)
Most problematic PPCP (according to calculated TU): Fish: Genfibrozil, Venlafaxine
Daphnia:Sertraline,
Algae:Sertraline, Caffeine,Losartan,Venlafaxine,Triclosan
Most problematic Pesticides (according to calculated TU): Fish: Malathion, Imazalil,
Daphnia: Tolytriazol, Azinphos-Ethyl and –Methyl, Malathion,Methiocarb, Imazalil,
Parathion-Ethyl
Algae: Terbutryne, Isoproturon, Tolytriazol, Simazine, Imazalil,
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Conclusions1
2
3
4
Ebro delta river samples collected in 2015/2016. Fish samples showed
PFOS as the most ubiquitous and accumulated compound in skin along
different species. As regards carboxylic acids, PFHxA was the most
ubiquitous one.
For sediment samples at Ebro delta, PFOA, PFNA and PFHpA were the
most detected compounds among carboxylic acids while PFOS was the
most abundant among sulfonates.
PFASs are a threat to dinking water. 2009 EPA set a prelimianry health
advisory limit of 400 ng/L for PFOA and 200 ng/L for PFOS.This year EPA
is expected to set a lifetime health advisory for PFOA. Major contribution
through tap water but beverage cans can also be a problem(Brazil).
For water samples at the Ebro delta , PFOA is the most ubiquitous while
PFPeA shows the highest concentrations.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
VIRTUAL SPECIAL ISSUE ON DRINKING WATER CONTAMINANTSPapers covering five areas:
(a) Arsenic, fluoride and other multiple inorganic toxic
substances at drinking water sources: groundwater and well water
(b) Micro-organic contaminants and trihalomethane
precursors at drinking water sources
(c) Microbiological contaminants at drinking water sources
(d) Drinking water treatment technologies
(e) Risk at drinking water distribution systems
Read the Articles Here:
journals.elsevier.com/science-of-the-total-environment
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
DCF
Identified in GW &
aquifer systems Pérez and Barceló., 2008
NO
H3C
NH
S
NO2
OO
NO
H3C
NH
S
OO
Nitro-SMX
Desamino-SMX
NO
H3C
NH
S
NH2
OO
Nitration
Deamination
Denitrification
Denitrification
Nödler et al. (2012) Barbieri et al., 2012
NH
Cl
Cl O
OH
NO2
Nitro-DCF
NH
Cl
Cl O
OH
Nitration
NitrosationNitroso-DCF
Denitrification
Nitrification
Nitrification
Identified in WWWTPs
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Nitrifying/denitrifying DCF & SMX TPs in WWi, WWe & SW
WWTP3
WWTP5
WWTP6WWTP1
WWTP2
WWTP7
WWTP4
Urban area of Barcelona (Catalonia, NE Spain)
SW5
SW6
SW7
Rubí StreamLlobregat RiverWWi WWe
NO2-DCF
NO-DCF
Des-SMX
NO2-SMX
< 30 ngL-1
in-sewer microbial transformation
Jelić et al. (2015)
0
1
2
3
4
5
6
7
8
9
TP339 TP323 NO2-SMX Des-SMX
0
2
4
6
8
10
12
14
16
18
20
TP339 TP323 NO2-SMX Des-SMX
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
TP339 TP323 NO2-SMX Des-SMX
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
TP339 TP323 NO2-SMX Des-SMX
0
1
2
3
4
5
6
7
TP339 TP323 NO2-SMX Des-SMX
WWeWWi
0
5
10
15
20
25
30
35
40
TP339 TP323 NO2-SMX Des-SMX
0
2
4
6
8
10
12
TP339 TP323 NO2-SMX Des-SMX
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
TP339 TP323 NO2-SMX Des-SMX
0
1
2
3
4
5
6
7
8
9
TP339 TP323 NO2-SMX Des-SMX
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
