Optical Chemical Sensors

for Environmental Analysis

R. A. Lieberman
September, 2009

1
 OPTICAL CHEMICAL SENSORS

 Optochemical Detection Techniques

 Optochemical Detection Instrumentation
 Optochemical Detection Formats

2
Optochemical Detection Techniques

3
 Direct Spectroscopy
 Definition: “Measuring the color of light to detect chemicals”
 Absorption/Reflectance
 Oldest chemical detection technique
 UV-Vis-IR still dominates environmental detection
 Modern frontiers: THz, deep UV(?)
 Luminescence
 Accepted standard for hydrocarbon detection
 Modern frontiers: Single-molecule detection
 Raman
 Practical at last (made possible by lasers & holofilters)
 Modern frontiers: Extreme signal enhancement (SERS)

4
 “Titration”
 Definition: “Using chemical reactions to detect
chemicals”
 Oldest analytical chemical detection technique
 Major thrust in late 19th and early 20th centuries
 Eclipsed by spectroscopy; revived in late 20th century
 Current practice ranges from “rediscovered” inorganic
reagents to fluorescent-labeled antibodies
 Modern frontiers:
 Increased analyte specificity (MIPs, “designed molecules”)
 Improved performance (q-dots; NIR dyes)
 New formats (optrodes, arrays, etc. – see following slides)

5
 Refractometry
 Definition: “Measuring refractive index to detect
chemicals”
 First used to measure concentrations in known solutions
 Total Internal Reflection (e.g., Abbe)
 Common in food, petrochemical, other industries
 Surface Plasmon Resonance
 Used in commercial biochemical detectors
 Modern frontiers: nanophotonics-enabled “plasmonics”

6
 Refractometry
 Optical path shift detection
 Grating-based (planar; long-period fiber Bragg)
 Interferometer-based (fiber optic M-Z/F-P, integrated optic)
 Propagation constant measurements
 Waveguide “pointer”
 Waveguide cutoff
 Ellipsometry (is this polarimetry?)
 Modern frontier: Coupling refractometry with
“titration” (e.g. DNA oligos, antibodies, other
recognition elements)

7
 Polarimetry
 Definition:“Measuring polarization to detect chemicals”
 Optical rotation measurement
 Classically used to measure sugar concentration
 Frontier: Chirality measurement for biomolecule detection
 Circular dichroism – rarely used in sensing (small signal, short
wavelengths)

Nephelometry
 Definition: “Measuring elastically scattered light to
detect chemicals”
 Most-used air quality measurement (particle count)
 Can be used to detect “titration” reactions

8
Optochemical Detection
Instrumentation

9
 Optical Elements
 Integrated Optic Waveguides
 Planar lightwave circuits (PLC) – generally SiO2 on Si;
fabricated using semiconductor processing techniques
 Polymer integrated optics
 Wide range of materials
 Many fabrication techniques: Embossing; “stamp-printing,” ink-jet
printing, photolithographic production
 Advanced Materials
 Nano-optical structures
 Metamaterials
 Controlled-geometry plasmonic features

10
Optochemical Detection Formats

11
 Optochemical Detection Formats
 Fiber-assisted direct spectroscopy
 Silica fiber technology deployed “everywhere”
 Chalcogenide & Fluoride gaining acceptance
 New frontier: new fiber designs (photonic crystal; photonic
bandgap; hollow-core) will double spectral range
 Fiber-assisted “titration”
 Fiber optrodes
 Distributed intrinsic chemical agent sensing
 Multipoint active chemical sensors (gratings/scattering
centers couple light to sensor element)

12
 Optochemical Detection Formats
 Fiber-assisted refractometry
 Tapered fibers
 Fiber-tip Fabry-Perot optrodes
 Long-period fiber Bragg gratings (FBGs)
 Fiber optic Mach-Zehnder interferometers
 Fiber optic SPR probes
 Simple “Fresnel reflectance” probes
 Fiber-assisted indirect measurements
 Strain-inducing coatings on fibers with FBGs
 Strain-inducing coatings on fiber interferometers
 Stain-inducing microbending on fibers in cables

