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Portable LIBS instrumentation can identify trace levels of environmental pollutants
Abstract
The integration of miniature fi ber optic spectrometers with small high peak power laser trans-mitters has lead to the development of a low-cost portable analytical instrument capable of real-time qualitative analysis. LIBS (Laser Induced Breakdown Spectroscopy) systems are now assembled with commercial off the shelf components to produce portable briefcase size elemen-tal analyzers that are capable of sustained battery operation in remote fi eld environments. In a typical LIBS system, a high peak power pulsed 1064 nm Nd:YAG laser is focused on a target material with virtually no sam-ple preparation. The pulse power, which is several MegaWatts, generates a plasma with an elemental line spectrum character-istic for the sample. This spectrum is then collected and analyzed for the elements present. The LIBS measurement and data analysis occurs within less than a second using any notebook computer.
... The Porta-LIBS-2000 from StellarNet, Inc. [49], which was an upgrade of a previous prototype [27], was one of the first fpLIBS instruments to appear on the market. The system included a Nd:YAG laser at 1064 nm operating with a laser energy of 30 mJ and with a 6-ns pulse width, and a high-resolution EPP2000 spectrometer covering the range of 200-1100 nm, with a resolution of 0.2 nm. ...
... An experiment was conducted in which 200 laser shots were accumulated on metallic Pb plus dry and moist soils that showed plasma temperatures, and consequent intensities of the Pb lines at 357, 364, 368 and 374 nm, which exhibited progressively more variations from homogeneous metallic Pb to inhomogeneous soil and from dry to moist soil, thus indicating that the physical nature of the sample has a strong influence on plasma parameters [26]. A calibration curve for Pb using the 405.8-nm line was developed on six laboratoryprepared soils containing between 0 and 3. Pierce et al. [49] used a low-cost bespoke fpLIBS system to determine the presence of hazardous and non-hazardous elements in various mud samples collected in a metal-contaminated watershed site located near a wood treatment facility in the Pacific Northwest (USA). A detailed study of the spectral features observed differences between the contaminated and non-contaminated samples. ...
The first part of this review describes laser-induced breakdown spectroscopy (LIBS) instrumentation for in situ measurement outside the laboratory, both prototype instruments and commercially available analyzers that can be operated by a single individual. Two types of devices are described – (i) field-portable type systems consisting of multiple units connected by an umbilical (fpLIBS) and (ii) handheld analyzers (hLIBS). The performance of
these two types of LIBS systems is compared with that of its primary competitor technology portable X-ray fluorescence spectroscopy (pXRF). The second part of the article reviews the results of both fpLIBS and hLIBS obtained in both research settings and for practical applications in various sectors where speed of analysis is often crucial. These include compositional screening of natural and manufactured materials, quality control of
manufacturing processes, identification of environmental contaminants, biomedical diagnostics, forensic analysis, and hazardous material identification in the industrial, environmental, geological, cultural heritage, agricultural, biological, nuclear and security sectors. The review concludes by highlighting the key trends and challenging future directions in making LIBS technology readily accessible for applications that demand easy
portability and fast analysis outside of the laboratory with instruments of compact dimensions and low weight but high performance, crucial features required for any portable device.
... The Porta-LIBS-2000 from StellarNet, Inc. [49], which was an upgrade of a previous prototype [27], was one of the first fpLIBS instruments to appear on the market. The system included a Nd:YAG laser at 1064 nm operating with a laser energy of 30 mJ and with a 6-ns pulse width, and a high-resolution EPP2000 spectrometer covering the range of 200-1100 nm, with a resolution of 0.2 nm. ...
... An experiment was conducted in which 200 laser shots were accumulated on metallic Pb plus dry and moist soils that showed plasma temperatures, and consequent intensities of the Pb lines at 357, 364, 368 and 374 nm, which exhibited progressively more variations from homogeneous metallic Pb to inhomogeneous soil and from dry to moist soil, thus indicating that the physical nature of the sample has a strong influence on plasma parameters [26]. A calibration curve for Pb using the 405.8-nm line was developed on six laboratoryprepared soils containing between 0 and 3. Pierce et al. [49] used a low-cost bespoke fpLIBS system to determine the presence of hazardous and non-hazardous elements in various mud samples collected in a metal-contaminated watershed site located near a wood treatment facility in the Pacific Northwest (USA). A detailed study of the spectral features observed differences between the contaminated and non-contaminated samples. ...
