Emerging Contaminants: Risk and Challenges for Water ...

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


• 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.


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


Science (Smarter Pest Control, Special issue – 16/08/2013)http://www.sciencemag.org/site/special/pesticides/index.xhtml

Global pesticide sales by region


NEONICOTINOIDS


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


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)


• 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


Article on drugs


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


•

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


•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)


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


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


WATER

SEDIMENT

Pharmaceuticals


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)


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,


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


WWTP as a pathway for aquatic contamination


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


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


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


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)


• 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


Accumulated loads (ng/L)

WW

TP

s


Perfluoroalkyl Substances (PFASs)Area of study Ebro Delta river

(Catalonia, Spain) WWTP IN

and OUT

Emissary

Irrigation

channels

Beach

Open sea

Estuary

Ebro river


Water samples – First campaign

Results

• The most frequent: PFOA

• The highest concentration: PFPeA

• The most polluted sample: WWTP IN


Risk Assessment and Pollutant Prioritization

III Jornada Agua y Sostenibilidad, Murcia, 15th December 201632Methods

For any compound i

Risk Assessment Methods


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


∑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)


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


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.


”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


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


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


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


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


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.


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


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,


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.


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


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


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


0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9


0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0


0

1

2

3

4

5

6

7


WWeWWi

0

5

10

15

20

25

30

35

40


0

2

4

6

8

10

12


0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0


0

1

2

3

4

5

6

7

8

9


0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0


WWi

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

4,5


0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0


0

1

2

3

4

5

6

7


WWeWWi

0

1

2

3

4

5

6

7

8

9

10


0

2

4

6

8

10

12


0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0


0,0

0,5

1,0

1,5

2,0

2,5

3,0


WWe

WWeWWi

WWeWWi

WWeWWi

WWeWWi


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


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


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


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


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


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


• 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


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


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


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:


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.


% 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


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


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


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


Hospital batch bioreactor

Non-Sterile treatment

Antibiotics

Cruz-Morato et al., STOTEN

Bioremediation of emerging pollutants from sewage

sludge by fungal bioaugmentation


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.


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


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


ARGs in water samples


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


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


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


Removal of pharmaceuticals from wastewater by fungal treatment andreduction of hazard quotients

Lucas et al. STOTEN (2016) In Press


Article on antibiotic resistant bacteria


| 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


Finally to address antibiotic resistance

new measures being introduced


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”


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


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)


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.


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


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

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