introduction: the role of fluorescence in water quality€¦ · introduction: the role of...
TRANSCRIPT
Introduction: the role of fluorescence in water quality
analysis
What is Fluorescence?Fluorescence is a type of luminescence.
(1) A molecule absorbs a high-energy photon…
(2) …and re-emits a lower-energy photon with a longer wavelength (fluorescence).
(3) Usually the absorbance is in the ultraviolet, and the emitted light is in the visible range, but this depends on the particular molecule.
Fluorescent molecules
potentially found in the
water environment
Naphthalene
Proteins
Stilbenes
Chlorophyll
‘Humic’ matter
Phenols
We can now ‘map’ fluorescence.
The above ‘map’ shows fluorescence intensities of an untreated wastewater at different locations in ‘optical space’. Organic molecules in the wastewater are fluorescing.
Y-axis: excitation energy. X-axis: emitted fluorescence wavelength. Z-axis: fluorescence intensity.
Time taken: < 1 minute. Greater sensitivity than absorbance.
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Organic matter fluorescence signatures
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
W
av
el
en
gt
h
(n
m)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Humic / fulvicsubstances
Fluorescentwhitening agents
Microbialmaterial
FluorescentDyes
Chlorophyll
1990 1992 1994 1996 1998 2000 2002 2004 2006
0
10
20
30
40
50
60
Num
ber
of papers
publis
hed p
er
year
Year
Journal papers with keywords "fluorescence and river and organic"
Journal papers with keywords "fluorescence" and wastewater and organic"
Rapid increase in academic publications
First ‘optical map’published (marine science)
First ‘optical map’(fresh and waste water)
Rapid technologicalimprovements
Improvements in technology
Excitation now possible in short UV (200-300 nm). 1990s limit was mid-UV; 1980s was long-UV.
Mass produced instruments.
Competitive market, off the shelf instruments with excellent software and accessories.
Appropriate analysis time.
A <1 minute ‘optical map’ today took ~15 mins (1990s) and ~2 hrs (1980s).
Increased portability.
LED sources, improved detectors, lighter batteries. Ongoing in 2000s
300 350 400 450 5000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 2 5 . 0 0
2 5 0 . 0 0
2 7 5 . 0 0
3 0 0 . 0 0
3 2 5 . 0 0
3 5 0 . 0 0
3 7 5 . 0 0
4 0 0 . 0 0
3 0 0 . 0 0 3 2 5 . 0 0 3 5 0 . 0 0 3 7 5 . 0 0 4 0 0 . 0 0 4 2 5 . 0 0 4 5 0 . 0 0 4 7 5 . 0 0 5 0 0 . 0 0
9 6 3 . 0 9
8 8 9 . 2 7
8 1 5 . 4 5
7 4 1 . 6 3
6 6 7 . 8 2
5 9 4 . 0 0
5 2 0 . 1 8
4 4 6 . 3 6
3 7 2 . 5 4
2 9 8 . 7 2
2 2 4 . 9 0
1 5 1 . 0 8
7 7 . 2 7
3 . 4 5
Fluorescence as a chemical water quality surrogate.
Surrogate for BOD in wastewater treatment.
Surrogate for TOC in drinking water treatment.
Surrogate for Chl-a in drinking water protection.
Process control:
Monitoring FWA fluorescence in wastewater treatment
Monitoring NOM fluorescence in drinking water treatment
Fluorescence as a rapid method of characterising organic matter
chemistry (aromacity, molecular weight) and function (metal binding,
hydrophobicity).
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
General water quality applications
Fluorescence as a chemical water quality surrogate.
Surrogate for BOD in wastewater treatment.
Surrogate for TOC in drinking water treatment.
Surrogate for Chl-a in drinking water protection.
Process control:
Monitoring FWA fluorescence in wastewater treatment
Monitoring NOM fluorescence in drinking water treatment
Fluorescence as a rapid method of characterising organic matter
chemistry (aromacity, molecular weight) and function (metal binding,
hydrophobicity).
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Fluorescence as a chemical water quality surrogate.
Surrogate for BOD in wastewater treatment.
Surrogate for TOC in drinking water treatment.
Surrogate for Chl-a in drinking water protection.
Process control:
Monitoring FWA fluorescence in wastewater treatment
Monitoring NOM fluorescence in drinking water treatment
Fluorescence as a rapid method of characterising organic matter
chemistry (aromacity, molecular weight) and function (metal binding,
hydrophobicity).
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Fluorescence as a chemical water quality surrogate.
Surrogate for BOD in wastewater treatment.
Surrogate for TOC in drinking water treatment.
Surrogate for Chl-a in drinking water protection.
Process control:
Monitoring FWA fluorescence in wastewater treatment
Monitoring NOM fluorescence in drinking water treatment
Fluorescence as a rapid method of characterising organic matter
chemistry (aromacity, molecular weight) and function (metal binding,
hydrophobicity).
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Fluorescence as a chemical water quality surrogate.
Surrogate for BOD in wastewater treatment.
Surrogate for TOC in drinking water treatment.
Surrogate for Chl-a in drinking water protection.
Process control:
Monitoring FWA fluorescence in wastewater treatment
Monitoring NOM fluorescence in drinking water treatment
Fluorescence as a rapid method of characterising organic matter
chemistry (aromacity, molecular weight) and function (metal binding,
hydrophobicity).
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Fluorescence as a chemical water quality surrogate.
Surrogate for BOD in wastewater treatment.
Surrogate for TOC in drinking water treatment.
Surrogate for Chl-a in drinking water protection.
Process control:
Monitoring FWA fluorescence in wastewater treatment
Monitoring NOM fluorescence in drinking water treatment
Fluorescence as a rapid method of characterising organic matter
chemistry (aromacity, molecular weight) and function (metal binding,
hydrophobicity).
300 400 500 600 7000
200
400
600
800
1000
Wavelength (nm)
Inte
nsity (
a.u
.)
Wa
ve
le
ng
th
(
nm
)
W a v e l e n g t h ( n m )
2 0 0 . 0 0
2 5 0 . 0 0
3 0 0 . 0 0
3 5 0 . 0 0
4 0 0 . 0 0
4 5 0 . 0 0
5 0 0 . 0 0
5 5 0 . 0 0
6 0 0 . 0 0
3 0 0 .0 0 3 5 0 .0 0 4 0 0 .0 0 4 5 0 .0 0 5 0 0 .0 0 5 5 0 .0 0 6 0 0 .0 0 6 5 0 .0 0 7 0 0 .0 0
9 6 2 . 0 0
8 8 6 . 0 0
8 1 0 . 0 0
7 3 4 . 0 1
6 5 8 . 0 1
5 8 2 . 0 1
5 0 6 . 0 1
4 3 0 . 0 1
3 5 4 . 0 2
2 7 8 . 0 2
2 0 2 . 0 2
1 2 6 . 0 2
5 0 . 0 2
- 2 5 . 9 7
Next....
So we now know what energy is needed to excite fluorescence in water samples.
What is the science of fluorescence? How is it measured?