III Jornada Agua y Sostenibilidad, Murcia, 15 th December 2016 Emerging Contaminants: Risk and Challenges for Water Quality. A Reconnaissance Study In Iberian River Basins Solutions using advanced treatment technologies in a Europe Damià Barceló 1,2 , Paola Verlicchi 3 , Sara Rodriguez - Mozaz 2 , Pablo Gago - Ferrero 1 , Daniel Molins - Delgado 1 , Silvia Diaz - Cruz 1 , Nicola Mastroianni 1 , Marianne Köck - Schulmeyer 1 , Cristina Postigo 1 , Bozo Zonja 1 , Miren Lopez de Alda 1 , Jaume Aceña 1 Sandra Perez 1 ,Maja Kuzmanovic 1 , Antoni Ginebreda 1 Gloria Caminal and Teresa Vicent 4 Santi Esplugas 5 and Yolanda Pico 6 1 IDAEA-CSIC, Department of Environmental Chemistry, Barcelona, Spain 2 ICRA - Catalan Institute for Water Research, Girona, Spain 3 University of Ferrara, Italy 4 Department of Chemical Engineering, UAB,Barcelona, Spain 5 Department of Chemical Engineering, UBarcelona, Spain 6 University of Valencia, Spain
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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,
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
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
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
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
Article on drugs
III Jornada Agua y Sostenibilidad, Murcia, 15th December 2016
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
WATER
SEDIMENT
Pharmaceuticals
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
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
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:
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.