13
Optochemical Detection Formats
 Integrated optic “titration”
 Waveguide arrays with sensor claddings
 Waveguide arrays with sensor cores
 Interferometers with sensor coatings
 Integrated optic refractometry
 Interferometers without coatings
 “Waveguide pointer”
 Plasmon waveguides
 Passive
 Active

14
ENVIRONMENTAL ANALYSIS
 Environmental Media
 Environments
 Chemical Targets

15
Environmental Media

16
Water
 Drinking water
 Recreational water
 Groundwater
 Open water

17
Air
 Indoor air
 Industrial emissions
 Local air contamination
 Global atmosphere

18
“Earth”
 Soil surface
 Other surfaces
 Subsuface

19
Fire
 Smoke detection
 Flame detection
 Combustion control/monitoring

20
Environments

21
Industrial/Commercial Environments
 Factories/Refineries
 Process control
 Legal compliance
 Health/safety
 Landfills
 Leakage
 Fire/toxin safety
 Mines
 Legal compliance
 Health/safety
 Other: Restaurants, hospitals, etc.
22
Consumer/Home Environments
 Indoor air quality
 Smoke detection
 Home water quality monitoring

23
 Agriculture/Wilderness Environments

 Lake, stream, ocean monitoring

 Pollution
 Chemical balance

 Marine/atmosphere interface (CO2 balance)

 Farm runoff characterization
 Agricultural soil quality measurement

24
Chemical Targets

25
Chemical Targets
 Natural
 Toxic minerals in groundwater (Arsenic, lead, other minerals)
 Smoke and fire byproducts (PAHs, etc.)
 Biotoxins (e.g. microcystin from cyanobacteria)
 Manmade
 Factory effluent
 Stack gases (NOx, SOx, CO, CO2)
 Liquid outfall (100’s of chemical bypoducts & waste products)
 “Fugitive emissions”
 Polyaromatic hydrocarbons
 other hydrocarbons
 Accidental releases
 Chlorine, ammonia, methyl isocyanate, other industrial products
 Reaction intermediaries & raw materials (oil)
 Purposeful releases
 Terrorist attack
 Industrial sabotage

26
OPTICAL CHEMICAL SENSORS FOR
ENVIRONMENTAL ANALYSIS --EXAMPLES
 Biotoxin Detection in Water
 Toxic Chemical Detection on Surfaces
 Toxic Chemical Detection in Air
 Stack Gas Monitoring
 Factory Effluent Monitoring
 Groundwater Monitoring
 Carbon Monoxide Monitoring
 Fire Precursor Detection

27
Biotoxin Detection in Water

28
Biotoxin Detection in Water

29
 Biotoxin Detection in Water
 Drop of water containing pathogens is applied on the
test strip.
 Sample reacts with the reagents on the test strip and is
transported across the membrane.
 Quantum dot (QD) conjugated reagents bind to the
spots on the microarray.
 QDs that emit at different wavelengths ensure that
cross reactivity or nonspecific binding can be identified.
 Measuring fluorescence signals from multiple quantum
dots at each spot
 improves specificity
 Increases the viability of multiplexed field test strips.
 Fluorescence of the QDs is measured with a portable
reader.
 Fluorescence intensity is related to the concentration of
toxin in the sample.
30
Lateral Flow Strip for Single Pathogen

31
 Lateral Flow Assay Process

Sample Migration
Sample Application

Pathogen Detection

32
 Multi-Pathogen Lateral Flow Strip

 Multiple QD-labeled
antibodies on reagent pad
 Multiple antibody “spots”
replace capture line
 Multiple antibody spots
also replace control line

33
 Quantum Dot Fluorescent Labels
Make Multianalyte Biosensors Practical
•“Unlimited” choice of emission wavelenghs
•Extremely broad excitation band
•Single wavelength can excite all fluorophores
•Large Stokes shift
•No photobleaching
•Same matgerial used in all fluorophores
•Same synthesis process for all fluorophores

