Fluorescence from airborne microparticles: dependence on size, concentration of fluorophores, and illumination intensity.

We measured fluorescence from spherical water droplets containing tryptophan and from aggregates of bacterial cells and compared these measurements with calculations of fluorescence of dielectric spheres. The measured dependence of fluorescence on size, from both droplets and dry-particle aggregates of bacteria, is proportional to the absorption cross section calculated for homogeneous spheres containing the appropriate percentage of tryptophan. However, as the tryptophan concentration of the water droplets is increased, the measured fluorescence from droplets increases less than predicted, probably because of concentration quenching. We model the dependence of the fluorescence on input intensity by assuming that the average time between fluorescence emission events is the sum of the fluorescence lifetime and the excitation lifetime (the average time it takes for an illuminated molecule to be excited), which we calculated assuming that the intensity inside the particle is uniform. Even though the intensity inside the particles spatially varies, this assumption of uniform intensity still leads to results consistent with the measured intensity dependence.

Single-shot fluorescence spectra of individual micrometer-sized bioaerosols illuminated by a 351- or a 266-nm ultraviolet laser.

Reproducible fluorescence spectra of individual 2- to 5-microm -diameter biological aerosol particles excited with a single shot from a Q -switched laser (266 or 351 nm) have been obtained with highly improved signal-to-noise ratios. Critical to the advance are crossed diode-laser trigger beams, which precisely define the sample volume, and a reflecting objective, which minimizes chromatic aberration and has a large N.A. for collecting fluorescence. Several allergens (red oak, meadow oat pollen, paper mulberry pollen, and puffball spores) have different fluorescence spectra. Bacillus subtilis fluorescence spectrum deteriorates at high 266-nm incident intensity. Dry riboflavin particles illuminated with a 351-nm light exhibit a new 420-nm fluorescence peak that grows nonlinearly with laser pulse energy.

Asymmetry parameter and aggregate particles.

We derive and examine the general expression for the scattering asymmetry parameter g. For aggregate particles, the asymmetry parameter is made up of two terms. One term accounts for interference effects of the electromagnetic fields radiating from the individual subsystems. The other term contains the effects of the interaction of the electromagnetic fields between these subsystems. Enhanced backscatter is one phenomenon resulting from these interactions. Numerical results demonstrate that interference effects play a dominant role when the separation distance between two-sphere aggregates is smaller than half the incident wavelength. As the separation distance becomes large, both interference and interaction effects drop off and the asymmetry parameter approaches that of the individual particle constituents.

Light-scattering intensity fluctuations in microdroplets containing inclusions.

A prominent characteristic of the light scattered from a microparticle containing inclusions is a fluctuation in the intensity that is due to the changing positions of the inclusions with respect to each other and the host droplet. We calculate the magnitude of these fluctuations for a host sphere containing a single eccentrically located spherical inclusion and experimentally measure the fluctuation amplitudes for host spheres containing multiple inclusions. We find that, for sufficiently small single inclusions, the amplitude of the scattering fluctuations increases approximately linearly with the area of the inclusion. For multiple inclusions, the fluctuation amplitude increases with concentration with an approximate power-law dependence.

Qualitative light-scattering angular correlations of conglomerate particles.

The scattering phase functions of micrometer-sized glycerol droplets containing spherical latex inclusions undergo random fluctuations with time. We measure scattering intensities in the near-forward and near-backward scattering directions and find them to have strong positive correlations during some time periods and strong negative correlations during other time periods. The characteristic time constants of these correlations are of the order of seconds. We calculate scattering correlations from two types of scattering system. Correlations from a two-sphere system generally are positive, whereas correlations from a sphere containing a single spherical inclusion may be both positive and negative. Calculations of correlations from our experimental data are consistent with diffusion of inclusions within the host droplet, rather than interference effects between the inclusions.

Nephelometer optical response model for the interpretation of atmospheric aerosol measurements.

A numerical model evaluating the response of a typical integrating nephelometer is described. The model incorporates the actual scattering geometry as well as the effects of a finite light source, detector size, and a nonideal Lambertian diffuser. An angular scattering weighting function is introduced to provide a tractable approach in numerical calculations and easy application. Using established size distribution ensembles associated with a few representative aerosol types, we compare the calculated response of a real nephelometer with that of an ideal, or perfect, nephelometer. The results indicate that, frequently, the nephelometer-produced aerosol-scattering coefficient is of the order of 10-20% too small; but for some naturally occurring aerosols, the difference may be as large as 40-50%. For a multiple-wavelength nephelometer, the response model can be employed to estimate the expected error in the aerosol-scattering coefficients directly from the measurements themselves.

Quantitative light-scattering angular correlations of conglomerate particles.

A quantitative analysis of the fluctuations in the scattering associated with micrometer-size glycerol droplets that contain spherical latex inclusions are performed. Scattering intensities at two angles (the near-forward and the near-backward directions) are measured as functions of time. We analyze these signals using two techniques. We find that calculated autocorrelation time constants associated with these signals are not consistent with current models based on interference of light scattering from latex inclusions that exhibit Stokes-Einstein diffusion. The intensity fluctuations at different scattering angles display extended periods of both positive and negative correlations with characteristic time constants of the order of seconds. The time constants associated with the cross correlations provide information on the physical parameters of the inclusions.