TP339 TP323 NO2-SMX Des-SMX
WWi
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
TP339 TP323 NO2-SMX Des-SMX
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
TP339 TP323 NO2-SMX Des-SMX
0
1
2
3
4
5
6
7
TP339 TP323 NO2-SMX Des-SMX
WWeWWi
0
1
2
3
4
5
6
7
8
9
10
TP339 TP323 NO2-SMX Des-SMX
0
2
4
6
8
10
12
TP339 TP323 NO2-SMX Des-SMX
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
TP339 TP323 NO2-SMX Des-SMX
0,0
0,5
1,0
1,5
2,0
2,5
3,0
TP339 TP323 NO2-SMX Des-SMX
WWe
WWeWWi
WWeWWi
WWeWWi
WWeWWi
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Acute toxicity to Vibrio fischeri:
CompoundNOEC
(mgL-1)
LOEC
(mgL-1)
EC20
(mgL-1)
EC50
(mgL-1)
DCF 5.0 7.1 10.7 22.9
NO2-DCF 0.01 1.8 4.9 11.7
NO-DCF 15.0 45.1 66.0 >100
SMX 10.0 48.4 109 >100
Des-SMX 1.0 62.5 76.9 89.3
NO2-SMX 5.0 5.0 14.8 41.4
DCF
SMX Des-SMX NO2-SMX
NO-DCFNO2-DCF
Bioluminescence inhibition test
EC50 obtained from the fitted inhibition curves
NO2-DCF more toxic than DCF.
Des-SMX and NO2-SMX
are more toxic than SMX.
But LOECs >
environmental levels
Rosal et al., 2010; Majewsky et al.,
2014; and Rubirola et al., 2014
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Transformations of human metabolite Lamotrigine N2-glucuronide
in the aquatic environment
• Lamotrigine (LMG) is an anticonvulsant drug used in the treatment of epilepsy and
bipolar disorder
• It is extensively metabolized in humans to produce predominantly N2-glucuronide
• One U.S. study revealed the environmental occurrence of LMG and its N2-glucuronide with
mean concentrations in wastewater of 488 and 209 ng/L, respectively
Lamotrigine
Zonja et al. (2016) ES&T. 50(1):154-64
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Lamotrigine-N2-glucuronide mass balance
Lamotrigine – N2 -glucuronide
OXO-LMG
TP257
Lamotrigine
Lamotrigine – N2 –glucuronide
TP 430
Mass balance of ̴ 90% for the glucuronide
Sum of biotransformation reactions
in activated sludge
Mass balance of lamotrigine N2-
glucuronide
of 500 ngL-1 concentration
Zonja et al. (2016) ES&T. 50(1):154-64
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Transformations of LMG-N2-G – How is OXO-LMG formed?
imine hydrolysis
deconjugation
oxidation of
glucuronide acid
N-methylation
N-oxidation
Deconjugation
NO imine
hydrolysis
biotic
transformationAmidine hydrolysis
Zonja et al. (2016) ES&T. 50(1):154-64
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Abiotic amidine and guanidine hydrolysis of Lamotrigine N2-glucoronide
pH stability of the lamotrigine N2-glucuronide:-Stability in HPLC water @ pH 4, 5, 6, 7, 8 and 9
-Stability in HOSpital, INFluent and
EFFluent wastewater @ pH 7, 8 and 9
-Solutions were buffered with different buffer solutions
-Stability over the course of 36 hours (1 sample every 3 h)
Formation of LMG-N2-G-TP433-Amd @ pHs 7 - 9
pH 7
pH 8
pH 9
If N=O, TP433-Amd
Zonja et al. (2016)
WatRes (100) 466-475
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Compounds WWTP 1 WWTP 2 WWTP 3
influent effluent influent effluent influent effluent
Bef
ore
th
e d
egra
da
tion
of
LM
G-N
2-G
LMG-N2-G (1) 7.623 ± 0.555 2.193 ± 0.165 0.525 ± 0.019 0.098 ± 0.006 0.103 ± 0.009 0.019 ± 0.001 [37Cl]/[35Cl] [%] 62 59 66 68 63 61