34
IOS Quantum Dot Fluorescence Spectra

35
 E. Coli Assay Response
10

8
Intensity, AU

6
y = 6E-05x + 3.2842
R2 = 0.9769

0
0 20000 40000 60000 80000 100000 120000
E. coli, CFU

36
Pseudomonas Aeruginosa Assay Response
6.00

5.00

4.00
Intensity (au)

3.00

2.00

1.00

0.00
0 1 2 3 4 5 6 7 8
4
PA cells (x10 )

37
Toxic Chemical Detection
on Surfaces

38
Toxic Chemical Detection on Surfaces

BioProbe® Optical
Fiber
Probe

Optical Light
Fibers Bacteria Signals
on Surface

Laptop PC

39
 BioProbe™ Operation
 Compound excitation /detection probe
 5mm diameter fiber bundle
 Customized probe head
 Can use single fiber
 LED source excites bacterial fluorescence
 Simplified detection unit selects for wavelengths
characteristic of living cells
 Can “tune” for selected biotoxins

40
“Life Detection” Through Autofluorescence

41
 BioProbe System Components

Probe Head (close-up)

Reader & Optical Cable
42
 Analysis Software

 Windows-driven GUI
 Computer-optimized
signal levels
 User-settable alarm
threshold

43
 System Performance

Linear Detection of Biomarker by BioProbe

1.6
1.4
S ig n a l L e v e l

1.2
1.0
0.8
0.6
0.4
0.0 0.2 0.4 0.6 0.8 1.0
Biomarker Concentration Factor
(Fraction of Toxic Level)

44
Monitoring Bacterial Biofilm Degradation
P. fluorescens Biofilm on Clear Polycarbonate
Treated with 37% Formalin
4900
Live biofilm covered w ith 200 μL
deionized w ater (4707 mV)
4700
Addition of another 5 drops
formalin (4485 mV)
4500
PMT output (mV)

Addition of 1 drop
formalin (4609 mV)
4300

Addition of 5-10 drops

4100 formalin (3870 mV)
Addition of 1 mL
formalin (3970 mV)
3900

3700
0 5 10 15 20 25
time (min)

45
BioProbe System Bacterial Response
Average Mean Voltage
Bacterial Bacterial Difference
Species Density between
(cfu/cm2) Bacteria and
Water (mV)
Pseudomonas
fluorescens 3.10 x 105 850
Pseudomonas
aeruginosa 5.09 x 106 800
Staphylococcus
aureus 1.25 x 107 580
Staphylococcus
epidermidis 1.84 x 107 750

46
 “Life Detection”
Differentiation betw een Live and Killed Bacteria by
BioProbe®
3500
live samples
3000
killed samples
Signal Level (mV)

2500
2000
1500
1000

500
0
Sample 1 Sample 2 Sample 3
Bacte rial Film s on Polym e r Surface

47
Toxic Chemical Detection in Air

48
Distributed Intrinsic Chemical Agent Sensing
and Transmission (“DICAST®”) System
 LINEAR sensor, not a “point sensor”
 Sensor cables respond to target chemical anywhere over
sensor length
 Optical fibers in the cables are intrinsically sensitive to
individual chemicals
 Two optoelectronic detection systems:
 “Alarm-style”
 Alerts user if even a single meter of cable is exposed
 Self-referenced phase-locked-loop gives high-sensitivity and low
false alarm rate
 Position-resolved:
 Locates precise position of chemical agent
 Self-referenced optical time domain reflectometry differentiates
between chemical and physical changes in fiber cable

49
 DICAST® Sensor Principle:
Chemically-Induced Cladding Loss
Chemical agent
Indicator molecules
embedded in cladding
n2
Glass fiber core
n1
Light Input
Output
Polymer fiber cladding

 Interaction of chemical agent with indicator in cladding changes

optical properties
 Light propagating through sensor fiber core interacts with cladding
through evanescent field
 Well-known cause of transmission loss in communications fiber

