Anna P. M. Michel

Laser-induced breakdown spectroscopy of bulk aqueous solutions at oceanic pressures: evaluation of key measurement parameters.

The development of in situ chemical sensors is critical for present-day expeditionary oceanography and the new mode of ocean observing systems that we are entering. New sensors take a significant amount of time to develop; therefore, validation of techniques in the laboratory for use in the ocean environment is necessary. Laser-induced breakdown spectroscopy (LIBS) is a promising in situ technique for oceanography. Laboratory investigations on the feasibility of using LIBS to detect analytes in bulk liquids at oceanic pressures were carried out. LIBS was successfully used to detect dissolved Na, Mn, Ca, K, and Li at pressures up to 2.76 x 10(7) Pa. The effects of pressure, laser-pulse energy, interpulse delay, gate delay, temperature, and NaCl concentration on the LIBS signal were examined. An optimal range of laser-pulse energies was found to exist for analyte detection in bulk aqueous solutions at both low and high pressures. No pressure effect was seen on the emission intensity for Ca and Na, and an increase in emission intensity with increased pressure was seen for Mn. Using the dual-pulse technique for several analytes, a very short interpulse delay resulted in the greatest emission intensity. The presence of NaCl enhanced the emission intensity for Ca, but had no effect on peak intensity of Mn or K. Overall, increased pressure, the addition of NaCl to a solution, and temperature did not inhibit detection of analytes in solution and sometimes even enhanced the ability to detect the analytes. The results suggest that LIBS is a viable chemical sensing method for in situ analyte detection in high-pressure environments such as the deep ocean.

Sequential-Pulse Laser-Induced Breakdown Spectroscopy of High-Pressure Bulk Aqueous Solutions

Sequential-pulse (or dual-pulse) laser-induced breakdown spectroscopy (DP-LIBS) with an orthogonal spark orientation is described for elemental analysis of bulk aqueous solutions at pressures up to ∼138 × 105 Pa (138 bar). The use of sequential laser pulses for excitation, when compared to single-pulse LIBS excitation (SP-LIBS), provides significant emission intensity enhancements for a wide range of elements in bulk solution and allows additional elements to be measured using LIBS. Our current investigations of high-pressure solutions reveal that increasing solution pressure leads to a significant decrease in DP-LIBS emission enhancements for all elements examined, such that we see little or no emission enhancements for pressures above 100 bar. Observed pressure effects on DP-LIBS enhancements are thought to result from pressure effects on the laser-induced bubble formed by the first laser pulse. These results provide insight into the feasibility and limitations of DP-LIBS for in situ multi-elemental detection in high-pressure aqueous environments like the deep ocean.

Single pulse laser-induced breakdown spectroscopy of bulk aqueous solutions at oceanic pressures: interrelationship of gate delay and pulse energy

The ability of oceanographers to make sustained measurements of ocean processes is limited by the number of available sensors for long-term in situ analysis. In recent years, laser-induced breakdown spectroscopy (LIBS) has been identified as a viable technique to develop into an oceanic chemical sensor. We performed single pulse laser-induced breakdown spectroscopy of high pressure bulk aqueous solutions to detect three analytes (sodium, manganese, and calcium) that are of key importance in hydrothermal vent fluids, an ocean environment that would greatly benefit from the development of an oceanic LIBS sensor. The interrelationship of the key experimental parameters, pulse energy and gate delay, for a range of pressures up to 2.76x10(7) Pa, is studied. A minimal effect of pressure on the peak intensity is observed. A short gate delay (less than 200 ns) must be used at all pressures. The ability to use a relatively low laser pulse energy (less than approximately 60 mJ) for detection of analytes at high pressure is also established. Na, Mn, and Ca are detectable at pressures up to 2.76x10(7) Pa at 50, 500, and 50 ppm, respectively, using an Echelle spectrometer.

Double pulse laser-induced breakdown spectroscopy of bulk aqueous solutions at oceanic pressures: interrelationship of gate delay, pulse energies, interpulse delay, and pressure

Laser-induced breakdown spectroscopy (LIBS) has been identified as an analytical chemistry technique suitable for field use. We use double pulse LIBS to detect five analytes (sodium, manganese, calcium, magnesium, and potassium) that are of key importance in understanding the chemistry of deep ocean hydrothermal vent fluids as well as mixtures of vent fluids and seawater. The high pressure aqueous environment of the deep ocean is simulated in the laboratory, and the key double pulse experimental parameters (laser pulse energies, gate delay time, and interpulse delay time) are studied at pressures up to 2.76x10(7) Pa. Each element is found to have a unique optimal set of parameters for detection. For all pressures and energies, a short (< or = 100 ns) gate delay is necessary. As pressure increases, a shorter interpulse delay is needed and the double pulse conditions effectively become single pulse for both the 1.38x10(7) Pa and the 2.76x10(7) Pa conditions tested. Calibration curves reveal the limits of detection of the elements (5000 ppm Mg, 500 ppm K, 500 ppm Ca, 1000 ppm Mn, and 50 ppm Na) in aqueous solutions at 2.76x10(7) Pa for the experimental setup used. When compared to our previous single pulse LIBS work for Ca, Mn, and Na, the use of double pulse LIBS for analyte detection in high pressure aqueous solutions did not improve the limits of detection.

Laser-induced breakdown spectroscopy of high-pressure bulk aqueous solutions.

