Laser Pulse Phenomena and Applications Part 14 potx

Pulse durations were measured using a made intensity auto-correlation for the transform-limited pulse, as well as for the various negatively chirped and positively chirped pulses Fig.. F

Hot Chemistry with Cold Molecules 381 second harmonic of Nd:YAG laser operating at a repetition rate of 1 kHz (Corona, Coherent Inc.) The chirped ultrafast laser pulses can be easily produced from our suitably modified compressor setup for the amplified laser system As we increase the spacing between the compressor gratings relative to the optimum position for minimum pulse duration of 50 fs,

we generate a negatively chirped pulse Conversely, we obtain the positively chirped pulse

by decreasing the inter-grating distance Pulse durations were measured using a made intensity auto-correlation for the transform-limited pulse, as well as for the various negatively chirped and positively chirped pulses (Fig 12) The pulses were further characterized by second harmonic frequency resolved optical gating (SHG-FROG) technique Fig 13a shows a typical SHG-FROG trace of our near transform-limited pulse that was collected using GRENOUILLE (Swamp Optics Inc.) In Fig 13b retrieved spectra and phase of the transform limited pulse is shown From this Fig 13b is found that phase of the laser pulse is constant within the bandwidth of the laser pulse and hence it is made sure that at optimal grating distances we get the shorter pulse which is transform limited In Fig 14a, we show the SHG spectrum of the of the transform limited pulses after frequency doubling with 50 μm type-1 BBO crystals as well as the spectrum of the transform-limited pulse collected with a HR-2000 spectrometer (Ocean Optics Inc.) From the Fig 14b, FWHM

home-of the near transform limited pulse is found to be ~18 nm The minimum time duration home-of a

transform limited pulse giving a spectrum with ∆λ (18 nm) at FWHM, central wavelength

(800 nm) and the speed of light (m/s) c: t K 02

c

λλ

Δ =

Δ ⋅ where K is the time-bandwidth product (K=0.441 for Gaussian pulse), ∆t is found to be 50 fs for 18 nm bandwidth pulse which is our transform limited pulse

The laser pulses are then focused with a lens (focal length = 50 cm) on a supersonically expanded molecular beam of n-propyl benzene at the centre of a time of flight chamber The polarization of the laser was horizontal as it enters the mass spectrometer and is perpendicular to ion collection optics The Mass spectra from our particular beam chamber constructed with dry-scroll pumps and turbo-molecular pump as described above has the advantage that it does not contain any extraneous water and hydrocarbon peaks and thus has better sensitivity for organic samples as reported here

-600 -400 -200 0 200 400 600 0.0

0.5 1.0 1.5 2.0

0 50 100 150 200 -150 -100 -50

400 600 800

Generation of Femtosecond chirped pulses:

Femtosecond chirped pulse can be easily generated by the compressor setup This pulse increases its frequency linearly in time (from red to blue) In analogy to bird sound this pulse is called a “chirped” pulse Our compressor setup (Fig 15) consists of a pair of grating and a high reflective mirror Our compressor gratings have 600 grooves/mm (Newport), and have throughput efficiency of 60% One of the gratings is placed on a translation stage By changing the distances between the two gratings and carefully aligning the optical paths at some optimal position a shorter near transform limited 50 fs laser pulse is generated The transform limited condition is confirmed by characterizing the laser pulses at transform limited condition

by measuring the SHG-Frog and autocorrelation trace As we increase the spacing between the two gratings relative to the optimum position we can generate negatively chirped pulse Conversely if we decrease the inter-grating distance we can generate positively chirped pulse

Hot Chemistry with Cold Molecules 383

An incident laser pulse of spectrum E0 (ω) will be shaped by the compressor setup and spectrum of the output will be E0 (ω)eiφω For a light pulse which is centered around ω0

having a reasonably small bandwidth, the total phase can be expanded around ω0 to second order in ω:

