Organic pollution: from classic Organic pollution from classic to emerging contaminants Walter Giger 3 dK l S i 12 A il 2010 3rd Kaplan Symposium, 12 April 2010
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Organic pollution: from classic Organic pollution from classic to emerging contaminantsg g
Walter Giger
3 d K l S i 12 A il 2010
g
3rd Kaplan Symposium, 12 April 2010
Organic Environmental Contaminantsg• Historic review
Heroes key players; milestones events; episodes• Heroes, key players; milestones, events; episodes
• Analytical methods• Systematics – Contaminant classes
• polarity-volatility diagram --> subgroups• classic versus emerging contaminants
• Recent case studies- nonylphenols - perfluorochemicals - benzotriazoles
• Outlook• What comes next?
First report on organic pollutants?p g p
12911291
17751775
19761976
1775S i l „Surgical
Observations“
Sir Percival Pottbenz(a)pyrene
Inventor of chromatography
Berichte der Deutschen botanischen Gesellschaft 24, 385 (1906).Mikhail Semenowitsch Tswett showed that green leaves contain more than one type of chlorophyll, and by 1906 he had devised an adsorption method of separating the pigments. .........Tswett called the new technique chromatographybecause the result of the analysis was 'written in colour' along the length of the adsorbent column.
Analytical methods - AySampling–Enrichment–Separation–DetectionComposite sampling – passive samplers
Solid-phase enrichment on-line enrichment
High-volume injection
ChromatographyChromatographyGas chromatography (GC) Liquid chromatography (LC)
Tandem methods:GC/MS LC/MS/MS LC/MS GC/GC/TOFMS LC/LC
High resolution methodsHRGC HPLC UPLCHRMS: multistage quadrupole, time-of-flight (TOF),
ion traps, Orbitrap
Analytical methods - By• Sensitivity, selectivity
• On-line enrichment, large volume injection
• Faster, more direct, on-line, real-time, sensors
• Target – non-target analyses – screening
• Validation quality assessment/control (QA/QC)• Validation, quality assessment/control (QA/QC)
Isomer specific analyses• Isomer specific analyses• Isotope measurements
Effect oriented analyses > biological and chemical analyses• Effect-oriented analyses –> biological and chemical analyses
Lab on a chip• Lab on a chip
Polarity-volatility diagramy y gHYDROPHILIC
POLARPOLARHYDROPHILICmobility in water
RIT
Y
AMPHIPHILICSEMI-
PO
LAR
VOLATILE NONPOLAR
AMPHIPHILICVOLATILE
P
gas exchangeNONPOLARLIPOPHILIC
lipid/surface
LIPOPHILICaccumulation
VOLATILE NONVOLATILE
VOLATILITY
Rachel Carson Rachel Carson (1907 – 1964)
1962
“Classic” organic contaminantsHYDROPHILIC
g
SURFAC-TANTSatrazine
NTAEDTA
PAN
atrazine
TY
DDT
PCBfreons
OLA
RIT DNAPL
PCB
PCDD / PCDF
petroleum
methane
PO
PAHmethane
VOLATILITY
VOLATILE NONVOLATILE
VOLATILITYLIPOPHILIC
First observation of effects caused by polar organic water pollutants?
Greek mythologyl t 1950 l 1960late 1950s, early 1960s1986
LAS
SO3-
branched ABS SO3-
branched ABS SO3
Schweizerhalle/Sandoz, 1986
Fische Rhein, 1986
The “Sandoz fire”
Giger, ESPR (2008)
The “Sandoz wave”
Bad Honnef km Bad Honnef km 640640
Giger, ESPR (2008)
The “Sandoz wave”
The “Sandoz wave”
Capel, Giger, Wanner EST (1988)
“Emerging” organic contaminantsHYDROPHILIC
g g g
drugsdiagnostics
hormonesIrgarol
drugsantibiotics
d ag ost csTY
hormones
polychlorinated
organo-
OLA
RIT polychlorinated
paraffins
phosphoric FRpolybrominated flame
retardants
PO
VOLATILITY
retardants
VOLATILE NONVOLATILE
VOLATILITYLIPOPHILIC
Polar persistent organic pollutantschelating agents
EDTA
surfactantsbenzotriazoles X-ray
contrast
RIT
Y
surfactantsTPBS, ABSLAS, SPC
APEOMTBE
benzothiazoles contrast media
perfluorinated compoundsPFOS, PFOA, PFBS
PO
LAR
pharmaceuticals
P
pharmaceuticalsantibiotics
VOLATILITY
Environmental endocrine disruptersTheo ColbornDianne Dumanowski
p
John Peterson Myers1996
John Sumpter Susan Jobling
Ana Soto
4-Nonylphenol
OHOH
H CH19C9
OOH O
OH
H Cn = 1–18
H C
H2C C H 2
H19C9H19C9
NPnEO
nonionic surfactants
Gas chromatogram of an extract gof a secondary sewage effluent, 1980
NP1EO
NP2EO
NPNP
OOH NPEO
b fH19C9
n = 5–20 biotransformation
OO
OH NP2EO
O
H19C9
NP1EOOH
H19C9
NP1EO
OHNP
H19C9
NPGiger et al. (2009). Environmental fate of
h li d i di t fi ld d l b t t diphenolic endocrine disruptors: field and laboratory studies. Philosophical Transactions of the Royal Society A – Mathematical, Physical and Engineering Sciences 367, 3941–3963.
