Isotopic determination with molecular emission using laser-induced breakdown spectroscopy and laser-induced radical fluorescence.

Molecular emission can be used for isotopic analysis in laser-induced breakdown spectroscopy (LIBS) due to its large isotopic shift. However, spectral weakness and interference have become the main flaws in molecular isotopic analysis, causing deterioration of quantitative accuracy and sensitivity. Here, to overcome these problems, laser-induced radical fluorescence (LIRF) was applied to enhance the molecular spectra and eliminate the spectral interference. The root mean square errors of cross validation (RMSECVs) of boron and carbon isotopes (11BO, 10BO, 12CN, and 13CN) improved to 2.632, 5.721, 5.990, and 1.543 at.%, as compared with 16.96, 35.79, 57.10, and 13.89 at.%, respectively, obtained in the case without LIRF. The limits of detection (LoDs) of 11BO, 10BO, 12CN, and 13CN were 0.9858, 0.8470, 1.606, and 1.193 at.%, respectively. This work demonstrates the feasibility of LIBS-LIRF to achieve isotopic determination with high accuracy and sensitivity.

One-point and multi-line calibration method in laser-induced breakdown spectroscopy.

The calibration-free laser-induced breakdown spectroscopy (CF-LIBS) and its variations are low cost, short time consumption, and high adaptability. However, seeking a more flexible and simple quantitative analysis method remains a challenge. A one-point and multi-line calibration (OP-MLC) was presented as a simple quantitative analysis method of LIBS. The results showed that OP-MLC-LIBS method can achieve quantitative analysis using only one standard sample, and the average relative errors (AREs) are 9, 22, 21 and 36% for Mn, Cr, Ni and Ti elements in six tested low-alloy steel samples, respectively. The method requires neither a large number of standard samples nor complicated calculations, which provides a flexible and low-cost quantitative analysis approach for development and application of LIBS.

Determination of boron with molecular emission using laser-induced breakdown spectroscopy combined with laser-induced radical fluorescence.

Boron is an essential element for industry, but it is hard to accurately and rapidly determine high boron content with conventional laser-induced breakdown spectroscopy (LIBS), due to the matrix and self-absorption effect. Using molecular emission is an alternative method for boron content analysis, but its weak spectra are major challenges. Here, boron monoxide (BO) radicals were used to establish calibration assisted by LIBS and laser-induced radical fluorescence (LIBS-LIRF). Two types of BO radical excitations, vibrational ground state excitation (LIRFG) and vibrational excited state excitation (LIRFE), were compared. The results showed that LIRFG achieved better sensitivity with a limit of detection of 0.0993 wt.%, while the LIRFE was more accurate with a root mean square error of cross validation of 0.2514 wt.%. In conclusion, this work provided a potential approach for molecular emission analysis with LIBS-LIRF.

Investigation on self-absorption at reduced air pressure in quantitative analysis using laser-induced breakdown spectroscopy.

The self-absorption at reduced air pressure for quantitative analysis of Mn and Cu elements in steel using laser-induced breakdown spectroscopy was investigated. The calibration curves of Mn and Cu elements at the air pressures of 100, 80, 50, 20, and 1 kPa were studied. The results show that, the nonlinearity of calibration curves which caused by self-absorption effects at atmosphere could be significantly improved by reducing the air pressure to 1 kPa, and the coefficients of determination (R2) of linear calibration curves of Mn and Cu lines are all higher than 0.99. The further study explored that the reason for the improvement was that the induced plasma became low density and the self-absorption coefficient was close to 1 when the air pressure reduced to 1 kPa.

Sensitive determinations of Cu, Pb, Cd, and Cr elements in aqueous solutions using chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy.

