water quality of lake paranoÆ: emerging pollutants - ufz · water quality of lake paranoÆ:...
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1Patrocinadopor
Funded by
IWASBrazil
ÁGUA‐DF
Water Water QualityQuality of Lake of Lake ParanoParanoáá::EmergingEmerging PollutantsPollutants
E. WorchE. Worch11, H. B, H. Böörnickrnick11, B. Steiniger, B. Steiniger11, M. Majewsky, M. Majewsky22, G. Abbt, G. Abbt‐‐BraunBraun22, F. H. Frimmel, F. H. Frimmel22, C. , C. CavalcantiCavalcanti33, C. Pinke, C. Pinke33
11 TU Dresden, Institute of Water TU Dresden, Institute of Water ChemistryChemistry22 Karlsruhe Institute of Technology, Karlsruhe Institute of Technology, ChairChair of Water of Water ChemistryChemistry33 CAESBCAESB
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito Federal Federal �� DFDF
June 4June 4‐‐6, 20136, 2013
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Introduction1
The main objective of the subproject „Water Quality“ consisted in the characterization of the water quality with respect to a future use of Lake Paranoá water for drinking water supply.
The significance of the study results in particular from the specific conditions of this urban lake located within the city of Brasilia.
Brasilia and the Federal District are characterized by:
o High population densityo Increasing populationo Limited water resources
The Lake Paranoá is the receiving water body for two municipal wastewater treatment plants.
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Introduction1
WWTP North
WWTP South
Possible location of future raw water extraction
Ribeirão do TortoCórrego do Bananal
Riacho FundoRibeirão do Gama
Source: CAESB
Source: CAESB
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Screening Strategy2
Before starting the experimental work two questions had to be answered:
o Which sampling points should be chosen? o Which compounds can we expect?
The sampling points were selected with help of CAESB.
The compounds were selected on the basis of experience from Europe and North America (compounds typical for wastewater-influenced surface waters)
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Diffuse input
Lake
WWTP
Households Hospitals Industry Agriculture
Diffuse input
Screening Strategy2
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Screening Strategy2
WWTP North
WWTP South
Sampling points
E
A
C
F
D
B
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Knowledge -occurrence?
Well known for long time (30 –40 years)
Known for 10 – 15 years (analytical limitations in the past)
Characteristics?Mostly non-polar / lipophilic, high accumulation potential; partly volatile
Mostly polar/hydrophilic, often with acidic/basic functional groups, low concentrations
Determination?Conventional enrichment (headspace, SPE, LLE) and analysis (LC/RP, GC)
Origin?Often from industry, agriculture, contaminated sites
Different sources (WWTPs, polar degradation products)
Modern MS-techniques (LC) or derivatization (GC)
Knowledge -fate/effects?
Extensively investigated Up to now - relatively poor
Classical Micropollutants vs. Emerging Pollutantse.g. pharmaceuticals and personal care products
e.g. pesticides, PAHs, halogenated compounds
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Screening Strategy2
o 92 different substances (typical for surface waters influenced by wastewater effluents)
o Sampling supported by CAESB and UnBo Analyses: carried out by TU Dresden & KIT o Analytical methods: GC/MS and LC/MS‐MS
o Pharmaceuticals (33)
o X‐ray contrast media (9)
o Algae toxines (4)
o Sweeteners (5)
o Pesticides (17)
o Perfluorinated tensides (2)
o Wastewater tracers (7)
o Corrosion inhibitors (2)
o Plasticisers (5)
o Personal care products (8)
Substance classes
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Pola
rity
Volatilityvolatile nonvolatile
lipophilic
hydrophilicComplexing Agents
SurfactantsX-ray contrast
mediaBenzotriazolesBenzothiazoles
MTBEPharmaceuticals
antibiotics
PFC
Analytical Method3
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Pola
rity
Volatilityvolatile nonvolatile
lipophilic
hydrophilic
Gas Chromatography
Liquid Chromatography
Analytical Method3
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Sample Pretreatment
Water Sample
Extraction, Enrichment
Filtration, pH-Adjustment,
…SPE
SPE, SEC, solvent
exchange ...
HPLC-MS/MS
Clean-up Separation Detection
Analytical Method
Analytical result
3
Note: LC/MS/MS was also a main topic of the capacity building activities
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4
DiclofenacIbuprofenNaproxen
Paracetamol
PhenazoneCaffeine
ParaxanthineTheobromine
AtenololMetoprolol
Sotalol
IohexolIopamidolIopromide
ClarithromycinErythromycin
RoxithromycinSulfamethoxazole
Trimethoprim
BezafibrateGemfibrozil
CetirizineLoratadine
CarbamazepineDiazepamPrimidone
TetrazepamCitalopram
FluoxetinSertralineAtrazine
Diuron1H-Benzotriazole
TolyltriazolePantoprazole
Cotinin
0 2000 4000 6000 8000 10000 12000Concentration in ng/L
WWPT effluents
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4
Problem: How to deal with a high number of data to give comprised information?
