Laser-induced Breakdown Spectroscopy Signal Enhancement Research Articles

Porous Chitosan Composite Membrane Tandem Laser-Induced Breakdown Spectroscopy for Detection of Metal Elements in Liquid Samples

Laser-induced breakdown spectroscopy (LIBS) is currently one of the most popular techniques for direct element analysis of solid samples. However, when directly used for liquid sample analysis, there are disadvantages, including sample splashing, plasma quenching, and poor signal stability. These problems can be overcome through liquid-solid matrix conversion; at the same time, LIBS signal enhancement can be realized, and the sensitivity of detection of liquid samples can be improved. For this research, the authors used chitosan (CS) as a raw material, and introduced poly(vinyl alcohol) (PVA) and polyethyleneimine (PEI) to finally synthesize a new type of porous membrane material with better stability and more functional group content. The membrane was used as a liquid-solid conversion matrix material combined with LIBS technology to successfully achieve rapid separation and detection of Cu, Ag, Pb, and Cr, and the corresponding detection limits can reach 0.038, 0.069, 0.012, and 0.009 mg/L, respectively. This method further improves the sensitivity of the LIBS method. Combining it with membrane materials will replace inactive membranes and open up a new way for the rapid analysis of solution samples using LIBS technology.

Laser-induced breakdown spectroscopy signal enhancement effect for argon caused by the presence of gold nanoparticles

The effect of the presence of nanoparticles (NPs) on the laser induced breakdown spectroscopy (LIBS) signal of argon gas was studied experimentally. 10–20 nm diameter gold NPs, produced by a spark discharge nanoparticle generator, were suspended in argon gas. The effect of particle size, number concentration and mass concentration, as well as laser pulse energy on the LIBS argon signal was systematically investigated. It was found that the breakdown threshold of the gas decreases considerably, facilitating the detection of Ar emission at such laser fluences, which do not allow plasma formation without the presence of the NPs. Our observations persist even at aerosol mass concentrations that are too low to allow the direct detection of nanoparticles. The effect, which is attributed to electron thermo- and field emission induced by the high intensity laser pulse, shows an asymptotically increasing magnitude with the aerosol mass concentration. The signal enhancement was found to be 102–104 and the effect is suggested to be useful in trace gas analysis or for the indirect detection of NPs. The achievable indirect aerosol mass concentration detection limit was estimated to be in the parts per trillion regime (as low as 50 ng·m−3), which is comparable to the best literature values reported for direct analysis.

Role of geometric configurations in optimizing the LIBS signal enhancement

The quest for improving the limits of trace elemental detection and reproducibility in Laser-Induced Breakdown Spectroscopy (LIBS) resulted in the development of novel methodologies for sample excitation and plasma collection. Efficient plasma collection and coupling to the detector is of utmost importance in LIBS studies for meaningful and logical data interpretations. Unfortunately, limited attention is paid to such critical aspects in comparison with the plethora of publications in advanced data analysis. In view of this, we probe the role of the different optical schemes on the collected plasma signal strength from three standard samples (Cu, Cd, Pb) while retaining all other experimental conditions such as laser energy, detector gain, gate width, and gate delay same. In addition, the role of coupling modalities on the plasma signal strength, an area not studied in depth, is investigated and found that the direct coupling scheme always provides better signal strength and repeatability. Moreover, the role of spectrographs in the measured signal strength is also investigated in detail for all the said standard samples. A comparative study elucidates that single shot experiments with low excitation pulse energies of the order of a few mJ are sufficient as compared to multi-short pulse laser excitation to provide the required limit of detection of the samples of interest which in turn makes the technique practically non-destructive. The efficacy of the optimized system was manifested by investigating idealistic and real-life samples viz. standard meals and teeth to differentiate between the normal and carious states. Our results reveal that the developed strategies may be useful in designing a robust system for fast ultra-trace elemental detection.