Laser-induced breakdown spectroscopy (LIBS) has followed a typical arc of technology development. Beginning in the laboratory setting, curiosity-driven researchers first pursued answers to questions about the fundamental physics of the methodology and then developed ever-better laboratory analytical systems. This, in turn, opened the door for investigations of practical applications in the laboratory that, when demonstrated, subsequently resulted in the development of portable and mobile LIBS systems for in-field LIBS analysis. Concurrently, LIBS technology moved from the research laboratory into the marketplace, first with the commercialization of the technology based on laboratory LIBS systems and, more recently, to the development of handheld LIBS analyzers. This chapter reviews this technology development and discusses different applications of handheld LIBS during the early years after its development.
... One of the first commercially available portable LIBS instruments was the Porta-LIBS-2000 from the StellarNet Inc. Company [80,81]. The device was housed in a suitcase containing a small chamber in which the analyzed samples could be placed. ...
... As can be seen from Table 2 the Kigre MK-367 laser is very popular in the LIBS community and has been implemented in many devices [31,63,64,73,74,80,81,83,84,87,88]. It is an Nd:YAG FLPSS laser, lasing on 1064 nm. ...
... This unit contained a Nd:YAG laser that emitted laser pulses with a wavelength of 1,064 nm and could detect electromagnetic radiation in the wavelength range from 200 to 1,100 nm on a CCD sensor (charge-coupled device). The 14.6-kg pLIBS system measured 18 x 33 x 46 cm and was no bigger than a briefcase [6]. Progressive technical advances and component miniaturisation of components led to the development of today's pLIBS analysers. ...
Portable laser induced breakdown spectroscopy (pLIBS) is an analytical method for determining the elemental composition of solid material surfaces. Field-portable devices are gaining increasing acceptance in the mineral resources sector, offering rapid, on-site chemical analysis.
... The MK-367 laser produced by Kigre Inc. is widely used in many portable LIBS instruments. [9,[25][26][27][28][29][30][31][32] It is a passively Q-switched Nd:YAG FLPSS laser that produces pulses at 1064 nm and can works at a repetition rate of 1/3 Hz, which can be up to 1 Hz with an actively cooled heat sink. The single pulse energy of this laser is 25 mJ with a pulse width of 4 ns and a raw beam diameter of 3 mm. ...
In this work, a compact laser induced breakdown spectroscopy (LIBS) instrument was developed based on a high energy lightweight laser source and an integrated control system, making the instrument well integrated and convenient to use. The instrument has a compact size of 45 cm ×36 cm ×45 cm and weights only 21 kg. The spectrometer operated in the range from 180 to 850 nm with a resolution of 0.15 nm, which was customizable. The client software was customized as the interface for process control and data acquisition. Some procedures were carried out to evaluate the performance of this instrument. First, the laser source worked at an average energy value of 116 mJ, with a relative standard deviation of 2.58% for 9999 laser pulses after continuously running for 3 hr. Second, qualitative analysis was performed to show the classification ability for copper mineral samples. Besides, the calibration curves were achieved by using the emission lines of Cu (I) 510.55 nm, Cu (I) 521.82 nm, Zn (I) 307.58 nm, and Zn (I) 328.23 nm, with the correlation coefficient R² of 0.97432, 0.9826, 0.97286, and 0.98176, and the limit of detection was shown to be 0.0365%, 0.0399%, 39.581 µg·g⁻¹, and 47.081 µg·g⁻¹, respectively. According to the evaluation results, the compact laser source was excellent for stable measurement and the proposed compact instrument performed well for the qualitative and quantitative elemental analysis with satisfied results. Therefore, the proposed LIBS instrument has potential to find applications in a variety of circumstances.
... Mobile, field-deployable, and stand-off LIBS systems have been developed for real-time chemical analysis outside the laboratory as a consequence of laser and spectrometer miniaturization, together with the use of optical fiber light delivery and collection and compact beam optics designs [61][62][63][64][65][66][67][68][69][70][71][72][73][74]. These include mobile instruments that can be readily transported to sites like museums and factories, suitcase-and backpack-type man-portable LIBS designs for use in the field, and telescopic stand-off LIBS systems that have been utilized for geological, environmental, industrial, and cultural heritage applications. ...