2

0

4 ln 2βτ

where τ is the pulse duration of the chirped laser pulse and τ0 is the chirp-free pulse duration of the transform limited pulse in FWHM Pulse durations were measured by intensity autocorrelation technique The experimental error in the chirp value calculated from the equation mentioned above is about ±9%

I O

Fig 15 Compressor setup, GR1, GR2- Garting, HR-high reflective mirror

3 Results and discussions

Our TOF design provides high resolution when it is used in conjunction with our skimmed supersonic molecular beam chamber Fig 16 shows the time of flight mass peak of n-propyl beanzene cation This was taken using femtosecond laser photo-ionization at 800 nm The resolution is defined as R = t/(2∆t), where t is the total flight time of the ion packet and ∆t is the FWHM of the peak In the case n-propyl benzene cation resolution R is found to be around 1113 (Fig 16) With careful adjustment of the voltages of the time of flight power supply and nozzle to skimmer distance to prevent turbulence on the skimmer, we have

HR

GR1

GR2

observed ion packet widths of ~10 ns Resolution R = t/2∆t = 22.1995/(2×0.0097) = 1113, our mass spectra can resolve the adjacent mass peaks in the range of m/z from 0 to 1113 amu

22.05 22.10 22.15 22.20 22.25 22.30 22.35 22.40 22.45 -0.2

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

time (microsecond)

Fig 16 Ion peak of n-propyl benzene cation

It has been known that the fragmentation processes in polyatomic molecules induced by an intense ultrafast laser field can sometimes exhibit sensitive dependence on the instantaneous phase characteristics of the laser field (Itakura et al., 2003; Pestrik et al., 1998; Mathur & Rajgara, 2003; Lozovoy et al., 2008, Goswami et al., 2009) Depending on the change in sign the chirped laser pulses, fragmentation could be either enhanced or suppressed Controlling the outcome of such laser induced molecular fragmentation with chirped femtosecond laser pulses has brought forth a number of experimental and theoretical effects in the recent years However, efforts are continuing for a specific fragment channel enhancement, which

is difficult since it also is a function of the molecular system under study Here we report the observation of a coherently enhanced fragmentation pathway of n-propyl benzene, which seems to have such specific fragmentation channel available We found that for n-propyl benzene, the relative yield of C3H3+ is extremely sensitive to the phase of the laser pulse as compared to any of the other possible channels In fact, there is almost an order of magnitude enhancement in the yield of C3H3+ when negatively chirped pulses are used, while there is no effect with the positive chirp Moreover, the relative yield of all the other heavier fragment ions resulting from interaction of the strong field with the molecule is not sensitive to the sign of the chirp, within the noise level

Study of aromatic hydrocarbons has indicated different fragmentation channels (DeWitt et al., 1997) A systematic study of aromatic compounds with increasing chain-length of substituent alkyl groups has indicated that the fragmentation process is enhanced as the chain-length of the alkyl substituent on the benzene ring increases We have chosen to apply chirped pulse fragmentation control on certain members of these systematically studied aromatic compounds In general, as reported previously for benzene and toluene, p-nitro toluene, we also find that chirping favors the formation of smaller fragments as compared to the heavier ones However, n-propyl benzene has the unique property of enhancing a particular fragmentation channel under the effect of chirp

We record the TOF mass spectra (Fig 17) of n-propyl benzene using linearly chirped and unchirped ultrafast laser pulses with constant average energy of ~200 mW Next, we compared the corresponding peaks in mass spectra by calculating their respective integrals

