ARRAY DETECTION SYSTEM; ENERGETIC MATERIALS; SENSOR TECHNOLOGY; LIBS; SPECTRA; AIR; FEMTOSECOND; WAVELENGTHS; TIME

In this work, comparative long-wave infrared (LWIR) laser-induced breakdown spectroscopy (LIBS) emission studies of two excitation sources: conventional 1.064 mu m and eye-safe laser wavelength at 1.574 mu m were performed to analyze several widely-used inorganic energetic materials such as ammonium and potassium compounds as well as the organic liquid chemical warfare agent simulant, dimethyl methylphosphate (DMMP). LWIR LIBS emissions generated by both excitation sources were examined using three different detection systems: a single element liquid nitrogen cooled Mercury Cadmium Telluride (MCT) detector, an MCT linear array detection system with multi-channel preamplifiers + integrators, and an MCT linear array detection system with readout integrated circuit. It was observed that LWIR LIBS studies using an eye-safe pump laser generally reproduced atomic and molecular IR LIBS spectra as previously observed under 1.064 mu m laser excitation. (C) 2017 Optical Society of America

CHLOROPHYLL FLUORESCENCE; WATER-STRESS; SALINITY; ACCUMULATION; THERMOGRAPHY; TEMPERATURE; EFFICIENCY; PROTEIN; SAMPLES; SYSTEM

Drought stress disrupts the balance of macro- and micronutrients and affects the yield of agriculturally and economically significant plants. Rapid detection of stress-induced changes of relative content of elements such as sodium (Na), potassium (K), calcium (Ca) and iron (Fe) in the field may allow farmers and crop growers to counter the effects of plant stress and to increase their crop return. Unfortunately, the analytical methods currently available are time-consuming, expensive and involve elaborate sample preparation such as acid digestion which hinders routine daily monitoring of crop health on a field scale. We report application of an alternative method for rapid detection of drought stress in plants using femtosecond laser-induced breakdown spectroscopy (LIBS). We demonstrate daily monitoring of relative content of Na, K, Ca and Fe in decorative indoor (gardenia) and cultivated outdoor (wheat) plant species under various degrees of drought stress. The observed differences in spectral and temporal responses indicate different mechanisms of drought resistance. We identify spectroscopic markers of drought stress which allow for distinguishing mild environmental and severe drought stress in wheat and may be used for remote field-scale estimation of plant stress resistance and health. (C) 2017 Optical Society of America

QUANTITATIVE-ANALYSIS; INSTRUMENT; ABSORPTION; PLASMA; COBALT; LEAD; SOIL; AIR

Spatially selective excitation was proposed to improve excitation efficiency in laser-induced breakdown spectroscopy combined with laser-inducedfluorescence (LIBS-LIF). Taking chromium (Cr) and nickel (Ni) elements in steels as examples, it was discovered that the optimal excitation locations were the center of the plasmas for the matrix of the iron (Fe) element but the periphery for Cr and Ni elements. By focusing an excitation laser at the optimal locations, not only excitation efficiency but also the analytical accuracy and sensitivity of quantitative LIBS-LIF were better than those with excitation at the plasma center in conventional LIBS-LIF. This study provides an effective way to improve LIBS-LIF analytical performance. (C) 2017 Optical Society of America

QUANTITATIVE-ANALYSIS; ENERGETIC MATERIALS; EMISSIONS; LIBS; WAVE

This is the first report of a simultaneous ultraviolet/visible/NIR and longwave infrared laser-induced breakdown spectroscopy (UVN + LWIR LIBS) measurement. In our attempt to study the feasibility of combining the newly developed rapid LWIR LIBS linear array detection system to existing rapid analytical techniques for a wide range of chemical analysis applications, two different solid pharmaceutical tablets, Tylenol arthritis pain and Bufferin, were studied using both a recently designed simultaneous UVN + LWIR LIBS detection system and a fast AOTF NIR (1200 to 2200 nm) spectrometer. Every simultaneous UVN + LWIR LIBS emission spectrum in this work was initiated by one single laser pulse-induced micro-plasma in the ambient air atmosphere. Distinct atomic and molecular LIBS emission signatures of the target compounds measured simultaneously in UVN (200 to 1100 nm) and LWIR (5.6 to 10 mu m) spectral regions are readily detected and identified without the need to employ complex data processing. In depth profiling studies of these two pharmaceutical tablets without any sample preparation, one can easily monitor the transition of the dominant LWIR emission signatures from coating ingredients gradually to the pharmaceutical ingredients underneath the coating. The observed LWIR LIBS emission signatures provide complementary molecular information to the UVN LIBS signatures, thus adding robustness to identification procedures. LIBS techniques are more surface specific while NIR spectroscopy has the capability to probe more bulk materials with its greater penetration depth. Both UVN + LWIR LIBS and NIR absorption spectroscopyhave shown the capabilities of acquiring useful target analyte spectral signatures in comparable short time scales. The addition of a rapid LWIR spectroscopic probe to these widely used optical analytical methods, such as NIR spectroscopy and UVN LIBS, may greatly enhance the capability and accuracy of the combined system for a comprehensive analysis. (C) 2017 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

