Occurrence, distribution and fate of pharmaceuticals as ... · Flow 3 (m /dan): 5.500 6.310 ......
Transcript of Occurrence, distribution and fate of pharmaceuticals as ... · Flow 3 (m /dan): 5.500 6.310 ......
Occurrence, distribution and fate of pharmaceuticals as chemical markers of contamination from urban sources in the vulnerable area of the Ebro Delta (Spain) Mira Čelić1, Meritxell Gros1, Marinella Farre2, Damia Barceló1,2, Mira Petrović1,3
ICRA-Catalan Institute for Water Research, Water Quality Area1, Girona, Spain
IDAEA-CSIC, Department of Environmental Chemistry2, Barcelona, Spain
Catalan Institution for Research and Advanced Studies3, Barcelona, Spain
OUTLINE
o Introduction
o Sources and routes of entry of pharmaceuticals
o INTEGRA-COAST project
o Objectives of the study
o Study area and sampling sites
o Analysis
o Target pharmaceuticals in water samples
o Extraction of water samples
o Target pharmaceuticals in sediment samples
o Extraction of sediment samples
o Quality parameters obtained during analysis
o Results
o Occurrence of PhACs in water samples
o Removal during wastewater treatment processes
o Occurrence of PhACs in sediment
o Conclusion
INTRODUCTION Sources and routes of entry of pharmaceuticals
sea water
PhACs are the contaminants of anthropogenic origin with the biggest input into the environment.
•After their consumption they are discharged into wastewaters.
•PhACs are partially removed during wastewater treatment processes, being discharged into receiving water bodies.
•Changes in river flow have one of the greatest effects on water quality (point source pollution is controlled by river flow).
•Up to now there have been a lot of studies on their occurrence in waste and surface waters but information about their presence in sea and coastal areas is still sparse.
INTEGRA-COAST PROJECT
INTEGRA-COAST study microplastics, nanomaterials, emerging organic contaminants (pharmaceuticals and personal care products, new pesticides, perfluoroalkyl substances and siloxanes) and marine biotoxins in a vulnerable coastal area.
The main goal of INTEGRA-COAST is to perform an integrated study of the fate, behaviour, and the river transport of emerging pollutants, nanomaterials and microplastics in estuaries, wetlands and coastal waters and to identify specific organic contaminants used as chemical markers of wastewater pollution.
• To assess the impact of WWTP discharges in coastal areas and protected ecosystems, with special focus on the contamination by pharmaceuticals.
• To study the fate and transport of a large number of multiple-class pharmaceuticals in riverine and coastal ecosystems (e.g. occurrence in water and sediments).
• To evaluate possible seasonal fluctuations in the occurrence and behavior of these contaminants in these ecosystems.
• Identify relevant pharmaceuticals as markers of urban pollution in coastal areas with the objective to include them in risk assessment schemes and future monitoring programs.
OBJECTIVES INTRODUCTION
Study area – the Ebro Delta
• wetland area of 320 km2
• the third largest delta in the Mediterranean Sea with high biological productivity
• highly relevant for conservation
• has a typical Mediterranean climate (with rainfall concentrated in autumn and spring (200–300 mm) and intense summer drought (<50 mm))
• c.a. 13% of its total surface is composed of natural lagoons, bays and marshes
• agricultural is one of the main activities such as rice and orchards.
