[Raman Signal Enhancement for Gas Detection Using a Hollow Core Optical Fiber].

Raman spectroscopy has been widely used for gas detection due to the advantages of simultaneous multiple species recognition, rapid analysis, and no sample preparation, etc. Low sensitivity is still a great limitation for Raman application. In this work a Raman system based on a hollow core optical fiber (HCOF) was built and the detection sensitivity for the gas was significantly improved. Also a comparison was carried out between the HCOF Raman system and back-scattering Raman system. The obtained results indicated that the HCOF Raman system could well enhance the signal while also for the background and noise. Using HCOF system, 60 folds signal enhancement was achieved with SNR improvement of 6 times for the N2 and O2 in air when comparing to the back-scattering system. While for the same signal intensity, with HCOF system the exposure time was well shortened to 1/60 and the noise was decreased to 1/2 than the back-scattering system.

[Joint Analyses of Na2SO4 Solution by Laser Induced Breakdown Spectroscopy and Raman Spectroscopy].

Spectroscopic sensor is becoming an important issue for the deep-sea exploration due to the advantages of multi-specie, multi-phases and stand-off detection. Different approach have been developing in recent years based on LIBS (Laser Induced Breakdown Spectroscopy) and Raman spectroscopy since Raman-LIBS are complementary techniques with the similar components and the capability of molecular and elementary analysis. In this work, we built a LIBS-Raman system and detected Na2SO4 in aqueous solution to evaluate the potential ocean application. With the same laser, spectrometer and detector, a hybrid of Raman and LIBS system was developed to realize the detection of anions and cations in the seawater. The optics was composed by two parts. Raman channel and LIBS channel, and the signal was collected by a Y type optical fiber bundle. The signal from two channels was separated by imaging on different arrays of the CCD detector. The Raman spectra of SO4(2-) and LIBS spectra of Na was successfully detected simultaneously when the pulse energy was above 3.6 mJ. However, due to the strong bremsstrahlung radiation of LIBS, the signal to noise ratio of Raman was significantly decreased as the laser energy increasing. The results manifested the great potential of Raman-LIBS combination for the underwater detection.

[Discrimination of Crude Oil Samples Using Laser-Induced Time-Resolved Fluorescence Spectroscopy].

The Laser-induced fluorescence spectra combined with pattern recognition method has been widely applied in discrimination of different spilled oil, such as diesel, gasoline, and crude oil. However, traditional three-dimension fluorescence analysis method, which is not adapted to requirement of field detection, is limited to laboratory investigatio ns. The development of oil identification method for field detection is significant to quick response and operation of oil spill. In this paper, a new method based on laser-induced time-resolved fluorescence combined with support vector machine (SVM) model was introduced to discriminate crude oil samples. In this method, time-resolved spectra data was descended into two dimensions with selecting appropriate range in time and wavelength domains respectively to form a SVM data base. It is found that the classification accurate rate increased with an appropriate selection. With a selected range from 54 to 74 ns in time domain, the classification accurate rate has been increased from 83.3% (without selection) to 88.1%. With a selected wavelength range of 387.00~608.87 nm, the classification accurate rate of suspect oil was improved from 84% (without selection) to 100%. Since the detection delay of fluorescence lidar fluctuates due to wave and platform swing, the identification method with optimizing in both time and wavelength domains could offer a better flexibility for field applications. It is hoped that the developed method could provide some useful reference with data reduction for classification of suspect crude oil in the future development.

[Research on the Quantitative Analysis for In-Situ Detection of Acid Radical Ions Using Laser Raman Spectroscopy].

Laser Raman spectroscopy as an in situ analytical technology can enable detailed investigation of the ocean environment. It is necessary to set up a quantitative analysis method based on laser Raman spectroscopy to understand the marine status in situ. In the laboratory investigations, varied concentration of HCO3(-), SO4(2-) and coastal waters of Qingdao are taken as the samples, operating 532 nm of laser, using fiber optic probes to simulate detection mode in situ. Raman spectra are analyzed using the method of internal standard normalization, multiple linear regression (MLR), general Partial Least Squares (PLS) and PLS based on dominant factor respectively in data processing. It was found that correlation coefficients of calibration curves are not high in internal standard normalization method and predicted relative errors on the prepared samples are much high, so internal standard normalization method cannot be effectively used in the quantitative analysis of HCO3(-), SO4(2-) in the water. And with the multiple linear regression, the analysis accuracy was improved effectively. The calibration curve of PLS based on dominant factor showed that the SO4(2-) and HCO3(-) of pre-made solution with correlation coefficient R2 of 0.990 and 0.916 respectively. The 30 mmol · L(-1) of SO4(2-) and 20 mmol · L(-1) of HCO3(-) in two target samples were determined with the relative errors lower than 3.262% and 5.267% respectively. SO4(2-) in the coastal waters as the research object was analyzed by above-mentioned methods, comparing with 28.01 mmol · L(-1) by ion chromatography. It was demonstrated that PLS based on dominant factor method is superior to the rest of the three analysis methods, which can be used in situ calibration, with the mean relative error about 1.128%. All the results show that analysis accuracy would be improved by the PLS based on dominant factor method to predict concentration of acid radical ions.