In this study, chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy (CR-SENLIBS) was for the first time applied to improve the detection sensitivities of trace heavy metal elements in aqueous solutions. Utilizing chemical replacement effect, heavy metal ions in aqueous solution were enriched on the magnesium alloy surface as a solid replacement layer through reacting with the high chemical activity metallic magnesium (Mg) within 1 minute. Unitary and mixed solutions with Cu, Pb, Cd, and Cr elements were prepared to construct calibration curves, respectively. The CR-SENLIBS showed a much better detection sensitivity and accuracy for both unitary and mixed solutions. The coefficients of determination R2 of the calibration curves were above 0.96, and the LoDs were of the same order of magnitude, i.e., in the range of 0.016-0.386 µg/mL for the unitary solution, and in the range of 0.025-0.420 µg/mL for the mixed solution. These results show that CR-SENLIBS is a feasible method for improving the detection sensitivity of trace element in liquid sample, which definitely provides a way for wider application of LIBS in water quality monitoring.

Background removal in soil analysis using laser- induced breakdown spectroscopy combined with standard addition method.

The matrix effect of powder samples, especially for soil samples, is significant in laser-induced breakdown spectroscopy (LIBS), which affects the prediction accuracy of the element concentration. In order to reduce this effect of the soil samples in LIBS, the standard addition method (SAM) based on background removal by wavelet transform algorithm was investigated in this work. Five different kinds of certified reference soil samples (lead (Pb) concentrations were 110, 283, 552, 675, and 1141 ppm, respectively) were used to examine the accuracy of this method. The root mean square error of prediction (RMSEP) was more than 303 ppm by using the conventional calibration method. After adoption of SAM with background removal by wavelet transform algorithm, the RMSEP was reduced to 25.7 ppm. Therefore, the accuracy of the Pb element was improved significantly. The mechanism of background removal by wavelet transform algorithm based on SAM is discussed. Further study demonstrated that this method can also improve the predicted accuracy of the Cd element.

Acidity measurement of iron ore powders using laser-induced breakdown spectroscopy with partial least squares regression.

Laser-induced breakdown spectroscopy (LIBS) with partial least squares regression (PLSR) has been applied to measuring the acidity of iron ore, which can be defined by the concentrations of oxides: CaO, MgO, Al2O3, and SiO2. With the conventional internal standard calibration, it is difficult to establish the calibration curves of CaO, MgO, Al2O3, and SiO2 in iron ore due to the serious matrix effects. PLSR is effective to address this problem due to its excellent performance in compensating the matrix effects. In this work, fifty samples were used to construct the PLSR calibration models for the above-mentioned oxides. These calibration models were validated by the 10-fold cross-validation method with the minimum root-mean-square errors (RMSE). Another ten samples were used as a test set. The acidities were calculated according to the estimated concentrations of CaO, MgO, Al2O3, and SiO2 using the PLSR models. The average relative error (ARE) and RMSE of the acidity achieved 3.65% and 0.0048, respectively, for the test samples.

Accuracy improvement of quantitative analysis in laser-induced breakdown spectroscopy using modified wavelet transform.

A modified algorithm of background removal based on wavelet transform was developed for spectrum correction in laser-induced breakdown spectroscopy (LIBS). The optimal type of wavelet function, decomposition level and scaling factor γ were determined by the root-mean-square error of calibration (RMSEC) of the univariate regression model of the analysis element, which is considered as the optimization criteria. After background removal by this modified algorithm with RMSEC, the root-mean-square error of cross-validation (RMSECV) and the average relative error (ARE) criteria, the accuracy of quantitative analysis on chromium (Cr), vanadium (V), cuprum (Cu), and manganese (Mn) in the low alloy steel was all improved significantly. The results demonstrated that the algorithm developed is an effective pretreatment method in LIBS to significantly improve the accuracy in the quantitative analysis.

Accuracy improvement on polymer identification using laser-induced breakdown spectroscopy with adjusting spectral weightings.

A new approach to polymer identification by laser-induced breakdown spectroscopy (LIBS) with adjusting spectral weightings (ASW) was developed in this work aiming at improving the identification accuracy. This approach has been achieved through increasing the intensities of specific characteristic spectral lines which are important to polymer identification but difficult to be excited. Using the ASW method, the identification accuracies of all 11 polymers were increased to nearly 100%, while the accuracies of PE, PU, PP and PC were only 98%, 74%, 90% and 98%, respectively, without using the ASW method.

Accuracy improvement of quantitative analysis by spatial confinement in laser-induced breakdown spectroscopy.