Laser-induced breakdown spectroscopy (LIBS) is a straightforward and versatile spectroscopic technique based upon the analysis of the spectral emission from laser-induced plasmas. LIBS has the far-reaching capability to provide rapid, in situ multielement detection of any material - solid, liquid, or gas. The field of LIBS has been rapidly maturing as a consequence of interest in LIBS for a broad spectrum of applications and the recent development of LIBS analytical systems by the commercial sector.
... Mobile, field-deployable, and stand-off LIBS systems have been developed for real-time chemical analysis outside the laboratory as a consequence of laser and spectrometer miniaturization, together with the use of optical fiber light delivery and collection and compact beam optics designs [61][62][63][64][65][66][67][68][69][70][71][72][73][74]. These include mobile instruments that can be readily transported to sites like museums and factories, suitcase-and backpack-type man-portable LIBS designs for use in the field, and telescopic stand-off LIBS systems that have been utilized for geological, environmental, industrial, and cultural heritage applications. ...
... The system was later used as a base for next one [105], which was used for geochemical analysis in [48,47] and for hazardous material detection [33]. Few commercial portable LIBS systems are nowadays available on the market: Easy LIBS from IVEA c ⃝(which integrates the compact laser developed in our lab) [51], PL100-GEO from Applied Spectra c ⃝ [82], LIBSCAN 25 from Applied Photonics c ⃝ [2], Porta-LIBS-2000 from StellarNet Inc. c ⃝ [110], and IDEALIBS from Bertin Technologies c ⃝. Most of them are heavy (up to 25 kg) and transportable rather than portable. ...
Laser Induced Breakdown Spectroscopy (LIBS) offers possibility for fast de- tection of sample composition without its preparation. For this reason it is attractive anywhere where the fast detection and no sample preparation are needed. As in many other branches the technical and scientific progress im- proves and spreads the possibilities of LIBS based devices and laboratory appa- ratuses. The time-resolved spectroscopy is allowed by spectrograph equipped with fast camera, broadband spectra can be acquired in single exposition by broadband spectrometers. Smaller and lighter laser sources together with com- pact spectrometers can be implemented to portable device and can be used out of laboratory. Computers offer quick data processing. The device named ChemCam installed on the NASA's next Mars rover, curiosity, is good exam- ple of high technology application in LIBS. However, there are still challenges and we hope that this work will be fruitful for anyone who is interested in the LIBS. The project of presented thesis was performed as a joint supervision project between the Department of Experimental Physics at Comenius University in Bratislava and Laboratiore Interdisciplinaire Carnot de Bourgogne at Univer- sit ́e de Bourgogne in Dijon. The aim of the project was to join experience from both laboratories, experience in laser constructions from Dijon and experience with spectroscopy from Bratislava. The both are essential for LIBS. In Bratislava the work was coordinated by prof.Pavel Veis and it was fo- cused on LIBS under the laboratory conditions. The time-resolved broadband spectrometry was used in the research. In order to achieve required spectra, the spectral response of the optical system was determined which was later used for the corrections. The research of self-absorption phenomena started in the last period with aim to use this effect, usually considered as negative, for the composition determination. In Dijon the work was supervised by Dr. Olivier Musset and directed toward development of LIBS device which could be used out of laboratory. The small 6 7 laser which was previously developed in the laboratory was implemented in the device. The development was successfully finished and testing process began in the last period of the thesis. The geological samples have been used for the testing process which was performed in deep cooperation with geologists. The first chapter comprises a brief introduction to LIBS. It is divided into some parts about laser induced plasma, laser induced breakdown and evolution of the plasma after breakdown. The section dealing with local thermodynamic equilibrium is also included. The section describes importance of LTE and the possibilities to determine this state. The second chapter is dedicated to the developed portable LIBS device. In the introduction, different type of LIBS devices are presented with their possibilities. Then the portable device developed in Dijon is described part by part with brief characteristic of developed software. The device possibilities and limits are sketched in the last section of the chapter with respect to results obtained in the testing process. The third chapter deals with capabilities of LIBS apparatus which was set up in the laboratory. The process of spectral response measurement and its results are presented and consequently used in next sections in process of plasma parameters determination. The composition of used samples are determined by using of calibration free method with aim to choose proper location in the plasma for which results are the most representative. The last chapter includes introduction to the subject of self-absorption phenomena. The simple model and basic theory are presented with suggestion how to use the phenomena in positive way. The simple experiment and its results are presented at the end of the chapter together with discussion about the possibilities and perspectives of the suggested method.