[Characterization of Time-Resolved Laser-Induced Fluorescence from Crude Oil Samples].

To evaluate the feasibility of laser induced time-resolved fluorescence technique for in-situ detection of underwater suspended oil spill, extensive investigations have been carried out with different densities of crude oil samples from six different wells of Shengli Oilfield in this work. It was found that the fluorescence emission durations of these crude oil samples were almost the same, the Gate Pulse Delay of DDG (Digital Delay Generator) in the ICCD started at 52ns and ended at 82ns with a width (FWHM) of 10 ns. It appears that the peak location and lifetime of fluorescence for different crude oil samples varied with their densities, and those with similar densities shared a similar lifespan with the closer peak locations of fluorescence. It is also observed that the peak of fluorescence remained the same location before reaching the maximum intensity, subsequently shift to longer wavelength as fluorescence attenuated from maximum intensity with a red shift among 17-30 nm varied with samples. This demonstrated that the decay rate of fluorescent components in the crude oils was different, and energy transfer between these components might exist. It is hoped that those obtained results and characteristics could be the useful information for identification of suspended spilled-oil underwater.

[Raman Signal Enhancement for Gas Detection Using a Near Concentric Cavity].

The detection of dissolved gases in seawater plays an important role in ocean observation and exploration. Raman spectroscopy has a great advantage in simultaneous multiple species detection and is thus regarded as a favorable choice for ocean application. However, its sensitivity remains insufficient, and a demand in enhancements is called! for before putting Raman spectroscopy to actual use in marine studies In this work, we developed a near-concentric cavity, in which laser beam could be trapped and reflected back and forth, for the purpose of intensifying Raman signals. The factors that would influence Raman signals were taken into account. The result show that the smaller angle between collection direction and optical axis of reflection mirror, the stronger the signal and signal to noise ratio (SNR) is. With a collection angle of 30 degrees, our Near-concentric Cavity System managed to raise the SNR to a figure about 16 times larger than that of common methods applying 90 degrees. Moreover, the alignment pattern in our system made it possible to excel concentric cavity with a 3 times larger SNR. Compared with the single-pass Raman signal, the signal intensity of our near-concentric cavity was up to 70 times enhanced. According to the obtained results of CO2 measurement, it can be seen that the new system provides a limit of detection(LOD) for CO2 about 0.19 mg x L(-1) using 3-σ criterion standard, and the LOD of 11.5 µg x L(-1) for CH4 was evaluated with the theoretical cross section values of CO2 and CH4.

[The investigation of humic acid by surface-enhanced Raman spectroscopy].

Humic acid (HA), which are organic compounds widely existing in the oceans, rivers and soil, has important significance for the environmental monitoring of soil and water. In this paper, ai ming at the problem of Surface-enhanced Raman Spectroscopy (SERS) applying for HA detection in water, the characteristics of the humic acid on silver colloids was studied by means of SERS. The influence of laser irradiation time, HA concentrations and pH value on the surface-enhanced effects of HA were investigated. The experimental results show that the SERS spectra of HA is ideal when the laser irradiation time between 20-30 min. The SERS of different HA concentrations was detected. It was found that the relative intensity at 1 379 cm(-1) increased as a linear function of the concentration of HA with correlation coefficient R2 of 0.993. The SERS of HA was found to be very sensitive to pH, the SERS spectra of HA was very weak at neutral pH, but at acidic pH and alkaline pH a remarkable increase of SERS intensity occurred. The SERS of HA in running water was detected too. The experimental results show that it is feasible to detect HA in natural water by means of surface-enhanced Raman spectroscopy.

[Water Raman spectrum suppression with low-pass filter in underwater in-situ Raman spectroscopy].

As a powerful tool for studying chemical structures, Raman spectroscopy has been used in aquatic environments in-situ measurement widely, and has been used in deep sea research recently. For underwater in-situ detection, O-H vibration Raman peak of water is inherent and strong compared with other dissolved matter's Raman signals. When the authors want to get a good SNR Raman signal of dissolved matter by increasing detection time, O-H vibration Raman peak of water will get to saturation easily, which influences other Raman signal's detection. In the present paper, a specially designed short-pass optical filter was used for suppression of water's O-H vibration Raman peak. The authors calculated the suppression effect of short-pass optical filter with linear and exponential edges. The simulation shows that exponential edge filter has better performance and can suppress water's O-H vibration Raman peak effectively. The experiment also proves the calculation results. With the suppression optical filter, the intensity of water's O-H vibration Raman signal and other dissolved matters' become similar. And the influence of suppression optical filter on other dissolved matters' Raman signal is little. So the suppression optical filter is feasible for in-situ underwater Raman spectroscopy.