Laser-induced breakdown spectroscopy (LIBS) is presented for detection of several Group I and II elements (e.g., Na, Ca, Li, and K), as well as Mn and CaOH, in bulk aqueous solution at pressures exceeding 2.76 × 107 Pa (276 bar). Preliminary investigations reveal only minor pressure effects on the emission intensity and line width for all elements examined. These effects are found to depend on detector timing and laser pulse energy. The results of these investigations have implications for potential applications of LIBS for in situ multi-elemental detection in deep-ocean environments.

In vivo measurement of mid-infrared light scattering from human skin

Two mid-infrared light sources, a broadband source from a Fourier Transform Infrared Spectrometer (FTIR) and a pulsed Quantum Cascade (QC) Laser, are used to measure angle-resolved backscattering in vivo from human skin across a broad spectral range. Scattering profiles measured using the FTIR suggest limited penetration of the light into the skin, with most of the light interacting with the stratum corneum layer of the epidermis. Scattering profiles from the QC laser show modulation patterns with angle suggesting interaction with scattering centers in the skin. The scattering is attributed to interaction of the laser light with components such as collagen fibers and capillaries in the dermis layer of the skin.

Spatial and temporal evolution of lead isotope ratios in the North Atlantic Ocean between 1981 and 1989

29� –68� W). In the early 1980s, 206 Pb/ 207 Pb ratios in the North African Basin averaged 1.193 ± 0.005 (1 s). Similar radiogenic ratios within the level of analytical precision (average 0.29%) were found in the Labrador and Iceland Basins (1.198 ± 0.006) and in the Norwegian Sea (1.196 ± 0.008). These radiogenic mixed layer signatures along with atmospheric global lead emission patterns suggest that most North Atlantic lead in the early 1980s was derived from North American leaded gasoline. Samples in the East Iberian Basin near Portugal and France showed lower 206 Pb/ 207 Pb ratios, between 1.167 and 1.182, indicating a significant influence of less radiogenic atmospheric lead transported from Europe and possibly the influence of the Rio Tinto acid mine drainage very close to shore in the Gulf of Cadiz. [Pb] across the entire North Atlantic Basin ranged between 54 and 145 pmol/kg, with the lowest values (54–74 pmol/kg) found at high latitudes (>65� N). In the late 1980s, surface waters in the western subtropical North Atlantic (North American Basin/ Sargasso Sea, >47� W) and in the eastern subtropical North Atlantic (North African Basin/Central Iberian Basin, 53%). These elemental and isotopic results demonstrate the strongly variable isotopic and elemental signatures of North American and European lead throughout the North Atlantic Ocean, frequently dominated by high 206 Pb/ 207 Pb and [Pb] North

Quantum cascade laser open-path system for remote sensing of trace gases in Beijing, China

Exploiting several key characteristics of quantum cascade (QC) lasers, including wide tunability and room- temperature operation, the Quantum Cascade Laser Open- Path System (QCLOPS) was designed for the detection of a range of trace gases and for field deployment in urban environments. Tunability over a wavelength range from 9.3 to 9.8 μm potentially provides the capability for monitoring ozone, ammonia, and carbon dioxide, a suite of trace gases important for air quality and regional climate applications in urban environments. The 2008 Olympic Games in Beijing, China drew attention to air quality problems in urban environ- ments. Prior to and during the Olympic games, regional air quality modifications through factory shutdowns, car restric- tions, and construction halts in Beijing and its surrounding areas created a unique test bed for new sensor technolo- gies such as the QCLOPS sensor. We report the design of this novel, open-path air quality sensor and the results of both laboratory tests and field trials during the 2008 Olympic Games in Beijing, China. C 2010 Society of Photo-Optical Instrumen-

In vitro measurements of physiological glucose concentrations in biological fluids using mid-infrared light

Mid-infrared transmission spectroscopy using broadband mid-infrared or Quantum Cascade laser sources is used to predict glucose concentrations of aqueous and serum solutions containing physiologically relevant amounts of glucose (50-400 mg/dL). We employ partial least squares regression to generate a calibration model using a subset of the spectra taken and to predict concentrations from new spectra. Clinically accurate measurements with respect to a Clarke error grid were made for concentrations as low as 30 mg/dL, regardless of background solvent. These results are an important and encouraging step in the work towards developing a noninvasive in vivo glucose sensor in the mid-infrared.

A quantum cascade laser-based water vapor isotope analyzer for environmental monitoring

A field-deployable mid-infrared quantum cascade laser-based spectrometer was designed and developed for measurements of H2(16)O and H2(18)O at 7.12 μm. H2(16)O and H2(18)O absorption features at 1390.52 cm(-1) and 1389.91 cm(-1), respectively, accessible within current tuning range of the laser, were targeted. The target lines were carefully selected to assure similar absorption levels and similar temperature sensitivities of the line strength due to comparable lower state energies. A real-time spectral fitting algorithm was implemented for isotopic concentration retrieval. Detection limits for H2(16)O and H2(18)O of 2.2 ppm and 7.0 ppb, respectively, were achieved at a dew point of 14 °C (volume mixing ratio of 15,766 ppm) in 1 s integration time, which resulted in a δ(18)O isotopic ratio measurement precision of 0.25‰. The ultimate minimum detection limits obtained after 160 s integration time for H2(16)O and H2(18)O, and δ(18)O measurements were 0.6 ppm, 1.7 ppb, and 0.05‰, respectively.