Hot Chemistry with Cold Molecules 385 under the peaks and normalizing them with respect to the molecular ion These results also conform to the case when we just compare the simple heights of the individual peaks When the linear chirp of the laser pulse is negative, the relative yields of the smaller fragment ion, such as, C3H3+ (mass to charge ratio, i.e., m/z = 39) is largely different from those obtained using transform-limited pulses or from the positively chirped pulses, as reflected in the Fig The relative yield of C3H3+ reaches maximum when the linear chirp coefficient (β, calculated by using the equation as mention earlier) is -8064 fs2 and pulse duration is of 450 fs We would like to point out that the fragment ion C6H5+ (m/z = 77) yield is more when the chirp is positive (β=+6246fs2), and this can be attributed to a different fragmentation pathway (Fig.18) However, the observation of enhancement for only one chirp sign implies that the observed enhancements are not due to the pulse width effects, they rather depend on the magnitude and sign of the chirp Hence coherence of the laser field plays an important role in this photofragmentaion process It is also seen that relative yields of the heavier fragments like C7H7+ (m/z = 91) is not affected by the sign of the chirp

0.2 0.4 0.6 0.8 1.0

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

0.2 0.4 0.6 0.8 1.0

Fig 18 Effect of chirping the laser pulse on the relative yield of different fragment ions shown in comparison to the integrated SHG intensity at the respective chirps

The relative yield of C7H7+ decreased in both the directions of the chirp and is at its maximum when the pulse is transform limited, indicating that the fragment yield only depends on the laser peak intensity as dictated by its pulse width We have also seen that the integrated SHG intensity at different chirp is symmetrically decaying around 0 fs2 (Fig 18), which confirms that there is nothing systematic in the laser pulse causing the enhancements in the fragmentation process

4 Conclusions

We have built a molecular beam chamber with linear time of flight mass spectrometer, which can be combined with femtosecond laser in a novel way to study the femtosecond coherent control of supersonically cooled molecules Our system is constructed with dryscroll pumps and turbo-pumps and is completely free from oil, which is very necessary for any femtosecond laser laboratory In fact, this oil-free capability ensures that the obtained mass spectra is free from extraneous hydrocarbon peaks, which, in turn, makes our system better sensitive in studying coherent control of organic samples as reported in this book chapter

We have demonstrated that the phase characteristics of the femtosecond laser pulse play a very important role in the laser induced fragmentation of polyatomic molecules like n-propyl benzene The use of chirped pulse leads to sufficient differences in the fragmentation pattern of n-propyl benzene, so that it is possible to control a particular fragmentation channel with chirped pulses Overall, as compared to the transform-limited pulse, negatively chirped pulses enhance the relative yield of C3H3+, C5H5+, while the relative yield

of C6H5+ increases in case of positively chirped pulse In fact, for the C3H3+ fragment, the enhancement is almost 6 times for the negatively chirped pulse (β = -8064 fs2) as compared

to that of the transform-limited pulse

5 References

Rousseau, D L J (1966) Laser chemistry, Chem Educ., 43, 566-570

Smalley, R E.; Wharton, L.; Levy, D H (1977) Molecular optical spectroscopy with

supersonic beams and jets, Acc Chem Res., 10, 139-145

Levy, D H (1981) The spectroscopy of very cold gases, Science, 214, 263-269

Zewail, A H (1980) Laser Selective Chemistry: Is It Possible? Phys Today, 33, 27

Bloembergen, N.; Zewail, A H (1984) Energy redistribution in isolated molecules and the

question of mode-selective laser chemistry revisited New experiments on the dynamics of collisionless energy redistribution in molecules possibilities for laser-selective chemistry with subpicosecond pulses, J Phys Chem., 88, 5459-5465

Brixner, T.; Gerber, G (2003) Quantum control of gas-phase and liquid-phase

femtochemistry, ChemPhysChem, 4, 418-438

Goswami, D (2003) Optical pulse shaping approaches to coherent control, Phys Rep., 374,

385-481

Levis, R J.; Menkir, G M.; Rabitz, H (2001) Selective Bond Dissociation and Rearrangement

with Optimally Tailored, Strong-Field Laser Pulses, Science, 292, 709-713

Hot Chemistry with Cold Molecules 387 Ahn, J.; Weinacht, T C.; Bucksbaum, P H (2000) Information Storage and Retrieval

Through Quantum Phase, Science, 287, 463-465

Vivie-Riedle, R de; Troppmann, U (2007) Femtosecond Lasers for Quantum Information