... Mobile, field-deployable, and stand-off LIBS systems have been developed for real-time chemical analysis outside the laboratory as a consequence of laser and spectrometer miniaturization, together with the use of optical fiber light delivery and collection and compact beam optics designs [61][62][63][64][65][66][67][68][69][70][71][72][73][74]. These include mobile instruments that can be readily transported to sites like museums and factories, suitcase-and backpack-type man-portable LIBS designs for use in the field, and telescopic stand-off LIBS systems that have been utilized for geological, environmental, industrial, and cultural heritage applications. ...
Applications of laser-induced breakdown spectroscopy (LIBS) have been growing rapidly and continue to be extended to a broad range of materials. This paper reviews recent application of LIBS for the analysis of geological and environmental materials, here termed "GEOLIBS". Following a summary of fundamentals of the LIBS analytical technique and its potential for chemical analysis in real time, the history of the application of LIBS to the analysis of natural fluids, minerals, rocks, soils, sediments, and other natural materials is described.
... Elemental detection and material identification can be readily achieved using chemometric analysis that compares acquired LIBS spectra against a pre-assembled spectral library. Mobile, field-deployable, and stand-off LIBS systems have been developed for real-time chemical analysis outside the laboratory as a consequence of laser and spectrometer miniaturization, together with the use of optical fiber light delivery and collection and compact beam optics designs6162636465666768697071727374. These include mobile instruments that can be readily transported to sites like museums and factories, suitcase-and backpack-type man-portable LIBS designs for use in the field, and telescopic stand-off LIBS systems that have been utilized for geological, environmental, industrial, and cultural heritage applications . ...
Laser-induced breakdown spectroscopy (LIBS) offers a means of rapidly distinguishing different geographic sources for a mineral because the LIBS plasma emission spectrum provides information on the chemical composition (i.e. geochemical fingerprint) of a geomaterial. An application of this approach with potentially significant commercial and political importance is the spectral fingerprinting of “conflict minerals” such as columbite–tantalite (“coltan”). Following a successful pilot study of a columbite–tantalite suite from North America, a more geographically diverse set of 57 samples from 37 locations around the world was analyzed using a commercially available LIBS system. The LIBS spectra were analyzed using advanced multivariate statistical signal processing techniques. Partial least squares discriminant analysis (PLSDA) resulted in a correct place-level geographic classification at success rates above 90%. The possible role of rare-earth elements (REEs) as a factor contributing to the high levels of sample discrimination was explored. These results provide additional evidence that LIBS has the potential to be utilized in the field as a real-time screening tool to discriminate between columbite–tantalite ores of different provenance.
Die tragbare laserinduzierte Plasmaspektroskopie (pLIBS) ist eine Analysemethoden zur Bestimmung der elementaren Zusammensetzung von Feststoffoberflächen. Tragbare Geräte setzen sich im Bereich der Rohstoffindustrie immer mehr durch und ermöglichen eine schnelle, chemische Vor-Ort-Analyse.
Laser-induced breakdown spectroscopy (LIBS) has been widely pursued for trace elemental determination in gases, solids, and liquids. Application to liquids has proved problematic due to high spatial confinement
of the LIBS plasma and rapid quenching of the excited-state emission. This work presents an alternative approach to trace metal determination in liquids in which 1.0 mL of liquid is deposited onto a carbon
planchet and then evaporated, thus transforming the liquid analysis to a solid surface analysis. Using optimized excitation and detection conditions, we have identified spectral regions for sensitive detection
of 15 metals (Mg, Al, Si, Ca, Ti, Cr, Fe, Co, Ni, Cu, Zn, As, Cd, Hg, Pb). The limit of detection (LOD) for the technique ranged from 10 ppb to 10 ppm for these elements. A 100 ppb LOD represents detection
of 130 picograms of metal (approximately 2 picomoles) in a single measurement calculated from the laser spot size on the sample. Scanning electron microscopy (SEM) images and energy-dispersive X-ray (EDX)
spectra of the samples provide insight into the observed reproducibility and linearity of the technique for several of the metals studied.