Three sampling campaigns:
• October-November 2015 (autumn)
• February-April 2016 (winter)
• June-July 2016 (spring-summer)
INTRODUCTION
Total number of 213 samples: 87 waters and 71 sediments
Sampling: 29 “hot-spots” sites
WWTP2 WWTP1
•wastewater IN/OUT •emissary •canals •Ebro river •lagoons •sea water (water/sediment)
Wastewater treatment plants (WWTP)
Edar Amposta (WWTP1)
Sant Carles de la Ràpita (WWTP2)
Served population: 19 805 14 262
Population equivalent (PE): 27.500 28.921
Flow (m3 /dan): 5.500 6.310
Type of the treatment: Biological with activated sludge
Biological with elimination of N with tertiary treatment
Analgesics/anti-inflammatories
Ketoprofen
Naproxen
Ibuprofen
Indomethacine
Acetaminophen
Salicylic acid
Diclofenac
Phenazone
Propylphenazone
Piroxicam
Tenoxicam
Meloxicam
Oxycodone
Codeine
Psychiatric drugs Carbamazepine
2-Hydroxycarbamazepine
10,11-epoxycarbamzepine
Acridone
Sertraline
Citalopram
Venlafaxine
Olanzapine
Trazadone
Fluxotine
Norfluxotine
Paroxetine
Diazepam
Lorazepam
Alprazolam
Antibiotics
Erithromycin
Azithromycin
Clarithromycin
Tetracycline
Ofloxacin
Ciprofloxacin
Sulfamethoxazole
Trimethoprim
Metronidazole
Metronidazole-OH
Dimetridiazole
Ronidazole
Cefalexin
To treat asthma Salbutamol
Histimine H2 receptor antagonists Loratadine Desloratadine Ranitidine Famotidine Cimetidine
Β-Blocking agents Atenolol Sotalol Metoprolol Propranolol Carzalol Nadalol
Cholesterol lowering agents
Atrovastatine
Pravastatine
Mevastatine
Antihypertensives Amlodipine Losartan Ibersartan Valsartan
Antihelmintics Albendazole Thiabendazole Levamisole
Diuretic
Hydroclorothiazide
Furosemide
Torasemide
Lipid regulators and cholesterol lowering drugs
Bezafibrate
Gemfibrozil
Pravastatin
Fluvastatin
Atrovastatin
X-ray contrast agents Iopromide
Anticoagulant Warfarin
Prostatic hyperplasia
Tamsulosin
Antiplatelet agent Clopidogrel
Sedation and muscle relaxation
Xylizine Tranquilizer Azaperone Azaperol
Synthetic glucocoticoid
Dexamethasone
Calcium channel blockers Diltiazem Verapamil Norverapamil Antidiabetic Glibenclamide
Target pharmaceuticals in water samples
Total=81 PhACs
ANALYSIS
Extraction of water samples
SAMPLE
PRE-TREATMENT
HPLC-ESI-MS/MS (QqLIT)
FILTRATION 0.7 µm/ 0.45 µm
Addition of 0.1% Na2EDTA
Addition of 34 isotopically labelled standards
500 mL sea water 100 mL river water and canals 50 mL effluent 25 mL influent
Elution with 6 mL MeOH
Analytical Protocol >>
EXTRACTION &
PRE-CONCENTRATION
Surrogate standards
Evaporation to dryness 1mL MeOH/H2O (10:90, v/v)
Gros et al., Journal of Chromatography A, 1248 (2012) 104-121
SPE OASIS HLB®
ANALYSIS
LC colum Purospher ® RP-18 (125x2mm) (5 µm) Quantification of target compounds: • MRM mode: two transitions [M+H]+ > 2 Products in PI [M-H]- > 2 Products in NI
HPLC-MS/MS
liquid chromatography coupled to tandem mass spectrometry
Analgesics/anti-inflammatories Acetaminophen Diclophenac Ibuprofen Indomethacine Ketoprofen Naproxen Mefenamic acid
Lipid regulators and cholesterol lowering drugs Bezafibrate Fenofibrate Gemfibrozil Mevastatin Pravastatin Atrovastatin
Macrolide antibiotics Erytromicin Roxithromycin Clarithromicin Josamycin Tylosin A
Β-blockers Atenolol Sotalol Metoprolol Timolol Nadalol Pindolol
Histimine H2 receptor antagonists Ranitidine Famotidine Cimetidine
Psychiatric drugs Diazepam Lorazepam Carbamazepine