Tomography of double-pulse laser-induced plasmas in the orthogonal geometry

The temporal evolution of laser-induced plasmas is studied in the orthogonal double-pulse arrangement. Both the pre-ablation mode (an air spark is induced above the sample surface prior to the ablation pulse) and the re-heating mode (additional energy is delivered into the plasma created by the ablation pulse) is considered. The plasmas are investigated in terms of the temporal evolution of their electron density, temperature, and volume. The plasma volumes are determined using a time-resolved tomography technique based on the Radon transformation. The reconstruction is carried out for both white-light and band-pass filtered emissivities. The white-light reconstruction corresponds to the overall size of the plasmas. On the other hand, the band-pass emissivity reconstruction shows the distribution of the atomic sample species (Cu I). Moreover, through spectrally resolved tomographic reconstruction, the spatial homogeneity of the electron density and temperature of the plasmas is also investigated at various horizontal slices of the plasmas. Our results show that the pre-ablation geometry yields a more temporally stable and spatially uniform plasma, which could be beneficial for calibration-free laser-induced breakdown spectroscopy (LIBS) approaches. On the contrary, the plasma generated in the re-heating geometry exhibits significant variations in electron density and temperature along its vertical axis. Overall, our results shed further light on the mechanisms involved in the LIBS signal enhancement using double-pulse ablation.

Laser-induced breakdown spectroscopy of ammonia gas with resonant vibrational excitation.

In this work, laser-induced breakdown spectroscopy (LIBS) of gaseous ammonia (NH3) molecules on- and off-resonant vibrational excitation was studied in open air. A wavelength-tunable, continuous wave (CW), carbon dioxide (CO2) laser tuned at a resonant absorption peak (9.219 µm) within the infrared radiation (IR) range was used to resonantly excite the vibration of the N-H wagging mode of ammonia molecules. A pulsed Nd:YAG laser (1064 nm, 15 ns) was used to break down the ammonia gas for plasma imaging and spectral measurements. In this study, plasmas generated with the ammonia molecules without additional CO2 laser beam irradiation and with additional CO2 laser beam irradiation with the wavelengths on- and off-resonant vibrational excitation of ammonia molecules were investigated and referred as LIBS, LIBS-RE-ON and LIBS-RE-OFF, respectively. The experimental results showed that the temporal and spatial evolution as well as electron temperature and density of plasmas induced with LIBS and LIBS-RE-OFF were consistent but differed from LIBS-RE-ON. Compared with LIBS and LIBS-RE-OFF, plasmas in LIBS-RE-ON showed larger spatial expansion and enhanced emission after a delay time of 1 µs in this study, as well as significantly enhanced electron temperature by ∼ 64%. Time-resolved electron temperatures and densities showed that the emission signal enhancement in LIBS-RE-ON can be primarily attributed to the electron temperature enhancement. Signal enhancement in LIBS indicated improved detection sensitivity. This study could inspire future works on LIBS for gas detection with improved sensitivity and selectivity probably by using ultrafast/intense laser-induced molecular breakdown/ionization with resonant vibrational excitation of molecules.

Triple-pulse LIBS: laser-induced breakdown spectroscopy signal enhancement by combination of pre-ablation and re-heating laser pulses

The goal of this work is to examine the effect of a third additional laser pulse on orthogonal double-pulse laser-induced breakdown spectroscopy (DP LIBS).

Laser-fluence dependence of signal enhancement in femtosecond double-pulse laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) based on femtosecond laser pulses has widely been used for analyzing chemical elements in samples. In this research, we achieved the double-pulse operation with a two-polarizer configuration, and the signal enhancement factor of 4–15 was observed as compared with the single pulse LIBS scheme. It is found that with the change in interpulse delay time between 0 and 150 ps, the laser-fluence dependence of the LIBS signal enhancement can be classified into three types that are characterized by the different behavior of linear and quadratic intensity increase, followed by the intensity saturation. Such different responses are presumably ascribable to the mechanisms of electron-ion relaxation and plasma reheating. Also, different behavior is seen for the signal enhancement with different laser intensity and beam diameter while the laser fluence is kept constant. This indicates that generally, the use of a larger beam diameter is recommended for increasing the signal enhancement factor.

Development of a LIBS system for in situ surface measurements during plasma exposure in PISCES-A.