Solution: Clustering of the results and definition of key compounds!
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4
Clustering method:
The results were clustered with regard to occurrence and concentration.
Occurrence: no occurrence, temporal occurrence, always above LOD
Concentrations:
Lake: < LOD, LOD-25 ng/L, 25-50 ng/L, > 50 ng/L
WWTPs: < LOD, LOD-100ng/L, 100-500 ng/L, > 500 ng/L
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
RelevanceNo relevance Low relevance Medium relevance High
relevance
Lake Paranoá(C)
31 9 5 5
WWTP South
16 4 14 16
No monitoring Low-frequencymonitoring
Medium-frequencymonitoring
High-frequencymonitoring
Recommendation for a future monitoring strategy
Results4Risk matrix
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Based on the results from the risk matrix the following compounds are recommended for high-frequency monitoring:
Phenazone, caffeine, atenolol, sulfamethoxazole, tolyltriazole, iohexol, iopromide, iopamidol, gemfibrozil, carbamazepine, and 1-H-benzotriazole
These compounds have either high/medium relevance in central point C or low relevance in C but high or medium relevance in A and thus future increase of the concentrations in the central branch of Lake Paranoá can be expected.
Results4
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
0%
20%
40%
60%
80%
100%
Week 1RiachoFundoBrunch
Week 1BananalBranch
Week 1GamaBranch
Week 1Torto
Branch
Week 1CentralBranch
Week 1Future
Intake Point
Corrosion inhibitorsPSMBPSSRIAntibioticsContrast MediaAntihypertensiveCaffeine and MetabolitesAnalgesics
Lago Paranoá: relative amounts of selected organic micropollutants
A EWWTPs
B D C FCentral Intake
Pesticides
Results4
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4
A
A
Point A
Central Point (C)
Point F (futureDWTP)
05.10.0919.10.09
08.03.1009.08.10
23.08.10
0
100
200
300
Con
cent
ratio
n in
ng/
L
05.10.0919.10.09
08.03.1009.08.10
23.08.10
0
100
200
300
400
Con
cent
ratio
n in
ng/
L
05.10.0919.10.09
08.03.1009.08.10
23.08.10
0
100
200
300
Con
cent
ratio
n in
ng/
L
05.10.0919.10.09
08.03.1009.08.10
23.08.10
0200400600
80010001200
Con
cent
ratio
n in
ng/
LFate of pollutants
Iohexol
Iopromide
Atenolol
Caffeine
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4 Perfluorinated compounds
Comparable to River Rhine and German WWTPs
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4Artificial sweeteners
Comparable to German surface waters (Rhine, Danube, Neckar) and WWTPs
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Results4
Sampling points:
‐Influent
‐After sand filtration
‐After ultrafiltration
‐After GAC treatment
Pilot Plant - Advanced Waste Water Treatment Using Ultrafiltration and Activated Carbon: Fate of Organic Micropollutants
Pesticides
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
0
2,000
4,000
6,000
8,000
10,000
12,000
0 1 2 3 4
Sampling point pilot plant
Conc
entr
atio
n in
ng/
L
Carbamazepine
Atenolol
Metoprolol
SMX
Phenazone
Iohexol
Tolyltriazol
Iopromide
Results4
Pilot Plant - Fate of Organic MicropollutantsResults of sampling campaigns 25.03.12 – 03.10.12
After GAC: concentration of all compounds < LOQ
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
o The water quality with respect to organic pollutants was assessed on the basis of analytical investigations of about 90 substances.
o The concentration levels are relatively low and comparable to the concentrations found in European or North American surface waters.
o There are only small differences between dry and rainy seasons.
o For most substances, the concentrations in the central part of the lake are much smaller than in the WWTP effluents due to dilutionand/or degradation.
Summary5
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
o A risk matrix could be established on the basis of concentration and occurrence.
o From the risk matrix 11 key compounds could be derived which canbe considered as indicators for the water quality.
o These key compounds are recommended for future monitoring and for testing the water treatment technology.
o Although the concentrations in the lake are relatively low, an appropriate treatment step, e.g. adsorption onto activated carbon, is recommended.
Summary5
Final Workshop Final Workshop ‐‐ Project IWAS Project IWAS ÁÁGUA DFGUA DFIntegrated Water Resources Management in Integrated Water Resources Management in DistritoDistrito FederalFederal
June 4June 4‐‐6, 20136, 2013
Thanks to:
o BMBF for funding
o all IWAS Água DF colleagues for good cooperation