Diuretic Hydrohlorothiazide Furosemide
Antihypertensive Nifuroxazide Enalapril
Sulfonamid antibiotics Sulfamethazine
Β-agonists Clenbuterol Salbutamol
Antidiabetic Glibenclamide
Other antibiotics Trimethoprim Chloramphenicol Metronidazole
Phenazone type of drugs Phenazone
Barbiturates Butalbital
Total=43 PhACs
ANALYSIS Target pharmaceuticals in sediment samples
PLE - ASE 300 Dionex
freeze-drying (-40 ºC, 0.044 bar) store at -20 ºC
Sample pre-treatment
Sample extraction
1g of sediment sample;
T=100ºC
methanol/water, 1/2 v/v
3 static cycles (5 min)
total flush volume 100% of cell
60s of nitrogen purge
SPE – extraction and clean-up
PLE extract (~22 mL) is diluted in 500
mL of HPLC water + 15mL Na2EDTA
SPE OASIS HLB®
Addition of 34 isotopically labelled standards
Elution with 8mL MeOH Reconsituted with 1mL MeOH/H2O (25:75, v/v)
Extraction of solid samples
HPLC-MS/MS (QqLIT)
Jelić et al., Talanta 80 (2009) 363-371
ANALYSIS
liquid chromatography coupled to tandem mass spectrometry
pressurized liquid extraction
Quality parameters obtained during analysis, recoveries (%) and method detection limits (MDL)
Recovery, % (n=3), ± RSD Sea Lagoons Canal Effluent Influent Analgesics/ant-inflammatories
59-114% 50-120% 56-146% 57-112% 59-110%
Lipid regulators and cholesterol lowering statin drugs
58-101% 60-96% 42-117% 70-99% 88-103%
Psychiatric drugs 63-114% 51-124% 41-147% 61-113% 55-115%
Histamine H1 and H2 receptor antagonist
62-124% 52-80% 40-95% 87-119% 50-112%
β-Blocking agents 71-126% 60-90% 57-120% 56-88% 57-109%
Duretic 85-101% 68-113% 53-91% 55-98% 63-76% Antidiabetic 87% 104% 97% 103% 112%
Antihypertensives 73-102% 60-90% 41-101% 51-85% 51-85%
Antiplstelet agent 91% 95% 86% 90% 60% Prostatic hyperplasia 110% 50-97% 100% 112% 56% To treat asthma 72% 82% 73% 117% 108% Anticoagulant 82% 123% 90% 76% 62% X-ray contrast agent 102% 52-85% 100% 94% 70%
Anti helmintics 55-120% 50-110% 50-115% 74-98% 60-112%
Synthetic glucocorticoid 80% 60-118% 82% 74% 65% Sedation and muscle relaxation
85% 123% 88% 83% 87%
Tranquilizer 90-92% 52-85% 93-100% 92-102% 76-92%
Antibiotics 63-121% 57-128% 53-116% 66-116% 61-120%
Calcium channel blocker 86-120% 60-127% 64-96% 83-115% 69-74%
MDL (ng/L) 0.01-7.2 0.01-9 0.03-15.2 0.2-26 0.2-50
ANALYSIS
Sediment Recovery (%)
Analgesics/antiinflammatories 60-118%
Phenayone type drugs 87-110% Lipid regulators and
cholesterol lowering statin drugs 77-115%
Psychiatric drugs 80-105%
Histamine H1 and H2 receptor antagonist 87-104%
Macrolide antibiotics 68-95%
Sulfonamid antibiotics 59-100%
Other antibioptics 75-93%
β-blockers 90-114%
β-agonist 84-111%
Diuretic 71-84%
Antidiabetic 89-116%
MDL (ng/g) 0.01-3.20
% removal WWTP_1st campaign
Elimination efficiency, %
0 10 20 30 40 50 60 70 80 90 100
bezafibrate
ibuprofen
naproxen
salicylic acid
ranitidine
atenolol
gemfibrozil
nadolol
atorvastatin
sulfamethoxazole
trimethoprim
diltiazem
desloratadine
clarithromycin
thiabendazole
oxycodone
hydrochlorothyazide
codeine
furosemide
albendazole
propanolol
valsartan
losartan
diazepam
tamsulosin
citalopram
>80%
(good removal)
Less then < 10 % removal
1st Campaing
RESULTS
Low to moderate removal rates were obtained for most compounds, except for analgesics and anti-inflammatories (>80%).
The pharmaceuticals belonging to the same
therapeutic groups show the similar removal for both
sampling campaing.