A laser-induced breakdown spectroscopy (LIBS) system has been developed with a Q-switched Nd:YAG laser (wavelength = 1064 nm and pulse width ∼5 ns) to conduct in situ surface measurements during plasma exposure in the PISCES-A linear divertor plasma simulator. The LIBS signal enhancement is obtained with both the magnetic field normal to the surface of a target and steady-state background plasma. Migration of sputtered Ta impurities onto the neighboring Cr surface is identified during He plasma exposure, only when cone structures are formed on the Cr surface. D retention in W during D plasma exposure is observed to decrease with increasing the sample temperature. The temporal evolution of D outgassing from W is measured in a time range of ∼10-420 s right after D plasma exposure. A power law fit, t -α , yields α ∼ 0.34 ± 0.09, which is nearly consistent with calculated and measured values.

Emission enhancement of laser-induced breakdown spectroscopy for aqueous sample analysis based on Au nanoparticles and solid-phase substrate.

In this paper, porous electrospun ultrafine fiber with a nanoparticle coating was proposed as an effective approach to enhance the laser-induced breakdown spectroscopy (LIBS) signal for metal ions in aqueous systems. It is known that the LIBS technique is very limited when used for liquid sample analysis. On the other hand, in practical applications, many LIBS measurements have been accomplished in a liquid environment. A signal enhancement method for aqueous sample LIBS analysis was presented in this work, where Au nanoparticles and a solid-phase support were combined for the first time for aqueous sample analysis with LIBS. The system operation was relatively simple, which only required Au nanoparticles being dropped onto the surface of porous electrospun ultrafine fibers before LIBS analysis. Significant signal enhancement was achieved due to the integration of the merits of the Au nanoparticles and the ultrafine fibers. Nanoparticles possess significant LIBS signal enhancement effects by providing several plasma ignition points and then causing more efficient emissions. In addition, Au nanoparticles could also help to decrease the breakdown threshold of target elements for LIBS analysis. The electrospun ultrafine fibers as solid-phase support can accommodate a larger volume of aqueous sample. Meanwhile, the aqueous solution on the fiber surface was easy to evaporate. The experimental results showed that the limits of detection (LODs) with this method were significantly improved, 0.5μg/mL for Cr, 0.5μg/mL for Pb, and 1.1μg/mL for Cu, respectively, compared with 2.0μg/mL for Cr and 3.3μg/mL for Cu in the previous research. In the proposed method, signal enhancement could be achieved without any extra equipment, which makes the LIBS technique feasible for direct measurement of an aqueous sample.

The mutual effect of metal sample and turboflame in LIBS signal enhancement

The main aim of the present study is to evaluate the mutual effect of copper sample and turboflame in laser induced breakdown spectroscopy (LIBS) signal enhancement. The use of copper sample leads to a signal enhancement in CN (B2Σ+–X2Σ+) 384.2–388.4 nm molecular transition, N742nm, N744nm, N746nm (a triplet generated by the fine splitting of the 2s22p2(3P)3s–2s22p2(3P)3p transition) and Hα, 656.3 nm (as a flame inductor) atomic lines analysis. Additionally, increase in copper sample temperature with flame can enhance the Cu atomic line intensities (as copper sample inductors). Moreover, in this paper, the comparison between turboflame and alcohol flame on LIBS analysis was studied. LIBS signal intensity variation in a turboflame and turboflame coupled with copper sample at different laser pulse energies indicated that the low laser pulse energy could be compensated by using a copper sample that is coupled with turboflame and improved LIBS signal enhancement. For flames analysis, the use of metal sample in LIBS method is demonstrated to be costeffective, compact, and capable of signal enhancement.

Ultrasonic Nebulizer Assisted LIBS: a Promising Metal Elements Detection Method for Aqueous Sample Analysis**supported by National Natural Science Foundation of China (No. 11104153)

A newly developed approach for trace metal elements detection for aqueous samples analysis is presented in this paper. The idea of this approach is to improve ablation efficiency by transforming the liquid sample into a dense cloud of droplets using an ultrasonic nebulizer. The resulting droplets are then subjected to analysis by laser induced breakdown spectroscopy (LIBS). A purpose-built ultrasonic nebulizer assisted LIBS (UN-LIBS) system has been applied to the analysis of aqueous samples at trace levels of concentration. Experimental investigations of solution samples were carried out with various dissolved trace metal elements (Mn, Zn, Cu, Pb, Fe, Mg and Na) using this approach. The characteristics of UN-LIBS signal of the elements were investigated regarding the lifetime and S/B ratio and the calibration curves for trace metal elements analyses. The obtained LODs are comparable or much better than the LODS of the reported signal enhancement approaches when the laser pulse energy was as low as 30 mJ. The good linearity of calibration curves and the low LODs shows the potential ability of this method for metal elements analysis application. The density of the electrons was calculated by measuring the Stark width of the line of Hα. The possible mechanism of the LIBS signal enhancement of this approach was briefly discussed.