50
 From Light Launch to Equilibrium –
the “Spatial Transient”

Source: Snyder, A.W. & Love, J.D., Optical Waveguide Theory

51
 DICAST® Sensor Fibers

 Conventional fiber
fabrication
 Patented optical design Cl2 HCN

 Proprietary sensory
cladding

H2S Sarin/Soman

52
 Hydrogen Cyanide Cladding Material
HCN 50PPM 50% RH 15 min

0.8
0.7
50 ppm-1min
0.6
0.5
Absorbance

0.4
0.3 Op. λ 532

0.2
0.1
0
-0.1
350 450 550 650 750 850
Wavelength (nm)

53
 Hydrogen Cyanide Sensor Fiber Performance
TEST031805-1

0
S ensor S ignal (dB /m )

-1

50ppm
50ppm
-2
5ppm
5ppm
5ppm
-3

-4

Chemical Exposure Begins

-5
0 60 120 180 240 300 360 420 480 540 600

Exposure Time (sec.)

Note: Integrative (dosimetric) response–

fibers respond faster to higher concentrations

54
Chlorine-Sensitive Cladding Material
Cl2 10 ppm 50% RH 2min

0.49 10 ppm 2min

0.39
absorbance

0.29
Op. λ 650

0.19

0.09

-0.01
300 350 400 450 500 550 600 650 700 750 800 850
Wavelength (nm)

Note: Response remains strong after 425 days @ 23ºC

55
 Chlorine Sensor Fiber Performance
SY63 Response 10 ppm Cl2/Air 10%RH

2.5

2
650 nm

1.5
dB

1 gas on
Absorbance

0.5
1310 nm
0
4 4.5 5 5.5 6 6.5 7
-0.5
Time (min)

56
Nerve Agent Sensor Cladding Material

Soman Response
Sarin Response

57
 DICAST® Sensor Cables

 Air-permeable sheath
 Lets air in to react with fibers
 Provides rugged protection against
shear stress
58
“Full Cable” DICAST® System Response
(Four Fibers, Two Wavelengths)
50ppm HCN 23C/50%RH

KEY
HYDROGEN CYANIDE FIBER
HYDROGEN SULFIDE FIBER
CHLORINE FIBER
NERVE AGENT FIBER

Solid: Visible
Dotted: Infrared
HCN on

59
DICAST® Optoelectronics

Position Resolved System

Zone-Alarm System

60
DICAST® Zone-Alarm Optoelectronics
 End-to-end fiber transmission measured
 Sensor cables linked to system through
commercial multimode cables
 Dual-wavelength illumination
 Visible: Responds to chemical agent
 Infrared: Reference wavelength
 Sources modulatedfrequencies
 Lock-in detection
 Eliminates stray light effects
 Increases signal-to-noise ratio

61
 Zone-Alarm DICAST® System
Metro Platform Test Site: 4 Fibers, 4 Zones
Passenger Platform Edge
480 ft
2 Std Cables

OUT1D

OUT1C
OUT1B
OUT1A

IN1D

IN1C

IN1B

IN1A

1D 1C 1B 1A IN2
spare spare spare spare
1DS 1CS 1BS 1AS IN3
OPEN
2D 2C 2B 2A 260 ft
OPEN 4 Std Cables
3D 3C 3B 3A

50 ft 80 ft 50 ft 80 ft 50 ft 80 ft 50 ft
From TC&C Room
1 Std Cable 2 Std Cables 1 Std Cable 2 Std Cables 1 Std Cable 2 Std Cables 1 Std Cable
1 Sensor Cable 1 Sensor Cable 1 Sensor Cable 1 Sensor Cable

SENSOR 1 (BROADBAND H2S) CABLE INVENTORY:

4 ea 50 ft 4-SENSOR DICAST CABLES
SENSOR 1 (BROADBAND H2S SPARE) 3 ea 50 ft 3-FIBER DISTRIBUTION CABLES
SENSOR 2 (CHLORINE) 6 ea 80 ft 3-FIBER DISTRIBUTION CABLES
2 ea 480 ft 4-FIBER DISTRIBUTION CABLE
SENSOR 3 (NERVE AGENT) 4 ea 260 ft 3-FIBER DISTRIBUTION CABLE

23July07 v5
62
Zone-Alarm DICAST® Software
 Local interface provides
immediate Safe/Alarm
status
 Neural net combines
data from four fibers to
eliminate false alarms
 Internet uplink provides
remote monitoring
capability