Conditional-firing aerosol-fluorescence spectrum analyzer for individual airborne particles with pulsed 266-nm laser excitation.

We report the operation of an aerosol-fluorescence spectrum analyzer capable of selectively measuring the fluorescence spectra of single micrometer-sized aerosol particles as they flow through the instrument. As the particle first traverses a cw 488-nm probe laser beam, the total fluorescence and elastic scattering are measured with photomultipliers. When the photomultiplier output levels meet preset logic conditions, a UV laser (at 266 nm) is fired and the particle fluorescence spectrum is recorded. Fluorescence spectra of biological airborne particles are presented. The ability of the analyzer to capture the fluorescence spectrum of one type of particle while ignoring others, based on the particle characteristics, is also demonstrated.

Conditional-sampling spectrograph detection system for fluorescence measurements of individual airborne biological particles.

We report the design and operation of a prototype conditional-sampling spectrograph detection system that can record the fluorescence spectra of individual, micrometer-sized aerosols as they traverse an intense 488-nm intracavity laser beam. The instrument's image-intensified CCD detector is gated by elastic scattering or by undispersed fluorescence from particles that enter the spectrograph's field of view. It records spectra only from particles with preselected scattering-fluorescence levels (a fiber-optic-photomultiplier subsystem provides the gating signal). This conditional-sampling procedure reduces data-handling rates and increases the signal-to-noise ratio by restricting the system's exposures to brief periods when aerosols traverse the beam. We demonstrate these advantages by reliably capturing spectra from individual fluorescent microspheres dispersed in an airstream. The conditional-sampling procedure also permits some discrimination among different types of particles, so that spectra may be recorded from the few interesting particles present in a cloud of background aerosol. We demonstrate such discrimination by measuring spectra from selected fluorescent microspheres in a mixture of two types of microspheres, and from bacterial spores in a mixture of spores and nonfluorescent kaolin particles.

Aerosol-fluorescence spectrum analyzer: real-time measurement of emission spectra of airborne biological particles.

We have assembled an aerosol-fluorescence spectrum analyzer (AFS), which can measure the fluorescence spectra and elastic scattering of airborne particles as they flow through a laser beam. The aerosols traverse a scattering cell where they are illuminated with intense (50 kW/cm(2)) light inside the cavity of an argon-ion laser operating at 488 nm. This AFS can obtain fluorescence spectra of individual dye-doped polystyrene microspheres as small as 0.5 µm in diameter. The spectra obtained from microspheres doped with pink and green-yellow dyes are clearly different. We have also detected the fluorescence spectra of airborne particles (although not single particles) made from various biological materials, e.g., Bacillus subtilis spores, B. anthrasis spores, riboflavin, and tree leaves. The AFS may be useful in detecting and characterizing airborne bacteria and other airborne particles of biological origin.

Random occurrence of stimulated Raman scattering emission from liquid water microdroplets.

Stimulated Raman scattering (SRS) spectra from micrometer-sized water droplets have been obtained in the range 2100 < Δν < 5100 cm-(1). A number of Raman bands have been individually identified (to our knowledge, for the first time), corresponding to fundamental OH- and OD-stretching vibrations and to vibrations of hydrogen-bonded molecular complexes. All bands exhibit the intense morphologydependent resonance features that are characteristic of SRS emission from microdroplets. SRS emission is apparently random from all bands; however, the frequency of occurrence varies widely, from bands where emission is seen on practically every laser shot to bands where emission is seen only once in > 10(4) laser shots. Possible causes of these noteworthy emission features are discussed, including the difficulty of coupling weak spontaneous Raman emission to both the intense pump beam and the morphologydependent resonances within the droplet.

Effects of submicrometer-sized particles on microdroplet lasing.

We report the threshold emission characteristics of lasing from microdroplets that consist of Rhodamine 6G dye in an ethanol solution that contains undoped polystyrene latex spheres. The addition of latex particles to the droplets suppresses lasing. Our findings indicate that, for a fixed Rhodamine 6G concentration and fixed pump intensity, lasing ceases when a certain total-threshold latex particle surface area is reached in the droplet, independent of latex particle size. A possible explanation for these findings is the Förster-assisted annihilation of Rhodamine 6G dye lasing levels, facilitated by the adsorption of dye molecules on the surfaces of latex particles.

Suppression of stimulated Raman scattering from microdroplets by seeding with nanometer-sized latex particles.

Stimulated Raman scattering (SRS) in laser-irradiated microdroplets is suppressed by the addition of nanometersized latex particles. The microdroplets consist of either pure ethanol or a solution of Rhodamine 6G dye in ethanol, seeded with latex particles having diameters of 50 < d < 500 nm. SRS emission occurs at droplet morphology-dependent resonances (MDR's) after either direct pumping by the incident 532-nm laser or indirectly whereby the pump laser first initiates dye lasing, which in turn pumps SRS. For large latex, we observe SRS suppression at a near-coincident threshold concentration independent of the presence of dye, whereas, for small latex, adding dye reduces the threshold concentration by more than an order of magnitude. These findings are consistent with the interpretation that for large latex ~1 particle must occupy the MDR mode volume at threshold, whereas for small latex the addition of particles facilitates Förster-assisted annihilation of both 532-nm and dye-lasing MDR pump photons.