Laser-induced breakdown spectroscopy application in environmental monitoring of water quality: a review.

Water quality monitoring is a critical part of environmental management and protection, and to be able to qualitatively and quantitatively determine contamination and impurity levels in water is especially important. Compared to the currently available water quality monitoring methods and techniques, laser-induced breakdown spectroscopy (LIBS) has several advantages, including no need for sample pre-preparation, fast and easy operation, and chemical free during the process. Therefore, it is of great importance to understand the fundamentals of aqueous LIBS analysis and effectively apply this technique to environmental monitoring. This article reviews the research conducted on LIBS analysis for liquid samples, and the article content includes LIBS theory, history and applications, quantitative analysis of metallic species in liquids, LIBS signal enhancement methods and data processing, characteristics of plasma generated by laser in water, and the factors affecting accuracy of analysis results. Although there have been many research works focusing on aqueous LIBS analysis, detection limit and stability of this technique still need to be improved to satisfy the requirements of environmental monitoring standard. In addition, determination of nonmetallic species in liquid by LIBS is equally important and needs immediate attention from the community. This comprehensive review will assist the readers to better understand the aqueous LIBS technique and help to identify current research needs for environmental monitoring of water quality.

Effect of laser pulse energy on orthogonal double femtosecond pulse laser-induced breakdown spectroscopy

In this paper, the effect of laser pulse energy on orthogonal double femtosecond pulse laser induced breakdown spectroscopy (LIBS) in air is studied. In the experiment, the energy of the probe pulse is changeable, while the pump pulse energy is held constant. At the same time, a systematic study of the laser induced breakdown spectroscopy signal dependence on the inter-pulse delay between the two pulses is performed. It is noted that the double pulse orthogonal configuration yields 2-32 times signal enhancement for the ionic and atomic lines as compared to the single pulse LIBS spectra when an optimum temporal separation between the two pulses is used, while there is no significant signal enhancement for the molecular lines in the studied range of the delay. It is also noted that the dependence of the enhancement factor for ionic and atomic lines on the inter-pulse delay can be fitted by Gaussian function. Furthermore, the electron temperature obtained by the relative line-to-continuum intensity ratio method was used to explain the LIBS signal enhancement.

Efficient plasma and bubble generation underwater by an optimized laser excitation and its application for liquid analyses by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) measurements were performed on bulk water solutions by applying a double-pulse excitation from a Q-Switched (QS) Nd:YAG laser emitting at 1064 nm. In order to optimize the LIBS signal, laser pulse energies were varied through changing of the QS trigger delays with respect to the flash-lamp trigger. We had noted that reduction of the first pulse energy from 92 mJ to 72 mJ drastically improves the signal, although the second pulse energy was also lowered from 214 mJ to 144 mJ. With lower pulse energies, limit of detection (LOD) for Mg in pure water was reduced for one order of magnitude (34 ppb instead of 210 ppb). In order to explain such a phenomenon, we studied the dynamics of the gas bubble generated after the first laser pulse through measurements of the HeNe laser light scattered on the bubble. The influence of laser energy on underwater bubble and plasma formation and corresponding plasma emission intensity were also studied by photographic technique. From the results obtained, we conclude that the optimal first pulse energy should be kept close to the plasma elongation threshold, in our case about 65 mJ, where the gas bubble has its maximum lateral expansion and the secondary plasma is still well-localized. The importance of a multi-pulse sequence on the LIBS signal was also analyzed, where the pulse sequence after the first QS aperture was produced by operating the laser close to the lasing threshold, with the consequent generation of relaxation oscillations. Low-energy multi-pulses might keep the bubble expansion large prior to the probing pulse, but preventing the formation of secondary weak plasmas in multiple sites, which reduces the LIBS signal. The short interval between the pre-pulses and the probing pulse is another reason for the observed LIBS signal enhancement.