LMG(2) 2.031 ± 0.114 4.897 ± 0.482 0.081 ± 0.027 0.378 ± 0.007 0.052 ± 0.012 0.072 ± 0.001 [37Cl]/[35Cl] [%] 60 64 46 64 63 63
SUM (1+2)a 9.654 (-27 %) 7.090 0.607 (-21 %) 0.477 0.155 (-41%) 0.091
N2-Me-LMG (3) n.d. 0.074 ± 0.007 n.d. 0.004 ± 0.001 n.d. <LOQ [37Cl]/[35Cl] [%] - 60 - 50 - 52
LMG-N2-Oxide (4) n.d. 0.078 ± 0.003 n.d. 0.011 ± 0.001 n.d. n.d. [37Cl]/[35Cl] [%] - 63 - 42 - -
SUM (1-4) 9.682 (-25 %) 7.242 0.608 (-19 %) 0.492 0.155 (-41%) 0.091
Aft
er t
he
deg
rad
ati
on
of
LM
G-N
2-G
OXO-LMG (5) 0.229 ± 0.047 1.204 ± 0.027 0.018 ± 0.006 0.094 ± 0.003 0.026 0.031 ± 0.008 [37Cl]/[35Cl] [%] 54 60 42 53 62 61
LMG-N2-G-TP433-Amd (6) 0.125 ± 0.024 n.d. n.d. n.d. n.d. n.d. [37Cl]/[35Cl] [%] 43 - - - - -
SUM (1-6) 10.036 (-16 %) 8.446 0.626 (-7 %) 0.585 0.181 (-33 %) 0.122
LMG-N2-G-TP430 (7) n.d. 1.062 ± 0.182 n.d. 0.052 ± 0.001 0.002 ± 0.001 0.008 ± 0.005 [37Cl]/[35Cl] [%] - 62 - 60 50 65
SUM all (1-7) 10.036 (-5 %) 9.508 0.626 (+2 %) 0.637 0.183 (-29 %) 0.130
-25 % -19 % -41 %
-5 % +2% -29 %Having in mind
ALL transformations
All transformations of LMG-N2-G - Mass balance in WWTPs
Zonja et al. (2016) ES&T. 50(1):154-64
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
• pharmaceuticals uptake by treated wastewater-irrigated root
crops (carrots and sweet potatoes)
• concentrations in the carrot leaves were in the following
order: carbamazepine > lamotrigine > caffeine
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Conclusions
o The identification of TPs of pharmaceuticals is still a laborious task but high-resolution MS in combination with analysis software (peak picking) holds greatpromise in assisting the automated data processing
o The major advantages of the suspect vs. targeted approach:
o generation of potential, environmentally relevant TPs under controlled
laboratory conditions
o rapid HR-MS-based screening of environmental samples for the
presence of these TPs with high confidence
o accelerated quantitative method development as compared to
conventional QqQ-MS-based analysis as no compound-specific MS
parameters need to be optimized
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Membrane technology
Membrane bioreactors (MBR)
Nanofiltration/ultrafiltration, MF
Reverse osmosis, RO
Eco-friendly- technologies: Fungal Biodegradation
Advanced oxidation or reduction technologies (mainly catalytic or
photocatalytic)
Porous Cyclodextrin Polymer
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
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
azith
rom
ycin
chlo
rote
tracy
clin
e
cita
lopr
am
clar
ithro
myc
in
doxy
cycl
ine
eryt
hrom
ycin
o-de
smet
hylv
anla
faxi
ne
oxyt
hetra
cycl
ine
rani
tidin
e
roxi
thro
myc
in
spira
myc
in
tetra
cycl
ine
tylo
sin
venl
afax
ine
ND
MA
FP
(%
)
0.01
0.1
1
10
100
NDMA Formation
Dichloramine and dissolved oxygen are critical for the formation of NDMASchreiber and Mitch, ES&T, 2006
•Investigated precursors :
Disinfection by-product formed when disinfecting with
chloramines, but its main source is tobacco, beer and cured meats,
Classified as a B2 carcinogen (EPA),
Some countries have guideline values for NDMA in DW
Australia 100 ng/L
California Department of Health 10 ng/L
