Integrating cavity based gas cells: a multibeam compensation scheme for pathlength variation

We present a four beam ratiometric setup for an integrating sphere based gas cell, which can correct for changes in pathlength due to sphere wall contamination. This allows for the gas absorption coefficient to be determined continuously without needing to recalibrate the setup. We demonstrate the technique experimentally, measuring methane gas at 1651nm. For example, contamination covering 1.2% of the sphere wall resulted in an uncompensated error in gas absorption coefficient of ≈41%. With the ratiometric scheme, this error was reduced to ≈2%. Potential limitations of the technique, due to subsequent deviations from mathematical assumptions are discussed, including severe sphere window contamination

Sensitive detection of methane at 3.3 μm using an integrating sphere and interband cascade laser

Detection of methane at 3.3μm using a DFB Interband Cascade Laser and gold coated integrating sphere is performed. A 10cm diameter sphere with effective path length of 54.5cm was adapted for use as a gas cell. A comparison between this system and one using a 25cm path length single-pass gas cell is made using direct TDLS and methane concentrations between 0 and 1000 ppm. Initial investigations suggest a limit of detection of 1.0ppm for the integrating sphere and 2.2ppm for the single pass gas cell. The system has potential applications in challenging or industrial environments subject to high levels of vibration

Spectrometer-based refractive index and dispersion measurement using low-coherence interferometry with confocal scanning

This paper describes a technique for measuring refractive index and thickness of transparent plates using a fibre-optic low-coherence interferometer. The interferometer is used to independently measure quantities related to the phase and group refractive indices, np and ng, of the material under investigation. Additionally, the dispersion of the phase index dependent quantity is measured by taking advantage of the range of wavelengths available from a broadband source. These three quantities are related to simultaneously yield np and ng as well as the geometrical thickness t of the sample. Measurements are presented for a range of transparent materials including measurements of the ordinary and extraordinary refractive indices of a birefringent sapphire window. The mean percentage errors across all the samples tested were 0.09% for np, 0.08% for np, and 0.11% for t

We are still largely in the dark as to whether incarceration reduces recidivism

One of the aims of prison is to reduce recidivism. Daniel P. Mears, Joshua C. Cochran, and Francis T. Cullen find, however, that research tells us little about the effects of prison on offending. They argue that if we want more effective punishment policy, we need better research on the conditions under which incarceration reduces recidivism or achieves other goals

Low-volume, fast response-time hollow silica waveguide gas cells for mid-IR spectroscopy

Hollow silica waveguides (HSWs) are used to produce long path length, low-volume gas cells, and are demonstrated with quantum cascade laser spectroscopy. Absorption measurements are made using the intrapulse technique, which allows measurements to be made across a single laser pulse. Simultaneous laser light and gas coupling is achieved through the modification of commercially available gas fittings with low dead volume. Three HSW gas cell configurations with different path lengths and internal diameters are analyzed and compared with a 30 m path length astigmatic Herriott cell. Limit of detection measurements are made for the gas cells using methane at a wavelength 7.82 μm. The lowest limit of detection was provided by HSW with a bore diameter of 1000 μm and a path length of 5 m and was measured to be 0.26 ppm, with a noise equivalent absorbance of 4.1×10 −4 . The long-term stability of the HSW and Herriott cells is compared through analysis of the Allan–Werle variance of data collected over a 24 h period. The response times of the HSW and Herriott cells are measured to be 0.8 s and 36 s, respectively

Influence of aberrations on confocal-based remote refractive index measurements

Confocal scanning combined with low-coherence interferometry is used to provide remote refractive index and thickness measurements of transparent materials. The influence of lens aberrations in the confocal measurement is assessed through ray-trace modeling of the axial point-spread functions generated using optical configurations comprised of paired aspherics and paired achromats. Off-axis parabolic mirrors are suggested as an alternative to lenses and are shown to exhibit much more symmetric profiles provided the system numerical aperture is not too high. The modeled results compare favorably with experimental data generated using an optical instrument comprised of a broadband source and line-scan spectrometer. Refractive index and thickness measurements are made with each configuration with most mirror pairings offering better than twice the repeatability and accuracy of either lens pairing

