William F. Pearman

Dual-pulse laser-induced breakdown spectroscopy with combinations of femtosecond and nanosecond laser pulses

Nanosecond and femtosecond laser pulses were combined in an orthogonal preablation spark dual-pulse laser-induced breakdown spectroscopy (LIBS) configuration. Even without full optimization of interpulse alignment, ablation focus, large signal, signal-to-noise ratio, and signal-to-background ratio enhancements were observed for both copper and aluminum targets. Despite the preliminary nature of this study, these results have significant implications in the attempt to explain the sources of dual-pulse LIBS enhancements.

Dual-pulse laser-induced breakdown spectroscopy in bulk aqueous solution with an orthogonal beam geometry

Use of dual-pulse laser-induced breakdown spectroscopy with an orthogonal spark orientation is presented as a technique for trace metal analysis in bulk aqueous solutions. Two separate Q-switched Nd:YAG lasers operating at their fundamental wavelengths are used to form a subsurface, laser-induced plasma in a bulk aqueous solution that is spectroscopically analyzed for the in situ detection of Ca, Cr, and Zn. Optimizing the key experimental parameters of proper spark alignment, gate delay (td), gate width (tb), and interpulse timing (deltaT) allowed experimentally determined detection limits of the order of micrograms per milliliter and submicrograms per milliliter. We present supporting evidence of a sampling mechanism that involves the formation of a cavitation bubble with the first pulse (E1) followed by analysis of that bubble with a second pulse (E2). The plasma created by E2 contains the analytically relevant information from the aqueous sample and often represents >250-fold enhancement over a single laser pulse with energy equal to E1 alone.

Temporal dependence of the enhancement of material removal in femtosecond–nanosecond dual-pulse laser-induced breakdown spectroscopy

Despite the large neutral atomic and ionic emission enhancements that have been noted in collinear and orthogonal dual-pulse laser-induced breakdown spectroscopy, the source or sources of these significant signal and signal-to-noise ratio improvements have yet to be explained. In the research reported herein, the combination of a femtosecond preablative air spark and a nanosecond ablative pulse yields eightfold and tenfold material removal improvement for brass and aluminum, respectively, but neutral atomic emission is enhanced by only a factor of 3-4. Additionally, temporal correlation between enhancement of material removal and of atomic emission is quite poor, suggesting that the atomic-emission enhancements noted in the femtosecond-nanosecond pulse configuration result in large part from some source other than simple improvement in material removal.

Surface-Enhanced Raman Spectroscopy for in Situ Measurements of Signaling Molecules (Autoinducers) Relevant to Bacteria Quorum Sensing:

Autoinducer (AI) molecules are used by quorum sensing (QS) bacteria to communicate information about their environment and are critical to their ability to coordinate certain physiological activities. Studying how these organisms react to environmental stresses could provide insight into methods to control these activities. To this end, we are investigating spectroscopic methods of analysis that allow in situ measurements of these AI molecules under different environmental conditions. We found that for one class of AIs, N-acyl-homoserine lactones (AHLs), surface-enhanced Raman spectroscopy (SERS) is a method capable of performing such measurements in situ. SERS spectra of seven different AHLs with acyl chain lengths from 4 to 12 carbons were collected for the first time using Ag colloidal nanoparticles synthesized via both citrate and borohydride reduction methods. Strong SERS spectra were obtained in as little as 10 seconds for 80 μM solutions of AI that exhibited the strongest SERS response, whereas 20 seconds was typical for most AI SERS spectra collected during this study. Although all spectra were similar, significant differences were detected in the SERS spectra of C4-AHL and 3-oxo-C6-AHL and more subtle differences were noted between all AHLs. Initial results indicate a detection limit of ∼10−6 M for C6-AHL, which is within the limits of biologically relevant concentrations of AI molecules (nM–μM). Based on these results, the SERS method shows promise for monitoring AI molecule concentrations in situ, within biofilms containing QS bacteria. This new capability offers the possibility to “listen in” on chemical communications between bacteria in their natural environment as that environment is stressed.