Technology, Chem Rev., 107, 5082-5100

Herschbach, D R (1987) Molecular Dynamics of Elementary Chemical Reactions, Angew

Chem Int Ed Engl., 26, 1221-1243

Assion, A.; Baumart, T.; Bergt, M.; Brixner, T.; Kiefer, B.; Sayfried, V.; Strehle, M.; Gerber, G

(1998) Control of chemical reactions by feedback-optimized phase-shaped femtosecond laser pulses, Science, 282, 919-922

Daniel, C.; Full, J.; Gonzalez, L.; Kaposta, C.; Krenz, M.; Lupulescu, C.; Manz, J.; Minemoto,

S.; Oppel, M.; Rosendo-Francisco, P.; Vajda, Š.; Wöste, L (2001) Analysis and control on η5-CpMn(CO)3 fragmentation processes, Chem Phys., 267, 247-260 Levis, R J.; Rabitz, H A (2002) Closing the Loop on Bond Selective Chemistry Using

Tailored Strong Field Laser Pulses, J Phys Chem A, 106, 6427-6444

Daniel, C.; Full, J.; González, L.; Lupulescu, C.; Manz, J.; Merli, A.; Vajda, S.; and Wöste, L

(2003) Deciphering the reaction dynamics underlying optimal control laser fields,

Science, 299, 536-539,

Weinacht, T C.; White, J L.; and Bucksbaum, P H (1999) Towards Strong Field

Mode-Selective Chemistry, J Phys Chem A, 103, 10166

Itakura, R.; Yamanouchi, K.; Tanabe, T.; Okamoto, T.; and Kannari, F (2003) Dissociative

ionization of ethanol in chirped intense laser fields J Chem Phys 119, 4179

Melinger, J.S.; Gandhi, S.R.; Hariharan, A.; Tull, J.X.; Warren, W.S (1992) Generation of

narrowband inversion with broadband laser pulses, Phys Rev Lett., 68, 2000-2003 Krause, J L.; Whitnell, R M.; Wilson, K R.; Yan, Y.; Mukamel, S (1993) Optical control of

molecular dynamics: Molecular cannons, reflectrons, and wave-packet focusers, J

Chem Phys., 99, 6562

Cerullo, G.; Bardeen, C J.; Wang, Q.; Shank, C V (1996) High Power Femtosecond Chirped

Pulse Excitation of Molecules in Solution, Chem Phys Lett 262, 362-368

Pastirk, I.; Brown, E J.; Zhang, Q.; and Dantus, M (1998) Quantum control of the yield of a

chemical reaction, J Chem Phys., 108, 4375-4378

Yakovlev, V V.; Bardeen, C J.; Che, J.; Cao, J.; Wilson, K R (1998) Chirped pulse

enhancement of multiphoton absorption in molecular Iodine, J Chem Phys., 108,

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Cao, J.; Che, J.; Wilson, K R (1998) Intra-pulse dynamical effects in multi-photon processes:

Theoretical analysis, J Phys Chem., 102, 4284-4290

Guilhaus, M (1995) Principles and instrumentation in time-of-flight mass spectrometry:

Physical and instrumental concepts, J Mass Spectrometry, 30, 1519-1532

Opsal, R B.; Owens, K G.; Reilly, J P (1985) Resolution in the Linear Time-of-Flight Mass

Spectrometer, Anal Chem., 57, 1884-1889

Mathur, D.; Rajgara, F A (2004) Dissociative ionization of methane by chirped pulses of

intense laser light, J Chem Phys., 120, 5616

Lozovoy, V V.; Dantus, M (2008) Femtosecond laser-induced molecular sequential

fragmentation of para-nitrotoluene, J Phys Chem A, 112, 3789-3812

Goswami, T.; Karthick Kumar, S K.; Dutta, A.; Goswami, D (2009) Control of laser induced

molecular fragmentation of n-propyl benzene using chirped femtosecond laser pulses, Chem Phys 360, 47-52