The Ontario Ministry of the Environment 40 ng/L
US EPA included in the Contaminant Candidate List 3
(CCL3)
NDMA is included in the plan of work of the rolling
revision of the WHO Guidelines for Drinking-water Quality
•NDMA:
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
sampling date
15/5
/201
5
20/5
/201
5
27/5
/201
5
19/6
/201
5
26/6
/201
5
1/7/
2015
9/7/
2015
15/7
/201
5
22/7
/201
5
29/7
/201
5
12/8
/201
5
14/8
/201
5
21/8
/201
5
26/8
/201
5
28/8
/201
5
ND
MA
FP
(ng/L
)
0
2000
4000
6000
8000
10000
12000
14000
NO
3
- (m
g/L
)
0
5
10
15
20
25
30
NDMA FP MBR in
NDMA FP MBR out
NO3
- MBR in
NO3
- MBR out
Fate of total and individual NDMA precursors through a
MBR pilot plant and the effect of changing aeration conditions
sampling date
15/5
/201
5
20/5
/201
5
27/5
/201
5
8/6/
2015
17/6
/201
5
26/6
/201
5
1/7/
2015
8/7/
2015
15/7
/201
5
22/7
/201
5
29/7
/201
5
12/8
/201
5
13/8
/201
5
21/8
/201
5
25/8
/201
5
26/8
/201
5
27/8
/201
5
% r
emo
val
(M
BR
)
0
20
40
60
80
100
120
Citalopram
Erythromycin
Venlafaxine
NDMA FP
nitrification
nitrification
no nitrification
no nitrification
•NDMA formation potential removal by the MBR is
superior during aerobic operation.
•The removal of specific NDMA precursors correlates
with the removal of NDMA formation potential (three
examples shown in the graph).
•NDMA formation potential in and out a MBR pilot
plant was studied following the specifications of
Mitc h (2003)´s formation potential test.
•The fate of 14 NDMA precursors (antibiotics and
other pharmaceuticals) was also monitored.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
% of NDMA FP identified
Compound
Conc.MBR influent
(ng/L)
Conc. MBR
effluent (ng/L)
azithromycin
max 2492.7 1103.2
min 378.3 168.9
average 1510.4 499.7
st. dev (n=17) 729.1 279.1
citalopram
max 360.6 298.2
min 205.6 162.4
average 303.8 220.5
st. dev (n=17) 46.4 36.1
erythromycin
max 549 143.2
min 16.3 8.3
average 90 37.8
st. dev (n=17) 115.3 32.1
venlafaxine
max 741.2 515.7
min 433.8 313.4
average 568 399.1
st. dev (n=17) 79.9 53.3
clarithromycin
max 367 302
min 202.4 <LOQ
average 306.1 75.6
st. dev (n=17) 50.2 94.3
o-desmethylvenlafaxine
max 5988.9 2002.5
min 2070.3 870.5
average 4196.5 1467.6
st. dev (n=17) 929.7 345.6
ranitidine
max 1091.4 165.8
min 83 28.2
average 365.1 71.8
st. dev (n=17) 271.7 37.3
The maximum % of NDMA FP
that could be explained by the
target compounds was:
-2.6 % in the MBR influent
-5.3 % in the MBR effluent
EQuan MAXTM technology coupled to a TSQ
Vantage QqQ (Thermo Fisher Scientific)
On-line extraction (2 mL), LOD<1pg injected,
only requiring filtration of the sample
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
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
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
0
20
40
60
80
100Antibiotics
Analgesics and anti-inflammatories
β-blockers
Histamine
Lipid regulators
Psychiatric drugs
WWTP
UV treatment
WWTP+ MF
WWTP+ MF + RO
61Rodriguez-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
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
RO
membrane
Secondary
effluent
(Pressure)
Tertiary
effluent
AOPs
UV/H2O2 performed better than ozone to remove the analyzed pharmaceuticals.