63
 Position-Resolved DICAST®
(10 cm)

t= 0.5 nsec

2 meters

t= 10 nsec

t= 20.5 nsec

Visible Wavelength Optical Time Domain Reflectometry (“OTDR”)

 Short pulse launched into fiber
 Rayleigh scattering returns fraction of light toward source
 Time-of-flight determines location sensed
 Optical loss between launch and location determines intensity
 In DICAST®: Plot indicates chemical dose versus location

64
14 Meter Fiber Exposed to 100 ppm Chlorine

0.25 dB/m

1.9dB/m

2.6dB/m

Exposure
20 sec
20 sec
30 sec

65
DICAST® System Specifications
Parameter Requirement
Sensitivity Alarm when one meter or more is exposed
to 10% of toxic dosage dosage
Specificity Will not alarm with defined interferants

Resolution Within 1 meter along fiber (OTDR)

Response time Less than 10 sec for toxic dose IDLH/LCT50

Less than 1 minute for 10% of toxic dose
Cable length 60 meters chemically sensitive;
300 meter leads
Cable lifetime Greater than 1 year

Calibration Electronic (no test gas needed)

False Alarm rate Less than 1%

66
Factory Effluent Monitoring

67
Continuous Flow Assay for Low Vapor
Pressure Toxic Industrial Compounds

68
Microsphere-Bound Displacement Assay

69
Labeled Microspheres (10 µm)

Labeled Beads Unlabeled Beads

70
Target Antigens

Carbaryl Diphacinone Parathion

[63-25-2] [82-66-6] [56-38-2]

Surrogate Antigens

71
 Quantum Dot Bio-Labeling
 CdSe core, ZnS shell quantum dots
 Coated with cysteine-lysine peptide chains
 Cysteine binds to QD
 Lysines bind to surrogate antigen

72
Fluorescence Excitation & Collection

73
Benchtop Model of Packaged System
 Package:
 Excitation
 Collection
 Flow cell
 External:
 Pump
 Reagent
 Computer
 Signal processing
 Power supply

74
Vortex Air Sampler/Extractor

 40 liters/min. flow rate

 70% collection efficiency
75
Displacement Immunoassay of Phenanthrene
5000 no loss of beads
4000
3000
Δ =1800 cps
2000
1000
0
450 500 550 600 650
 Surrogate antigen: 2-aminonaphthalene
 Sample: 150 ppm phenanthrene

76
Continuous Flow Water Effluent Monitoring

 Same platform as
LVP-TIC monitor
 Ab/Ag system for
new targets (e.g.,
PAHs, pesticides)
 Water pump
replaces air
concentrator

77
Groundwater Monitoring

78
 Techniques for In Situ Monitoring
 Remote fiber optic spectroscopy
 Excitation fiber carries laser light downhole
 Collection fiber returns Raman & fluorescence to spectrometer
 Neural network identifies & quantifies pollutants
 Locally replenished liquid optrode
 Liquid-phase irreversible chemical indicator system
 “Dissolving solid” supplies continuous stream of reagent
 Excitation & collection through separate fibers
 Neural network identifies & quantifies pollutants
 Active chemical refractometry
 Long-period fiber grating diffracts light to cladding modes
 Target compound swells chemically selective coating
 Neural network identifies & quantifies pollutants

79
Raman Spectra of Target Compounds

80
Mixed Raman Spectrum – 3 Targets

81
Mixed Raman Spectrum – CHCl3 in Water

82
Fluorescence Spectra of Target Compounds

83
Mixed Spectra: Groundwater & Targets
6
Gr.water
Norm. Luminescence

5
4
Benzene
3 1500ppm
2 Toluene
1 120ppm
0 Xylene
6ppm
-1240 340 440
nm

84
Hybrid Neural Network Design

85
User Interface: Presenting Purity

GNDB
benze
tolue
xylen
GNDA

0% 20% 40% 60% 80% 100%

True Ratios “Zoom In” on Targets

86
 Solid-Phase Replenished Optrode

Controlled-Release
Polymer

 Groundwater diffuses through porous membrane

 Reaction consumes reagent
 New reagent released by polymer
 Optical path avoids high-concentration reservoir
87
Creating Color From Chlorinated Compounds
 A strong base abstracts the acidic proton to generate trihalomethyl
anion
HO-+ HCX3 H2O + :CX3-