Energy-transfer-assisted lasing from microdroplets seeded with fluorescent sol.

We report observations of lasing emission from liquid microdroplets of Fluorescein 548 dye in ethanol, seeded with submicrometer-sized fluorescent sol. An incident pump laser excites fluorescein dye molecules, which in turn couple energy to sol-dye molecules, generating lasing in the sol. The pump laser can also generate fluorescein lasing in the droplets, which may excite lasing in the sol. Other noteworthy findings include the absence of sol emission for larger sol and the presence of sol emission, even without any observable fluorescein emission, for smaller sol. All emissions are at wavelengths corresponding to morphology-dependent resonances of the droplet. Studies of the dependence of these emissions on pump laser intensity and sol concentration suggest that they are driven either by Förster energy transfer between fluorescein dye molecules and dye within the sol or by enhanced radiative transfer that occurs when fluorescein emission couples to morphology-dependent resonances of the droplet microcavity.

Observations of stimulated Raman scattering and laser-induced breakdown in millimeter-sized droplets.

We report the first observations, to our knowledge, of nonlinear optical effects in large (millimeter-sized) droplets. Stimulated Raman scattering (SRS) and laser-induced breakdown (LIB) are simultaneously observed in acoustically levitated millimeter-sized glycerol droplets irradiated by either a frequency-doubled (532-nm) or a frequency-tripled (355-nm) Nd:YAG laser. The two processes, which occur above a nearly coincident irradiation threshold, are conjectured to arise from a common initiation mechanism: self-focusing. LIB generates vapor bubbles within the droplet, resulting in the quenching of SRS emission.

Aerosol-induced laser breakdown thresholds: effect of resonant particles.

Laser intensity thresholds for the onset of stimulated Raman scattering and the breakdown in resonant micro-meter-sized droplets are reduced to below those for nonresonant droplets by a factor of ~ 3. This reduction is most likely caused by the enhancement of electromagnetic energy (photon) densities within the droplets over and above that in nonresonant droplets. The magnitude of the threshold reduction for breakdown is consistent with the assertion that (1) input (pump) wavelength resonances that initiate plasma have cavity Q's of ~ 10(4) and (2) finite regions of high-electromagnetic-energy density within the droplet, with dimensions of the order of the Debye length, are required to initiate plasma.

Multiple superheating thresholds of micrometer-sized droplets irradiated by pulsed CO(2) lasers.

Two distinct superheating fluence thresholds have been measured for micrometer-sized droplets of liquids irradiated by pulsed CO(2) lasers. The lower, deformation, threshold results in minimal droplet mass loss, whereas the higher, disintegration, threshold (which is well defined only if observed several tens of microseconds after the heating laser pulse) leads to droplet fragmentation into many microparticles and vapor. Deformation thresholds are nearly coincident for either long (10-micros) or short (0.4-micros) laser pulses. Disintegration thresholds are higher for long-pulse irradiation and increase with decreasing absorption. A qualitative explanation is given for these phenomena based on the effects of surface tension, thermal conduction, and thermally induced optical inhomogeneities.

Observations of Descartes ring stimulated Raman scattering in micrometer-sized water droplets.

Stimulated Raman scattering (SRS) from micrometer-sized droplets, which results from coupling of spontaneous Raman emission to droplet morphology-dependent resonances (MDR's), exhibits unique characteristics. Spatial patterns consist of bright SRS arcs on the droplet rim. A second source of SRS emission has recently been observed from a ringlike region encircling the droplet axis near the geometric focus (the Descartes ring). Investigation of the time and spectral characteristics of Descartes ring SRS and its suppression by the addition of absorptive dye to the droplet reveals it to be an additional manifestation of droplet MDR's. We conjecture that the Descartes ring results when the MDR light is scattered by refractive-index inhomogeneities produced by the intense pump field within the droplet.

Physical basis for Descartes ring scattering in laser-irradiated microdroplets.

Stimulated Raman scattering from laser-irradiated microdroplets is observed from two distinct spatial regions, the droplet rim and a ringlike region encircling the laser beam axis on the droplet shadow face (the Descartes ring). With the use of two pulsed laser beams, a perturbing beam and a delayed stimulated-Raman-scattering pump beam, the physical mechanism for Descartes ring scattering is investigated. Evidence is obtained of a persistent mechanism that continues even after the perturbing laser pulse is turned off. This mechanism is tentatively identified as electrostriction. The possible existence of an additional prompt mechanism that requires overlap between perturbing and pump laser pulses is also discussed.

Delay of explosive vaporization in pulsed laser-heated droplets.

Measurements of time delays for explosion of pulsed CO(2) laser-heated droplets are presented. A simple model based on classical nucleation theory in superheated liquids, which neglects heat and mass transport, is used to interpret the data. The model shows good agreement with the experimental observations.