DeWitt, M J.; Peters, D W.; Levis, R J (1997) The Photoionization/Dissociation of Alkyl

Substituted Benzene Molecules Using Intense Near-Infrared Radiation, Chem Phys

218, 211-223

19

UV-Laser and LED Fluorescence Detection of Trace Organic Compounds in Drinking Water

and Distilled Spirits

Anna V Sharikova and Dennis K Killinger

University of South Florida

USA

Current methods for the analysis of drinking water and many other liquids often call for the use of reagents and may require extensive sample preparation (American Public Health Association, 1989) For the case of water supplies and water treatment plants, this analysis is usually carried out once every few days or weeks (Killinger & Sivaprakasam, 2006) Most of the analysis is usually conducted using classical analytical chemical techniques, such as mass spectrometry, liquid chromatography, or fluorescence based or tagged reagents (Crompton, 2000) These analytical techniques are sensitive and provide accurate assessment

of the chemistry related to the quality of the liquids However, they often take considerable time and are usually not performed in real-time, especially for the case of a flowing process line On the other hand, previous fluorescence spectroscopic measurements of ocean water

by Coble showed that deep-UV excitation of naturally occurring organic compounds in water can yield significant and unique fluorescence signals in the near UV to visible wavelength range without the need to use additional reagents or sample preparation (Coble, 1996; Coble, 2007) As a result, we have been studying deep-UV laser-induced-fluorescence techniques for the detection of trace species in water and other liquids with the goal of using the natural fluorescence of trace species in the water or liquid samples and being able to provide readings within the time span of a few seconds

Toward this goal, we have developed a reagentless deep-UV laser and UV-LED induced fluorescence (LIF) system to detect and continuously observe in real time trace levels of colored dissolved organic matter (CDOM) or Dissolved Organic Compounds (DOCs) in water and distilled spirits, such as drinking water, and related water/alcohol based liquids with a sensitivity exceeding that of commercial spectrofluorometers Our system has been used to detect ppb trace levels of plasicizer Bisphenol-A (BPA) that have leached into drinking water, and has detected and monitored trace levels of DOCs within ocean currents (Killinger & Sivaprakasam, 2006; Sivaprakasam et al 2003; Sivaprakasam & Killinger, 2003) Recently, our LIF system has been used to measure fluorescence of reverse osmosis processed water and different types of drinking water (Sharikova & Killinger, 2007; Sharikova & Killinger, 2010) These LED/LIF applications have now been extended to additional water related samples, including humic acid samples, tannic acid and chlorinated water samples, juices, coffee, and several wines and distilled spirits; these recent results are presented in this paper

Our compact LIF system used either frequency tripled or forth harmonic diode pumped Nd:YAG lasers operating at 266 nm and 355 nm, or deep-UV LEDs (265 nm, 300 nm, 335 nm, and 355 nm) as UV excitations sources The emitted fluorescence was measured over the range

of 240–680 nm Strong emission near 450 nm was observed for the DOCs in water, while emission bands near 340 nm were evident from distilled spirits and wine It is important to note that one of the main advantages of using a deep-UV excitation wavelength, such as 266

nm, is that the emission fluorescence is separated in wavelength from the Raman emission of water (near 310 nm for 266 nm excitation), and thus yields greater sensitivity and wavelength selectivity than previous systems using lasers operating near 400 to 550 nm In addition, as a point of reference, our laser based LIF system had a detection sensitivity for the fluorescence standard solution of quinine sulfate on the order of 0.1 ppb The average laser power was approximately 30 times that of the LED, but differences in the signal intensity due to the difference in the laser and LED excitation intensity were consistent with theory

Our studies show that deep-UV light emitting diodes (LEDs) are good alternative light sources for our LIF system, which would make the apparatus cheaper and more compact