To improve the accuracy of quantitative analysis in laser-induced breakdown spectroscopy, the plasma produced by a Nd:YAG laser from steel targets was confined by a cavity. A number of elements with low concentrations, such as vanadium (V), chromium (Cr), and manganese (Mn), in the steel samples were investigated. After the optimization of the cavity dimension and laser fluence, significant enhancement factors of 4.2, 3.1, and 2.87 in the emission intensity of V, Cr, and Mn lines, respectively, were achieved at a laser fluence of 42.9 J/cm(2) using a hemispherical cavity (diameter: 5 mm). More importantly, the correlation coefficient of the V I 440.85/Fe I 438.35 nm was increased from 0.946 (without the cavity) to 0.981 (with the cavity); and similar results for Cr I 425.43/Fe I 425.08 nm and Mn I 476.64/Fe I 492.05 nm were also obtained. Therefore, it was demonstrated that the accuracy of quantitative analysis with low concentration elements in steel samples was improved, because the plasma became uniform with spatial confinement. The results of this study provide a new pathway for improving the accuracy of quantitative analysis of LIBS.

Field measurements suggest the mechanism of laser-assisted water condensation.

Because of the potential impact on agriculture and other key human activities, efforts have been dedicated to the local control of precipitation. The most common approach consists of dispersing small particles of dry ice, silver iodide, or other salts in the atmosphere. Here we show, using field experiments conducted under various atmospheric conditions, that laser filaments can induce water condensation and fast droplet growth up to several µm in diameter in the atmosphere as soon as the relative humidity exceeds 70%. We propose that this effect relies mainly on photochemical formation of p.p.m.-range concentrations of hygroscopic HNO(3), allowing efficient binary HNO(3)-H(2)O condensation in the laser filaments. Thermodynamic, as well as kinetic, numerical modelling based on this scenario semiquantitatively reproduces the experimental results, suggesting that particle stabilization by HNO(3) has a substantial role in the laser-induced condensation.

Oval-like hollow intensity distribution of tightly focused femtosecond laser pulses in air.

The propagation of a tightly focused femtosecond laser pulse in air has been investigated. Unlike long-distance self-guided propagation of short laser pulses, a novel oval-like hollow distribution of the laser intensity is observed in the experiments and reproduced by the numerical simulations. The formation of the hollow structures can be explained by the interplay between ionization-induced refraction and Kerr self-focusing.

Porcine dermal collagen as a wound dressing for skin donor sites and deep partial skin thickness burns.

Collagen was extracted by pepsin digestion from porcine skin, and collagen membrane was prepared by salt precipitation. The porcine collagen membrane was evaluated as a burn wound dressing in deep partial skin thickness burn wounds in rats. Burn wounds, 4 x 4 cm, were inflicted by exposure of skin to 75 degrees C for 15 s followed by de-epithelialization. Wound healing was assessed by planimetry of epithelialization on day 10 after injury. Open wounds exhibited 24 per cent of wound area re-epithelialized. Collagen membrane dressing significantly improved the healing to 69 per cent of wound area (P < 0.0001). In a completely separate experiment, the porcine collagen membrane was applied as a wound dressing to the donor sites of burn patients, and its effect on wound healing was compared with that of a petroleum jelly gauze dressing. The donor sites covered with petroleum jelly gauze had re-epithelialized by an average of 14.5 days (ranging from 13 to 16 days) after wounding. The wounds dressed with collagen membrane demonstrated a significant increase in the healing rate. Complete re-epithelialization was observed by 10.3 days (ranging from 10 to 12 days) after wounding (P < 0.0001).

Coverage of full skin thickness burns with allograft inoculated with autogenous epithelial cells.

Since the supply of unburned autograft skin may be insufficient to cover very extensive burns, we have prepared allograft skin inoculated with a suspension of uncultured autogenous epithelial cells and grafted this material on to full skin thickness loss wounds. There was a satisfactory 'take' and permanent healing of this mixture of heterogeneous dermis and autogenous epidermis in two out of four patients. In this preliminary report we describe the clinical and histological observations which indicate that in the two patients with successful graft 'take' the epithelial cells proliferated and formed a continuous pale-coloured layer on top of the heterogeneous dermis between 30 and 40 days after application.