Atenolol and Carbamazepine appeared as the most ozone resistant pharmaceutical.
Paroxetine and Trimethoprim required high H2O2 doses to achieve acceptable eliminations.
Comparison betwen UV/H2O2 and Ozone
Pharmaceutical mitigation by AOPs
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Hospital batch bioreactor
Non-Sterile treatment
Antibiotics
Cruz-Morato et al., STOTEN
Bioremediation of emerging pollutants from sewage
sludge by fungal bioaugmentation
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
A Alsbaiee et al. Nature 1-5 (2015) doi:10.1038/nature16185
P-CDP outperforms NAC for the rapid removal of a complex mixture of pollutants
at environmentally relevant concentrations.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
CAS (conventional activated sludge processes)
MBR + O3/UV and other AOPs
Ph-Chem (flocculation, coagulation…) as a pretreatment
MBR + NF/RO
MBR + O3 + PAC
Ch-Ph+CAS+PAC+Chl
Ch-Ph+Filt+Chl
MBR+Chl
MBR+(NF/RO)
MBR+O3+PAC+
Sand FiltrMBR+O3+(UV/H
2O2)MBR+PAC/UV
MBR+O3/UV
MBR+O3/
TiO2
Ch-Ph
MBR+UV
WHERE?
Most Investigated Treatments for hospital effluent
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Ecofriendly treatment alternatives such as white-rot-fungi -
Trametes versicolor are able to remove recalcitrant PPCPs and other pollutants
from WWTP
Degradation of PPCPs in sludge was demostrated with T. versicolor in sterile and
non-sterile systems
Removal performance was better in solid-phase biopiles than bioslurry reactors
Enhaced removal was obtained for several compounds when T. versicolor was
employed, respect to non-bioaugmentated systems
Urban and hospital wastewaters, after the treatment process, contribute to
antibiotic pollution and ARG
Ozonation, sand filtration, sorption and PAC are ineffective for reduction of ARG
but effective for other types of pollutants
Conclusions
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
blaTEM ermB qnrS
sulI tetW Total
0
2
4
6
8
10
0
2
4
6
8
10
- 10
- 8
- 6
- 4
- 2
0
- 10
- 8
- 6
- 4
- 2
0
Ab
so
lute
co
ncen
trati
on
Lo
g (
AR
G c
op
ies /
ml)
Rela
tive
co
ncen
trati
on
Lo
g (
AR
G c
op
ies /
16S
rR
NA
co
pie
s)
Absolute (bars) and relative (diamonds) concentrations of ARGs in the different
water samples
ARGs in water samples
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Fungal treatment of veterinary hospital wastewater
2 Bioreactors• Inoculated (Fungi) • Control
2 Analytical procedures• Chemical (Antibiotics)• Molecular (ARGs)
Experimental design
Triplicates samples at• time = 0 days• time = 15 days
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Summary: WWTP vs fungal treatment
Rela
tive c
on
cen
trati
on
[L
og
(A
RG
co
pie
s / 1
6S
rR
NA
co
pie
s)]
WWTPUrban wastewater
ng/L Fungal treatmentVeterinary hospital wastewater
ng/L
80%
70%
45%
48%
Lucas et al. Chemosphere 152 (2016) 301-308
Rodriguez-Mozaz et al. Water Research 69 (2015) 234-242
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Removal of pharmaceuticals from wastewater by fungal treatment andreduction of hazard quotients
Lucas et al. STOTEN (2016) In Press
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Article on antibiotic resistant bacteria
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
| 79
Selected papers from 2012 up till now covering four
areas:
• The origin of the problem. Presence in hospitals and
wastewater treatment plants
• Occurrence and risk in water, soil, sediment and river
catchments
• Human Health risk through drinking water
• Removal technologies.