It should be noted that the research presented in this paper is directed toward the development of new optical spectroscopic measurement techniques which have the potential to offer enhanced capabilities over conventional water monitoring and liquid analysis However, while its sensitivity has been shown to be in the sub-parts per billion for standard fluorescing compounds used in fluorescence research, such as quinine sulfate, it needs to be further quantified and evaluated against conventional analytical chemistry instruments before it can be used as an on-line analytical instrument for water monitoring Such comparisons are currently being conducted and will be reported later

2 Experimental setup

Our Laser and LED induced fluorescence system is similar to that of a conventional spectrofluorometer, but has a sensitivity several orders of magnitude better Commercial spectrofluorometers often use UV lamps and wavelength selecting spectrometers for the emission source, and single or double monochromators with Photo-multiplier Tubes or CCD detecting arrays for fluorescence detection (Albani, 2007) Often the signal processing is conducted using a chopped CW beam and lock-in amplifier signal detection Our LIF system uses a high PRF (pulse-repetition-frequency) laser running at about 8,000 pulses/second as the excitation source (or a pulsed LED source running at about 330 pulses/second), and a high-speed boxcar integrator which detects and stores the fluorescence photon signal for each pulse

In addition, our system uses multiple excitation beams and double-pass collection optics to increase the fluorescence signal Our past work has shown that this combination has enhanced the sensitivity of our laser-induced-fluorescence system by two to three orders of magnitude over conventional spectrofluorometers, depending upon the spectrometer and optical detector configuration used (Sivaprakasam & Killinger, 2003) Details of our current LIF system follow

2.1 Description of the apparatus

Our fluorescence measurements were performed using a system shown in Fig 1 The schematic diagram of the apparatus is shown in Fig 2 The light source was one of the following: a microchip laser, 266 nm or 355 nm (JDS Uniphase, Models NU-10110-100 and NV-10110), or a LED operating at 265 nm, 300 nm, 335 nm or 355 nm (Sensor Electronic Technology, Inc., UVTOP® series) A silicon APD photodetector (New Focus, Model 1621)

UV-Laser and LED Fluorescence Detection of Trace Organic Compounds

was used to trigger data acquisition with the laser source; the LEDs were software-triggered The laser beam passed through the optical quartz cell (Spectrocell Inc., Model RF-3010-F) several times, for which plane mirrors on the sides of the cell were used The fluorescence signal was collected at a right angle to the excitation beam with a concave mirror (Optosigma, Model 035-0130) and a fused silica lens (Optosigma, Model 014-0490) It passed through one of the 19 different narrow (10nm) bandpass optical filters ranging from 265 nm

to 685 nm before being focused onto a PMT (Hamamatsu, Model H6780-03) One of the absorption cut-off filters (CVI Laser, Models CG-WG-280-2.00-2 and CG-WG-295-2.00-2) was used to block Rayleigh and Raman scattering All filters were mounted on a stack of motorized filter wheels (CVI Laser, Models AB-302 and AB-304) The PMT signal was acquired by a gated integrator and boxcar averager unit (Stanford Research System, Model SR-250) Data collection and filter wheel control was handled by LabVIEW software through

a computer interface unit (Stanford Research System, Model SR-245) and serial bus

2.2 Laser and LED characteristics

The Q-switched microchip lasers produced 0.4 ns, 0.3-0.4 μJ pulses at a repetition rate of 8 kHz The beam size was on the order of 1 mm

The LEDs were operating in a 10 μs, 50 mA drive current regime with a 330 Hz repetition rate The output light pulse energy was approximately 7 nJ (with the exception of 22 nJ for the 355 nm LED) It was noted that the LEDs also had an out-of-band emission in the visible region As an example, this can be seen in Fig 3 that shows the measured output power of the 265 nm LED (LED265) as a function of wavelength and of drive current This is a log plot

of the intensity and shows that the out-of-band LED emission had a peak value of about 1% compared to the peak emission at 265 nm

Fig 1 Experimental system: optics box (left) and electronics box (right)