0 10 20 30 40 50 60 70 80 90 100
naproxen
bezafibrate
salicylic acid
ranitidine
atenolol
gemfibrozil
nadolol
atorvastatin
ciprofloxacine
sulfamethoxazole
trimethoprim
diltiazem
desloratadine
clarithromycin
thiabendazole
oxycodone
azaperone
hydrochlorothyazide
clopidrogel
codeine
furosemide
propanolol
valsartan
carbamazepine
losartan
diazepam
tamsulosin
Elimination efficiency, %
>80%
(good removal)
% removal _2nd campaign
2nd Campaing
RESULTS
Important - Dilution factor
the natural water bodies receiving effluents discharge
has the same chemical profile as wastewater effluents, detected in µg/L range.
Wastewater effluents are main source of pharmaceuticals in
river waters
0,00
2000,00
4000,00
6000,00
8000,00
10000,00
12000,00
14000,00
WWTP2 effluent Emissary Sant Carles WWTP2 effluent Emissary Sant Carles
1st Campaing 2nd Campaing
Co
nce
ntr
atio
n (n
g/L
)
0,00
2000,00
4000,00
6000,00
8000,00
10000,00
12000,00
14000,00
16000,00
18000,00
WWTP1 effluent DownstreamWWTP1
WWTP1 effluent DownstreamWWTP1
1st Campaing 2nd Campaing
Co
nce
ntr
atio
n (n
g/L
)
Calcium channel blocker
Antibiotics
Tranquilizer
Synthetic glucocorticoid
Anti helmintics
X-ray contrast agent
Anticoagulant
To treat asthma
Prostatic hyperplasia
WWTP2
WWTP1
Concentration of pharmaceuticals in WWTP effluents and in receiving natural water bodies
1,00
10,00
100,00
1000,00
10000,00
1 2 1 2 1 2 1 2 1 2 1 2
Canal A Canal B Canal C Canal D1 Canal D2 Canal D3
Co
nce
ntr
atio
n (
ng
/L)
Analgesics/ant-inflammatories Lipid regulators and cholesterol lowering statin drugs
Psychiatric drugs Histamine H1 and H2 receptor antagonist
β-Blocking agents Duretic
Antidiabetic Antihypertensives
Antiplstelet agent Prostatic hyperplasia
To treat asthma Anti helmintics
Synthetic glucocorticoid Tranquilizer
Antibiotics Calcium channel blocker
Concentration range 1 – 464.2 ng/L
Canals
Canals are used to assist in the growing of agricultural crops, thus water quality
requirements are essential. Water from this canals could be significant route of crop
contamination. dried
Sea water and lagoons
1,0
10,0
100,0
1000,0
10000,0
1 2 1 2 1 2 1 2 1 2 1 2
Bay Alfalcs A(beach)
Bay Alfalcs B(shore)
Bay Alfalcs C(inside)
Bay Fangar A(beach)
Bay Fangar B(shore)
Bay Fangar C(inside)
Co
nce
trat
ion
(n
g/L)
Antibiotics
Tranquilizer
Antihypertensives
Duretic
β-Blocking agents
Psychiatric drugs
Analgesics/ant-inflammatories
Concentration range 1-20 ng/L
ibuprofen acetaminophen salicylic acid phenazone
Atenolo Sotalol Hydrochlorothyazid Ibersartan varsartan
Iopromide tiabendazole
0,1
1,0
10,0
100,0
1000,0
1 2 1 2 1 2 1 2 1 2 1 2
Tancada A (shore) Tancada A (inside) Buda A (shore) Buda B (inside) Encanizada A (shore) Encanizada A (inside)
Co
nce
ntr
atio
n (
ng/
L) Salycilic acid
the most abundant compound with max conc. 252.8 ng/L
Sea water
Lagoons
Frequency of detection in water samples
•acetaminophen
•ibuprofen
•salicylic acid
• phenazone
•valsartan
• irbersartan
•thiabendazole
•iopromide
•atenolol
•clarithromycin
0 20 40 60 80 100
actaminophen
valsartan
thiabendazole
iopromide
venlafaxine
azaperone
ketoprofen
prophyphenazone
10,11-epoxyCBZ
sotalol
clarithromycin
naproxen
diclofenac
bezafibrate
atorvastatin
alprazolam
cimetidine
furosemide
glibenclamide
clopidrogel
levamisol
diltiazemsea water