Technical nonylphenol: Mixture of isomers ith diff t l lk l with different nonyl alkyl groups
NP112
NP NP35 NP
NP194
NP111
NP143
NP9
194 NP143
NP152NP65
NP128
Bob Eganhouse,Giger et alEST, 2009.
Different biodegradation ratesf l h l iof nonylphenol isomers
% NPuninoculated controls
1 mg/ml minimal medium
80
100
HONP1
g
cometabolically degraded
60HO
NP9
NP2
g
40HO
HO
NP112
Mixture of 5 NP isomers
growth substrates
0
20
HO
NP93
Mixture of 5 NP isomers
0 10 20days of incubation
The more highly branched an isomer — the faster the degradationenvironment: shifting of the isomers composition
Gabriel et al. Appl. Environ. Microbiol. 2005, 71, 1123
Cleavage of the alkyl group yielding nonanoles
S. xenophagum BayramS. cloacae
t strain TTNP3α
quaternary carbon atom
HO
HO
unknown mechanismHO
N112OHNP112not further utilizednot further utilized
Gabriel et al. Appl. Environ. Microbiol. 2005, 71, 1123
Estrogenic activities l h l i YES Anonylphenol isomers – YES-Assay
Factor 1003.0
E2 BL Mixed Isomers NP1
acto 00
Kohler, Gabriel,G
nm2.5
NP2 NP9 NP10 NP14 NP65 NP70 NP93 NP111
Giger,Routledge, Sumpter,Thiele
banc
e 54
0 n
2.0NP111 NP112 NP152 NP170 NP194
EST, 2008.
Abso
rb
1 0
1.5
0 5
1.0
Molar Concentration
1e-12 1e-11 1e-10 1e-9 1e-8 1e-7 1e-6 1e-5 1e-40.5
Risk assessment of nonylphenol y p
• Differential degradation and different effects of nonylphenol isomers need to be taken into account and should be fully evaluatedevaluated.
• There might be a need for some gkind of a toxicity equivalence factor system as is used for PCB and PCDD/PCDF.
Perfluorinated compounds (PFCs)pProperties
b th h d h bi d l h bi- both hydrophobic and oleophobic→ Surface treatment: Carpets, clothings,
leather and paper products etcleather and paper products, etc.
ATOFINA commercial
Textile ProtectionCarpet Protection Paper
Excerpt of 3M commercial www.swisspack.ch
→Fluoropolymer production, electroplatingSpeciality chemicals
Textile Protection
→ Speciality chemicals
PFC target analytesPFC target analytesg yg y
Abbreviations:F2C
CF C
F2C
C
F2C
C
F2C
SO -PFOS
PF..: perfluoro...FT..: fluorotelomer...