Fig 2 Schematic diagram of the experimental apparatus

UV-Laser and LED Fluorescence Detection of Trace Organic Compounds

To block this out-of-band light, a VIS-blocking, UV-passing filter (CVI Model CG-UG-11) was used with our LED sources Figure 4 shows the spectral output power of the LEDs with and without the filter using a linear scale for the intensity The beam size within the sample cell was about 5 mm

0.00E+00

5.00E-051.00E-041.50E-04

3 Data and results

Our LIF system was used to measure a considerable variety of water related liquids including tap water, Reverse Osmosis (RO) treated ground water, and other water quality related substances These results are shown in the following

3.1 Experimental conditions and settings for liquid samples

The liquid samples were stored, when necessary, in the dark and cold Water samples were not further processed Wine samples were diluted to 10 mL per 1 L with distilled water Humic substances (International Humic Substances Society, 1R101N, 1S103H, 1S104H) were prepared as 10 mg per 500 mL of distilled water

A flow cell with a linear flow rate of 5 cm/s was used to minimize photobleaching With each bandpass filter, 1000 measurements were taken, which lasted a few seconds per filter setting including filter switching time Boxcar averaging setting was 300 samples The sensitivity setting was adjusted for each sample to maximize the signal The spectra were compensated for filter bandwidth and transmission, PMT quantum efficiency and gating integrator/boxcar averager sensitivity

3.2 Reverse Osmosis processed ground water and drinking (tap) water

Ground water taken from a shallow well at USF was processed by a Reverse Osmosis unit at Prof Carnahan's lab (Carnahan, 2006) The fluorescence spectra of ground water before and after RO treatment using 266 nm laser excitation is shown in Fig 5 The broad peak observed around 470 nm in the untreated water is typical of the organic compounds usually

present in such samples (Coble, 2007) After the RO treatment, the fluorescence signal decreased significantly, especially on the short-wavelength side The signal from distilled water is shown for comparison

0 400

Distilled water

Fig 5 Fluorescence of ground water before and after reverse osmosis treatment, 266 nm laser excitation

Tap water in our lab was continuously monitored for a period of a week (see Fig 6) As can

be seen, the flowing tap water, Fig 6(a), had a greater range of variation than a sample recirculated through the system, Fig 6(b) Certain repetitiveness of the running water signal might be indicative of the water usage patterns at our university The initial growth in the recirculated signal was due to plastic leaching from the soft tubing used in the pump

We have also tested tap water collected from different locations in the US (Fig 7) All samples were taken directly from residential tap water except for the Tampa location, where

an on-line water filter in a drinking fountain was present For all samples, settings were the same during data acquisition As can be seen, the fluorescence spectra obtained with 266 nm laser excitation, (a), and 265 nm LED, (b), were different only in overall intensity Comparing the spectra from different locations, one can see that all possessed two large peaks centered around 420 and 460 nm, as well as smaller peaks on the sides However, both the absolute and relative intensity of the peaks varied with the location, serving as an indication of the difference in both the total concentration and the species of organic compounds present in the sample

The signal-to-noise ratio (SNR) was calculated for the set of tap water samples as a difference between peak fluorescence of the sample and the distilled water (reference) signals divided by double the standard deviation of 1000 measurements The results were typically in the 300-900 range for the laser sources, and around 30-190 for the LEDs (Sharikova & Killinger, 2010) For example, at 266 nm, the laser pulse energy was about 100 times greater than the LED pulse energy, but the SNR values differed only by a factor of 10 being about 296 for the laser LIF and about 26 for LED excitation for the Ann Arbor water data The reason for the stronger than expected signal with the LED excitation may be due

to differences in the light excitation and fluorescence overlap volume in the LED configuration or sample photobleaching in the case of the lasers

UV-Laser and LED Fluorescence Detection of Trace Organic Compounds

(a)

(b) Fig 6 Week long continuous tap water monitoring with 266 nm laser excitation: (a) running tap water; (b) recirculated tap water