lagoons
canals
Antihelmintics
Analgesics/anti-inflammatories
Antihypertensives
X-ray contrast agents β-blocking agents
Antibiotics
Sediment samples with influence of WWTPs discharges
0,000
5,000
10,000
15,000
20,000
25,000
Upstream of WWTP1 Downstream WWTP1
Co
nce
ntr
atio
n (
ng/
g)
0,000
2,000
4,000
6,000
8,000
10,000
12,000
14,000
16,000
18,000
20,000
Emissary SCr WWTP2 Canal C (WWTP2)
Co
nce
ntr
atio
n (
ng/
g)
Lipid regulators and cholesterol lowering statin drugs
Β-agonist A
nal
gesi
cs/a
nti
infl
amm
ato
rie
s β
-blo
cke
rs
Antidiabetic
Antibiotics
Sulfonamide antibiotics
Antidiabetic
β-b
lock
ers
An
alge
sics
/an
tiin
flam
mat
ori
es
Lipid regulators
Concentration range 0.09 -7.08 ng/g
Concentration range 0.01 -5.98 ng/g
WWTP1
WWTP2 The total concentration levels were up to 20 ng/g
Sediment samples
0,00
1,00
2,00
3,00
4,00
5,00
6,00
7,00
8,00
Bay AlfalcsA (beach)
Bay AlfalcsB (shore)
BayAlfalcs C
(open sea)
Bay FangarA (beach)
BayFangar B(shore)
Bay FangarC (open
sea)
Co
nce
ntr
atio
n (
ng/
g)
0,00
2,00
4,00
6,00
8,00
10,00
12,00
14,00
16,00
Canal A Canal B Canal C Canal D1 Canal D4
Co
nce
ntr
atio
n (
ng/
g)
Canals
0,00
1,00
2,00
3,00
4,00
5,00
6,00
7,00
8,00
9,00
Tancada A(shore)
Tancada A(inside)
Buda A(shore)
Buda B(inside)
EncanizadaA (shore)
EncanizadaA (inside)
Canal VellA (shore)
Co
nce
ntr
atio
n(n
g/g)
Analgesics/antiinflammatories
Phenayone type drugs
Lipid regulators and cholesterol lowering statin
Psychiatric drugs
Histamine H1 and H2 receptor antagonist
Macrolide antibiotics
Sulfonamid antibiotics
Other antibioptics
β-blockers
β-agonist
Diuretic
Antidiabetic
Sea
Lagoons
0.01-4.54 ng/g
0.11-2.81 ng/g
0.06-3.42 ng/g
ketoprofen
ranitidine
ketoprofen
Frequency of detection in sediment samples
0 20 40 60 80 100
diclofenac
bezafibrate
ranitidine
erythromycin
chloramphenicol
ketoprofen
ibuprofen
phenazone
pravastatin
metronidazole
furosemide
Indomethacine
actaminophen
atrovastatin
sotalol
naproxen
gemfibrozil
carbamazepine
cimetidine
sulfamethaxzine
clarithromycin
metoprololsea
lagoon
canal
•Histamine H2 receptor antagonists
ranitidine
diclofenac bezafibrate ibuprofen
erythromycin chloramphenicol
o Levels of PhACs detected in waste, river, canals, lagoons and sea water
indicate that they are widespread pollutants along the Ebro Delta.
o Wastewater treatment plants proven to be an important source of pollution
for water bodies, as well as for sediment.
o The compounds reaching the sea water coming from WWTP discharges
were from the several therapeutical groups: analgesics/anti-inflammatories
(such as acetaminophen, ibuprofen, salicylic acid, phenazone), β-blocking
agents (atenolol, sotalol, ibersartan, valsartan) and diuretics drugs
(iopromide, thiabendazole).
o The compounds most widely detected in sediments were: diclofenac,
bezafibrate, ranitidine, ibuprofen, erythromycin, chloramphenicol.
CONCLUSION
This work is supported by:
The Spanish Ministry of Economy and Competitiveness through the coordinated project TRANSFORM COAST (CGL- 2014-56530-C4-4-R) Generalitat de Catalunya (Consolidated Research Groups 2014 SGR 291–ICRA and 2014 SGR 418 Water and Soil Quality Unit). M.Celic acknowledges for grant for PhD received from the Spanish Ministry of Economy and Competitiveness (BES-2015-072297).
ACKNOWLEDGMENTS