 The unstable conjugate base loses a halide ion and generates a

divalent carbon species known as carbene
:CX3- X- + :CX2

 This electron-deficient intermediate, reacts with molecules such as

pyridine, forming a highly colored product [Fujiwara, 1917]
 The traditional Fujiwara chemistry (pyridine/OH-) used alkalis
(NaOH and KOH) in water -- insoluble in pyridine. Reaction product
is formed only at the interface.
 Andersen and Andersen [1990] showed a single-phase Fujiwara
system that utilized pyridine and a hindered nitrogen base,
specifically a tetraalkylammonium hydroxide
 IOS has developed all-solid-phase Fujiwara chemistry, using solid
pyridine derivatives

88
Improving on Fujiwara
HO-+ HCX3 H2O + :CX3-
:CX3- X- + :CX2

89
 Multiple Color-Producing Reactions
(chloroform 10 ppm)

1,2-Bis(4-Pyridyl)-Ethane 1,2-Bis(2-Pyridyl)-Ethylene
(0.2 M in THF) and TBAH (0.2M) (0.2 M in THF) and TBAH (0.2M)

4,4'-Dimethyl – 2,2'-Dipyridyl
(0.2 M in THF) and TBAH (0.2M)
90
Calibration Curve for Chloroform

91
Photobleaching Resets Reaction

92
Relocatable Groundwater Monitoring
Using a Cone Penetrometer

93
 Fiber Bragg Gratings

 Periodic variation in waveguide core refractive index

 Short-period gratings strongly reflect wavelengths
that are integral multiples of the grating period
 For extremely long periods, guided modes in fiber
core are scattered into cladding modes

94
Fiber Bragg Grating Spectral Behavior

95
Single Mode FBG Reflection Spectrum
Measured with IOS System

96
Long-Period Fiber Bragg Gratings
100
Transmittance 80
60
40
20
0
550 600 650 700 750
W a v e le ng th (nm )
 For multimode fibers, Long Period Bragg Gratings
(LPGs) yield very rich transmission/reflection spectra
 Coupling to cladding surface means that spectrum of
LPG depends on refractive index outside of cladding
 Æ Can access the environment directly from the core
(CLADDING evanescent field coupling
97
 Example: 49 ppm Kerosene vapor
in Contact With Surface of LPG-Fiber

98
Solid-Phase Extraction Coatings Enhance
LPG Response to Target Compounds
 Differential permeability
 Permeable to target vapors
 Reduced permeability for other compounds

 Solvent-induced refractive index shifts

 “Dilution” – average of two indices in volume
 Swelling – increases volume

99
Kerosene-Aquasil-LPG Interaction
Transmittance (%)

100
80
60
40
20
0
500 550 600 650 700 750 800
Wavelength (nm)

100
Response of LPG Fiber to 63 ppm Decane
Coating: LLNL UR3

101
Response of UR3-LPG Fiber to 76 ppm Octane
Transmittance (%)
100
80
60
40
20
0
560 610 660 710 760
Wavelength (nm)

102
 LPG Fiber Response to Solvent Vapors
(Coating: Aquasil)
100
Transmittance (%)

80
60
40
20
0
560 610 660 710 760
Wavelength (nm)

Dichloromethane Decane Toluene BKG

103
 LPG Fiber Response to Solvent Vapors
(Coating: UR3)
100
Transmittance (%)

80
60
40
20
0
660 680 700 720 740 760
Wavelength (nm)

Dichloromethane Decane Toluene BKG

104
Error Histogram for 100 Measurements

105
Environmental Air Quality
Monitoring

106
Environmental Gas Monitoring

Photodetector
Lightsource

Neural
Network

O2

CO2

CO

Photodetector H2 O

107
 Multi-Gas Air Quality Monitoring
 Chemically active sensors
 Optrodes
 Indicator-doped porous-glass PICs
 Multiple analytes
 Multiple indicators and
 Multiple reference channels
 Multiple wavelengths
 Neural net signal processing
 Removes cross-response
 Improves quantitation