Virtual Special Issue:
Antibiotic Resistance in the Environment
www.elsevier.com/locate/STOTEN
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Finally to address antibiotic resistance
new measures being introduced
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Solutions
The Need of More Information on Pharmaceutical residues in the
Environment
Residues in sediments, biota, links with ecological status, hydrogeological
regime and biodiversity-impacts on Microbial communities(Biofilm) +
Macroinvertebrates (Chironomus)
Advanced and Low Cost (if possible) Waste Water Treatment,
including ARG removal
MBR, White rot fungi (WRF) and MF-RO
Dedicated treatment for hospital effluents-PPCPs and ARG,i.e. Hybas(hybrid
biofilm and Activated Sludge system)
EU and Swiss Strategy- advanced treatment processes
The Low-Dose Prescribing Concept/ 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”
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Around 100 WWTPs (out of 750) are the target WWTPs
(interested in the upgrading)
47 Target compounds (out of 240 screened compounds)
22 Pharmaceuticals Atenolol, azithromycin, bezafibrate, carbamazepine,
carbamzaepine(TP), clarythromycin, diatrizoate, diclofenac,
erythromycin, ethinylstradiol, ibuprofen, iomeprol,
iopamidol, iopromide, mefenamic acid, metformin,
metoprolol, naproxen, sotalol, sulfamethoxazole, N4-
acetilsulfamethoxazole, trimethoprim
13 Biocides 2,4-dichlorophenoxyacid, carbendazim, diazinon,
diethiltoluamide (DEET), dimethoate, diuron, glyphosate,
AMPA, irgarol, isoproturol, MCPA, mecocrop-p, triclosan
5 Endocrine
disruptors
Bisphenol A, estradiol, estrone, nonilphenol, PFOS
7 others Acesulfame, benzotiasole, benzotriazole, EDTA,
methylbenzotriazole, NTA, sucralose
Target compounds and target WWTPs
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Ozonation
Micropollutants can be largely
eliminated (> 80 %) with 12–15 g
PAC/m³ of wastewater
An ozone dosage of 3–5 g O3/m³ of
wastewater is required for
elimination of the majority of
micropollutants (>80 %)
The use of PAC does not significantly
increase the energy requirement of a
WWTP (< 5% excluding filters).
Energy consumption of the
WWTP is increased by 10–30%. 83
Recommended technologies for upgrading
Powdered activated carbon (PAC)
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
Lessons learned
In choosing the sequence, adopt treatments that can induce different removal mechanisms. In this way, compounds of different chemical charcateristics can be removed simultaneously.
Biological processes represent a necessary step in the removal of pharmaceutical compounds. Their removal efficiencies depend on many factors.
Up to now, advanced oxidation processes are the most efficient and promising treatments, in particular ozonation and O3/UV.
Source separation is another possibility. For instance, urine/faecis separation or segregation of toilet discharges produced in wards/departments with higher impact . They are expensive and in any case they can be adopted only in new hospital buildings.
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
85
Lessons learned
Membrane bioreactors MBRs retain bacteria more effectively and in
particular strains of antibiotic-resistant bacteria (Dagot, 2012)
In MBR, higher SRT and less sludge load F/M enhance the development of
bacteria colonies able to attack more recalcitrant compounds. MBR
smaller flocs favor the contact with micro-contaminants and enhance
their degradation. Higher contact surface favor sorption processes..
Main removal mechanisms: metabolic and co-metabolic + sorption onto
sludge
Efficient solid/liquid separation by means of an ultrafiltration membrane.
Porous Cylcodextrin Polymers, promizing technology?
Ozonation, sand filtration, adsorption on PAC are ineffective for the
reduction of ARG, but effective on other types of micro-pollutants.
More treatments like white-rot-fungi able to remove ARG
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
IDAEA-CSIC teamICRA team
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)
The SOLUTIONS project has received funding from the European
Union’s Seventh Framework Programme for research, technological
development and demonstration under grant agreement no. 603437