Multipass Capillary Cell for Enhanced Raman Measurements of Gases

A simple Raman multipass capillary cell (MCC) is described that gives 12-to 30-fold signal enhancements for non-absorbing gases. The cell is made by coating the inside of 2-mm inner diameter silica capillary tubes with silver. The device is very small and suitable for remote and in situ Raman measurements with optical fibers. Application of the MCC is similar to previously described liquid core waveguides but, unlike the latter devices, the MCC is generally more applicable to a wide range of non-absorbing gases.

Quantitative measurements of CO2 and CH4 using a multipass Raman capillary cell.

Raman measurements of two common gases are made using a simple multipass capillary Raman cell (MCC) coupled to an unfiltered 18 around 1 fiber-optic Raman probe. The MCC, which is fabricated by chemical deposition of silver on the inner walls of a 2 mm inner diameter glass capillary tube, gives up to 20-fold signal enhancements for nonabsorbing gases. The device is relatively small and suitable for remote and in situ Raman measurements with optical fibers. The optical behavior of the MCC is similar to previously described liquid-core waveguides and hollow metal-coated waveguides used for laser transmission, but unlike the former devices, the MCC is generally applicable to a very wide range of nonabsorbing gases.

Underwater measurements using laser induced breakdown spectroscopy

New data is presented related to high-pressure underwater laser-induced breakdown spectroscopy measurements. LIBS calibration curves in high-pressure water are shown for elements that are relevant to hydrothermal vent fluid chemistry. The use of internal standards in high-pressure solutions is shown, and the use of hydrogen and oxygen, produced from decomposition of water by the LIBS plasma, as an internal standard for underwater LIBS measurements is demonstrated. The use of double-pulse LIBS for high pressure underwater measurements provides improved sensitivity but it is shown that the technique is limited by reduction in the size of the laser-induced vapor bubble with increased solution pressure.

Characterization of the Ag Mediated Surface-Enhanced Raman Spectroscopy of Saxitoxin

The rapid detection and quantification of saxitoxin (STX) is reported using surface-enhanced Raman spectroscopy (SERS) with a colloidal hydrosol of silver nanoparticles. Under the conditions of our experiments, the limit of detection (LD) for STX using SERS is 3 nM, with a limit of quantification (LQ) of 20 nM. It is shown that the SERS method is rapid, with spectra being collected in as little as 5 seconds total integration time for a 40 nM STX sample. In order to improve the signal-to-noise ratio, SERS spectra were generally collected with a total integration time of 1 minute (6 accumulations of 10 seconds each), with no need for extensive sample work-up or substrate preparation. Based on these results, the SERS technique shows great promise for the future detection and quantification of STX molecules in aqueous solutions.

Raman Analysis of Common Gases Using a Multi-Pass Capillary Cell (MCC)

The Raman analysis of common, non-absorbing gases was performed using an 18@1 fiber-optic probe coupled to a multi-pass capillary cell (MCC) for signal enhancement. The MCC is fabricated by metal-coating, using silver or other highly reflective metals, the inside of a 1-2 mm diameter glass capillary using commercially available silvering solutions and provides enhancements up to 30-fold over measurements using the fiber-optic probe alone. The design of the MCC is simple and the device is easy to incorporate into an experimental setup making it suitable for remote and in-situ analysis. Although the MCC is functionally similar to liquid-core waveguides that have been previously described in the literature, the MCC is not based on total internal reflection and so the refractive index of the analyte is not important to the operation of the device. The principle of operation of the MCC is similar to mirror-based multiple pass Raman cells, however, the MCC is not expensive, alignment is trivial and an optical path length up to several meters in length is possible. With our first-generation silver-coated MCCs, limits of detection were determined to be 0.02% and 0.2% for CH4 and CO2 respectively. In this talk we will discuss optimization of the MCC and issues involved in its use.