108
Four-Optrode Long-Term Exposure
(Nitrogen Background)
Photodetector1
1500 Photodetector2
Photodetector3
Photodetector4

1000
Incident Light Power

500

0
0 50 100 150 200 250 300 350 400
Time (min)

109
Four-Optrode Long-Term Exposure
(Ambient Environment)
1000

900

800

700
Incident Light Power

600

500

400

300
Photodetector1
Photodetector2
200 Photodetector3
Photodetector4

100

0
0 50 100 150 200 250 300 350 400 450
Time (min)

110
Vaska’s Complex as a CO Indicator

111
Spectral Response to Carbon Monoxide

112
Carbon Monoxide Optrode Response

113
 Carbon Dioxide Optrode
(“Severinghaus Optrode”)
 CO2 (aq) + H2O —— > H2CO3 (Kh = 2.6 X 10-3)

 H2CO3 + H2O <—— > HCO3- + H3O+ (K1 = 2.2 X 10-4)

 HCO3- + H2O < —— > CO32- + H3O+ (K2 = 2.5 X 10-10)

•CO2 shifts carbonate equilibrium

•Resulting pH triggers change in fluorescent indicator

114
Fluorescence Response of CO2 Optrode

115
CO2 Response Curve

116
Neural Net Deconvolution of
Multichannel Data

117
Fire Precursor Detection
3048 & 3084 & 3097

118
Fire Precursor Detection in Aircraft
 Heated materials emit
vapors & gases
 Carbon monoxide
 Formaldehyde
 Polymer/monomer
 Gases have distinct
NIR spectra
 Optical detection of
precursors “detects
fire before it occurs”

119
Carbon Monoxide Absorption Spectrum

120
Conventional Modulation Spectroscopy
Modulation
(Pressure, Stark)

Measurem ent Reference

a) Cell
Cell
Broadband
Light Source
Bandpass Filter Detector
Optical Fiber
(Multim ode)
Measurem ent Reference
b) Cell Cell
Broadband
Light Source

Modulation
(Frequency, Shift)

121
Multi-Wavelength Modulated Fiber Laser

122
Thermo-Stabilized Multiline Laser

123
7-Line Fiber Laser Tuned for CO

124
20 ppm CO Detected With Multi-line Laser

125
 Optical Chemical Sensors:
Good for Environmental Analysis!
TEST031805-1
5000 no loss of beads
1

0
4000
3000
Δ =1800 cps
Sensor Signal (dB/m)

-1

50ppm

-2
50ppm
5ppm
2000
5ppm

-3
5ppm
1000
-4 0
-5
0 60 120 180 240 300 360 420 480 540 600
450 500 550 600 650
Exposure Time (sec.)

100

Transmittance (%)
80
60
40
20
0
660 680 700 720 740 760
Wavelength (nm)

45 Dichloromethane Decane Toluene BKG

40 5000 5000 5000 5000 5000
Signal (Arbittrary Units)

PR3 PR3
35
30 2500
2500 C
Cl
k1
25
20 1000 Cl Ir CO Ir CO
1000
15 500 500 k1
250 250 O
10 CO
5 0 0 0 0 PR3 PR3
0 50 100 150 200
Time (min)

126
Thanks to…
Funders
 National Science Foundation
(NSF)
 National Institutes of Health
(NIH)
 National Aeronautics and
Space Administration (NASA)
 Environmental Protection
Agency (EPA)
 U.S. Department of Defense
 U.S. Department of State
Audience
 YOU!
Workers
 Dr. Glenn Bastiaans
 Ms. Manal Beshay
 Dr. Kishology Goswami
 Mr. Jeffrey Iida
 Dr. Lothar Kempen
 Dr. Edgar Mendoza
 Dr. Vladimir Rubtsov
 Dr. Indu Saxena
 Dr. Roland Suri
 Dr.Igor Ternovskiy
 Dr. Srivatsa Venkatasubbarao
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