An optical fiber hydrogen sensor using a palladium-coated ball lens

A self-referenced optical fiber refractometer using a ball lens as a sensor head has been developed and characterized. A 350-μm ball lens created at the tip of a single mode fiber has been coated with a 40-nm optically thin layer of palladium that reacts with hydrogen to form a hydride, which has a lower reflectivity than pure palladium. Optical reflectance measurements from the tip of the ball lens were performed to determine the hydrogen response. The change in reflectivity is proportional to the hydrogen concentration in the range 0% to 1% hydrogen in air with a detection limit down to 10 ppm (1σ) in air. This technique offers a simple sensor head arrangement, with a larger sampling area (~40 times) than a typical single-mode fiber core. A statistical image analysis of a palladium film, with cracks created by accelerated failure, confirms that the anticipated sensor area for a ball lens sensor head has a more predictable reflectivity than that of a bare fiber core

X-ray Insights Into Interpreting CIV Blueshifts and Optical/UV Continua

We present 0.5-8.0 keV Chandra observations of six bright quasars that represent extrema in quasar emission-line properties -- three quasars each with small and large blueshifts of the CIV emission line with respect to the systemic redshift of the quasars. Supplemented with seven archival Chandra observations of quasars that met our selection criteria, we investigate the origin of this emission-line phenomenon in the general context of the structure of quasars. We find that the quasars with the largest CIV blueshifts show evidence, from joint-spectral fitting, for intrinsic X-ray absorption (N_H ~ 10^22 cm^-2). Given the lack of accompanying CIV absorption, this gas is likely to be highly ionized, and may be identified with the shielding gas in the disk-wind paradigm. Furthermore, we find evidence for a correlation of alpha_uv, the ultraviolet spectral index, with the hardness of the X-ray continuum; an analysis of independent Bright Quasar Survey data from the literature supports this conclusion. This result points to intrinsically red quasars having systematically flatter hard X-ray continua without evidence for X-ray absorption. We speculate on the origins of these correlations of X-ray properties with both CIV blueshift and alpha_uv and discuss the implications for models of quasar structure.Comment: 9 figs, 25 pages, AASTeX; accepted for publication in A

Uncovering the Neoproterozoic Carbon Cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter1,2. Neoproterozoic carbonate records contain unusualand large negative isotopic anomalies within long periods (10–100 million years) characterized by d13C in carbonate (d13Ccarb) enriched to more than +5 per mil. Classically, d13Ccarb is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments2–4, which can be linked to oxygen accumulation through the stoichiometry of primary production3,5. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of d13Ccarb and d13C in organic carbon (d13Corg) will covary, offset by the fractionation imparted by primary production5. The documentation of several Neoproterozoic d13Ccarb excursions that are decoupled from d13Corg, however, indicates that other mechanisms6–8 may account for these excursions. Here we present d13C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple d13Ccarb excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis7,8 or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir6. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret d13Ccarb anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals9–11.Earth and Planetary Science

Energy Starved Candidatus Pelagibacter Ubique Substitutes Light-Mediated ATP Production for Endogenous Carbon Respiration

Previous studies have demonstrated that Candidatus Pelagibacter ubique, a member of the SAR11 clade, constitutively expresses proteorhodopsin (PR) proteins that can function as light-dependent proton pumps. However, exposure to light did not significantly improve the growth rate or final cell densities of SAR11 isolates in a wide range of conditions. Thus, the ecophysiological role of PR in SAR11 remained unresolved. We investigated a range of cellular properties and here show that light causes dramatic changes in physiology and gene expression in Cand. P. ubique cells that are starved for carbon, but provides little or no advantage during active growth on organic carbon substrates. During logarithmic growth there was no difference in oxygen consumption by cells in light versus dark. Energy starved cells respired endogenous carbon in the dark, becoming spheres that approached the minimum predicted size for cells, and produced abundant pili. In the light, energy starved cells maintained size, ATP content, and higher substrate transport rates, and differentially expressed nearly 10% of their genome. These findings show that PR is a vital adaptation that supports Cand. P. ubique metabolism during carbon starvation, a condition that is likely to occur in the extreme conditions of ocean environments