[Experimental investigation of Pb in soil slurries by laser induced breakdown spectroscopy].

Laser induced breakdown spectroscopy (LIBS) has been shown to be a promising technique for element analysis with many advantages including on-line, real time, standing off and multi-element detection capability. In the present paper, the LIBS experiments for Pb in slurry samples were carried out with the motivation of developing an in-situ sensor for monitoring heavy metal. A Q-switched Nd : YAG laser operating at 532 nm with repetition frequency of 10 Hz was utilized to generate plasma on the prepared slurry samples, which were doped with same weight manganese as reference and varied concentration of lead. The induced plasma emission was recorded by CCD. The LIBS signals at PbI 405.78 nm and MnI 403.07 nm from the slurry samples were investigated. It was found that the intensity ratio of I(Pb)/ I(Mn) increased as a linear function of the concentration of Pb with correlation coefficient R2 of 0.994 9. The obtained results show that LIBS with conjunction of referent element could be developed as a potential technique for contamination analysis of soil slurries. The main influence factors in LIBS signal detection were also discussed.

Direct-detection Doppler wind measurements with a Cabannes-Mie lidar: a. Comparison between iodine vapor filter and Fabry-Perot interferometer methods.

Atmospheric line-of-sight (LOS) wind measurement by means of incoherent Cabannes-Mie lidar with three frequency analyzers with nearly the same maximum transmission of ~80% that could be fielded at different wavelengths is analytically considered. These frequency analyzers are (a) a double-edge Fabry-Perot interferometer (FPI) at 1064 nm (IR-FPI), (b) a double-edge Fabry-Perot interferometer at 355 nm (UV-FPI), and (c) an iodine vapor filter (IVF) at 532 nm with two different methods, using either one absorption edge, single edge (se-IVF), or both absorption edges, double edge (de-IVF). The effect of the backscattered aerosol mixing ratio, R(b), defined as the ratio of the aerosol volume backscatter coefficient to molecular volume backscatter coefficient, on LOS wind uncertainty is discussed. Assuming a known aerosol mixing ratio, R(b), and 100,000 photons owing to Cabannes scattering to the receiver, in shot-noise-limited detection without sky background, the LOS wind uncertainty of the UV-FPI in the aerosol-free air (R(b)=0), is lower by ~16% than that of de-IVF, which has the lowest uncertainty for R(b) between 0.02 and 0.08; for R(b)>0.08, the IR-FPI yielded the lowest wind uncertainty. The wind uncertainty for se-IVF is always higher than that of de-IVF, but by less than a factor of 2 under all aerosol conditions, if the split between the reference and measurement channels is optimized. The design flexibility, which allows the desensitization of either aerosol or molecular scattering, exists only with the FPI system, leading to the common practice of using IR-FPI for the planetary boundary layer and using UV-FPI for higher altitudes. Without this design flexibility, there is little choice but to use a single wavelength IVF system at 532 nm for all atmospheric altitudes.

Direct-detection Doppler wind measurements with a Cabannes-Mie lidar: b. Impact of aerosol variation on iodine vapor filter methods.

Atmospheric line-of-sight (LOS) wind measurement by means of incoherent Cabannes- Mie lidar with three frequency analyzers, two double-edge Fabry-Perot interferometers, one at 1064 nm (IR-FPI) and another at 355 nm (UV-FPI), as well as an iodine vapor filter (IVF) at 532 nm, utilizing either a single absorption edge, single edge (se-IVF), or both absorption edges, double edge (de-IVF), was considered in a companion paper [Appl. Opt. 46, 4434 (2007)], assuming known atmospheric temperature and aerosol mixing ratio, Rb. The effects of temperature and aerosol variations on the uncertainty of LOS wind measurements are investigated and it is found that while the effect of temperature variation is small, the variation in R(b) can cause significant errors in wind measurements with IVF systems. Thus the means to incorporate a credible determination of R(b) into the wind measurement are presented as well as an assessment of the impact on wind measurement uncertainty. Unlike with IVF methods, researchers can take advantage of design flexibility with FPI methods to desensitize either molecular scattering for IR-FPI or aerosol scattering for UV-FPI. The additional wind measurement uncertainty caused by R(b) variation with FPI methods is thus negligible for these configurations. Assuming 100,000 photons from Cabannes scattering, and accounting for the Rb measurement incorporated into the IVF method in this paper, it is found that the lowest wind uncertainty at low wind speeds in aerosol-free air is still with UV-FPI, ~32% lower than with de-IVF. For 0.050.07, the IR-FPI outperforms all other methods. In addition to LOS wind uncertainty comparison under high wind speed conditions, the need of an appropriate and readily available narrowband filter for operating the wind lidar at visible wavelengths under sunlit condition is discussed; with such a filter the degradation of LOS wind measurement attributable to clear sky background is estimated to be 5% or less for practical lidar systems.