S lf t
CF2
F3C CF2
CF2
SO3
PFOAF2C
F2C
F2C COO-
...S: ...sulfonate
...A:...acid/carboxylate
PFOA CCF2
F3CC
CF2
CCF2
COO
F2 F2 F2 H2
...SA: …sulfonamide
..OH: ..alcoholX :
6:2 FTS
F F F F
CCF2
F3CC
CF2
CCH2
CSO3
-
..X.:B butyl (C4)Hx hexyl (C6)
F2C
CF2
F3C
F2C
CF2
F2C
CF2
F2C
SNH
O O
2PFOSA
y ( )O octyl (C8)N nonyl (C9)D decyl (C10)
8:2 FTOHF2C
CF
F3C
F2C
CF
F2C
CH
H2C
OHCF
F2C
O O
D decyl (C10)F2 F2 H2F2
PFCs: Global DistributionPFCs: Global Distribution
The Glatt River Valley
WWTP WWTP 77RR33
y
WWTPWWTP 66
RR33
WWTP WWTP 66
WWTP WWTP 55
WWTP WWTP 44
WWTPWWTP 33
WWTP WWTP 22RR22
WWTP WWTP 11
WWTP WWTP 33
RR11
Influent EffluentBassersdorf PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 40.3 12.5 20.7 19.2 25.6 8.5minimum 10.9 10.4 10.3 15.1
Per-fluorinated minimum 10.9 10.4 10.3 15.1
average 18.5 12.5 12.9 16.2 19.2 8.5
Blach PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 85.3 33.8 12.1 33.9 59.6 15.5minimum 8.2 16.9 11.9 13.7 21.4 8.7
fluorinated acids
in minimum 8.2 16.9 11.9 13.7 21.4 8.7average 34.8 25.3 12.0 22.7 30.4 11.0
Dbendorf PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 889 56.1 103.7 580 47 107.2minimum 212 20 2 10 3 140 15 7 15 1
in wastewater
ffl tminimum 212 20.2 10.3 140 15.7 15.1average 468 35.3 38.0 310 34.6 52.8
Fllanden PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 137 28.5 154 48.5minimum 37 9 15 4 71 9 13 8
effluentsin the
minimum 37.9 15.4 71.9 13.8average 71.4 22.0 103 27.6
Glattfelden PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 161 18.3 32.3 242 28 36.5minimum 74 9 8 8 12 6 90 14 6 15 9
Glatt valley,Switzerlandminimum 74.9 8.8 12.6 90 14.6 15.9
average 117 13.0 23.7 144 20.4 25.3
Kloten-Opfikon PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 237 65.3 97.3 202 41.7 127minimum 86 2 25 1 97 3 86 8 31 3 16 4
SwitzerlandConcentrations,
/Lminimum 86.2 25.1 97.3 86.8 31.3 16.4average 134 37.4 53.6 119 35.4 53.6
Niederglatt PFOS PFOA PFHxS PFOS PFOA PFHxSmaximum 144 22.1 14.6 155 31.7 18.5minimum 48 9 6 4 7 5 64 3 11 6 9 4
ng/L
minimum 48.9 6.4 7.5 64.3 11.6 9.4average 77.5 16.7 10.7 92.4 18.8 14.3
Glatt-Rhine PFOS PFOA PFHxSmaximum 71.5 10.2 18.5
i i 28 5 8 6 14 7
Huset et al. (2008) ES&T
Concentrations in the Glatt River
100 PFBS
75
ng/L
)PFHxSPFOSPFHpAPFOA
50
ntra
tion
(n PFOA
25Con
cen
0Schwerzenbach Oberglatt Rheinsfelden
Average concentrations: PFBS 4 ng/L
(R1) (R2) (R3)
PFHxS 12 ng/L PFHpA 1 ng/LPFOS 49 ng/L PFOA 7 ng/L Huset et al. (2008) ES&T
PFOS Mass Flows (g/day)(g y)Equivalent measured and calculated mass flows indicate no removal processes occur
45
M d M Fl ( /d )
WWTPs account for all observed increases in PFOS mass flows
35
40
day)
Measured Mass Flow (g/day)River onlyCalculated mass flow (g/day)River + WWTPs effluent
20
25
30
Flow
(g/d River WWTPs effluent
10
15
20
Mas
s
0
5
10
0Schwerzenbach
(R1)Oberglatt
(R2)Rheinsfelden
(R3)Huset et al. (2008) ES&T
PFOS and total PFCAs in digested sewage sludge
Sun, Alder, Giger, et al. inin preparation
Benzotriazoles
HH
N
HN
N
HN
N
N
H3CN
N
H3C
1H-Benzotriazole (BTr) Tolyltriazole (TTr)Methyl-1H-benzotriazole
(4-TTr and 5-TTr)
Uses of benzotriazoles
Anticorrosive agents/additives in:• airplane deicing and anti-icing fluids (ADAFs)
Cancilla et al. Environ. Toxicol. Chem. 22, 134 (2003), ( )
Cancilla et al. Environ. Sci. Technol. 32, 3834 (1998)