MOLECULAR ISOTOPIC SPECTROMETRY; MASS-SPECTROMETRY; AB-INITIO; EMISSION-SPECTRA; ALO; AL2O; ABSORPTION; CHEMISTRY; SURFACE; SYSTEM

Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al2O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al2O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O-2 chemistry in air. (C) 2017 Optical Society of America

SPATIAL CONFINEMENT; BEAM GEOMETRY; SPECTROSCOPY; IMPROVEMENT; EXPOSURE

The inevitable problems in laser induced breakdown spectroscopy are matrix effect and statistical fluctuation of the spectral signal, which can be partly avoided by utilizing a proper confined unit. The dependences of spectral signal enhancement on relative permittivity were studied by varying materials to confine the plasma, which include polytetrafluoroethylene( PTFE), nylon/dacron, silicagel, and nitrile-butadiene rubber (NBR) with the relative permittivity 2.2, similar to 3.3, 3.6, 8 similar to 13, 15 similar to 22. We found that higher relative permittivity rings induce stronger enhancement ability, which restricts the energy dissipation of plasma better and due to the reflected electromagnetic wave from the wall of different materials, the electromagnetic field of plasma can be well confined and makes the distribution of plasma more orderly. The spectral intensities of the characteristic lines Si I 243.5 nm and Si I 263.1 nm increased approximately 2 times with relative permittivity values from 2.2 to similar to 20. The size dependent enhancement of PTFE was further checked and the maximum gain was realized by using a confinement ring with a diameter size of 5 mm and a height of 3 mm (D5mmH3mm), and the rings with D2mmH1mm and D3mmH2mm also show higher enhancement factor. In view of peak shift, peak lost and accidental peaks in the obtained spectra were properly treated in data progressing; the spectral fluctuation decreased drastically for various materials with different relative permittivities as confined units, which means the core of plasma is stabilized, attributing to the confinement effect. Furthermore, the quantitative analysis in coal shows wonderful results-the prediction fitting coefficient R-2 reaches 0.98 for ash and 0.99 for both volatile and carbon. (C) 2017 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

EMISSION-LINES; ALUMINUM; PLASMAS; COAL

A novel self-absorption-free laser-induced breakdown spectroscopy (SAF-LIBS) technique is proposed to directly capture the optically thin spectral line by matching the measured doublet atomic lines intensity ratios with the theoretical one. To realize the experimental SAF-LIBS, the integration time, the fiber collection angle, and the delay time are optimized. The optically thin conditions are validated by comparing the linearity of Boltzmann plots with the traditional self-absorption (SA) correction method and evaluating the SA coefficients. The applicability and limitation of SAF-LIBS on element concentration and laserenergy are also discussed. Univariate quantitative analysis results show that, compared with ordinary LIBS, the average absolute error of aluminum concentration has been reduced by an order of magnitude, which proves that this SAF-LIBS technique is qualified to realize accurate chemical composition measurements. (C) 2017 Optical Society of America

INDUCED BREAKDOWN SPECTROSCOPY; BORON ISOTOPIC RATIO; ABLATION PLASMAS; EMISSION FEATURES; INFRARED-SPECTRA; ENERGY-LEVELS; LIBS; NANOSECOND; SPECTROMETRY; PERFORMANCE

We report on the observation of uranium monoxide (UO) emission following fs laser ablation (LA) of a uranium metal sample. The formation and evolution of the molecular emission is studied under various ambient air pressures. Observation of UO emission spectra at a rarefied residual air pressure of similar to 1 Torr indicates that the UO molecule is readily formed in the expanding plasma with trace concentrations of oxygen present within the vacuum chamber. The persistence of the UO emission exceeded that of the atomic emission; however, the molecular emission was delayed in time compared to the atomic emission due to the necessary cooling and expansion of the plasma before the UO molecules can form. (C) 2017 Optical Society of America