• engine coolants and oils in automobilesg• industrial cooling systems
• silver protection in dishwasher detergents• silver protection in dishwasher detergents
• plastic stabilizerstif i i h t i• antifogging in photo processing
Benzotriazole in wastewater24 wastewater treatment plants
120120 averageelimination:30%
80 80
100
80
100
80
30%
50
60
70
60
L B
T
70
60
50
60
20
30
40
20
40µg/L
40
30
20
40
20
0
10
20
0
20
ff
20
1020
Primary effluents, n = 33 secondary effluents, n = 61
Voutsa, Schaffner, Giger, Environ. Sci. Pollut. Res., 2006
Benzotriazole in the Glatt River
20
RheinsfeldenBackground at Rheinsfelden
Glatt river20
15
10
SchwerzenbachOberglattBackground at Rheinsfelden
10
5
0wee
k
Airport0
30
25 calculated weeekly BT loadsused at the Zurich airportduring the deicing season
Load
kg/
w
total 0 13 t20
15
10
L total 0.13 t
27.10.03 17.11.03 8.12.03 29.12.03 19.1.04 9.2.04 1.3.04 22.3.04 12.4.04 3.5.04
5
027.10.03 17.11.03 8.12.03 29.12.03 19.1.04 9.2.04 1.3.04 22.3.04 12.4.04 3.5.04
DateGiger, Schaffner, et al., EST, 2006
Benzotriazole in Swiss lakesGreifensee Lake Zurich
(Zollikon)Lake Zurich
(Thalwil) Lake Geneva
0
10
0 100 200 300 4000
20
0 40 80 120 160
00 50 100 150 200 250
0
5
0 300 600 900 1200
10
20
20
40
50
100
5
10 Benzotriazole ng/L
epth
m
30
40
60
80
150
200
15
20
De
50
60
100
120
250
25
30 0.16 t 0.76 t 18 t
700 4 8 12 16
1400 5 10 15
300
0 5 10 15 20 25
350 5 10 15 20 25 30
Temperature °C
Giger, Schaffner et al. EST, 2006
What’s next?What s next?
Novel contaminants of concern
polarHYDROPHILIC
polar POPs additives
substitutes
TY
biocidal
OLA
RIT productsmetabolites
new POPs PO
VOLATILITY
VOLATILE NONVOLATILELIPOPHILIC
Emerging contaminants – 2010Emerging contaminants 2010• Sucralose, • Metabolites/degradates acesulfame and other artificial
of:• Pesticides,
sweeteners• Nanomaterials
,metolachlor
• Pharmaceuticals• Polyfluorinated pharmaceuticals
• Pharmaceuticals,e.g. diclofenac, sulfamethoxazolepharmaceuticals
• Polar disinfection byproducts
sulfamethoxazole• X-ray contrast
mediabyproducts media
Potential candidate polar POP (1)
SucraloseSucraloseSucraloseSucraloseArtificial sweetenersArtificial sweeteners
AcesulfameAcesulfame
Potential candidate polar POP (2)
TorcetrapibTorcetrapib
Potential candidate POPs (3)
QuickTime™ and aTIFF (Uncompressed) decompressor
are needed to see this picture.
Th “ b t di t ” D l d !Th “ b t di t ” D l d !The “asbestos disaster” as Damocles sword !The “asbestos disaster” as Damocles sword !
Functionalized fullerenes and carbon nanotubes, Functionalized fullerenes and carbon nanotubes, e.g. multisulfonates, e.g. multisulfonates,
––> nanopolars in the aquatic environment> nanopolars in the aquatic environmentp qp q
Natural organic matter (NOM)Not new, but still unsolved.Not new, but still unsolved.
AcknowledgmentsgEva Molnar, Christa McArdell, Dimitra Voutsa, Alfredo Alder Hans Peter Kohler Niels JonkersAlfredo Alder, Hans-Peter Kohler, Niels Jonkers, Christoph Ort, Christian Schaffner, Hongwen Sun,Felix Wettstein at EawagFelix Wettstein at Eawag
Jennifer Field, Carin Huset, Aurea Chiaia, Douglas Barofsky t O St t U i itat Oregon State University
–> The Giger Group 1972–2007Brochure downloadable: www.eawag.ch/giger-groupBrochure downloadable: www.eawag.ch/giger group
The EndThe End
Th k Thanks f tt ti !for your attention !
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