We report a simple sub parts per million (sub-ppm) detection method for heavy metals in water by laser-induced breakdown spectroscopy (LIBS). Filter papers were used as the substrates for both transforming aqueous solutions to solid samples and for pre-concentrating dissolved heavy metal ions. The amount of sample uptake was 1.2 g by soaking a filter paper. This provides limit-of-detection (LOD) values of 2.7 and 0.36 ppm for Pb and Cr, respectively. The LODs could be improved remarkably by pre-concentrating the heavy metal ions. When a 40 g sample solution was evaporated on a filter paper, the LODs of 75 and 18 parts per billion (ppb) were obtained for Pb and Cr, respectively. Moreover, by either increasing the evaporated amount of sample solution or applying an argon gas flow, further improvement of the LODs was found to be very promising. The LIBS spectra of tap water were recorded using the pre-concentration method and are discussed in comparison with the results from inductively coupled plasma atomic emission spectroscopy (ICP-AES). We could observe strong emission lines of Ca, Mg, K, Cu, and Sr in the tap water, of which concentrations were determined to be 6.3, 1.3, 1.1, 0.64, and 0.046 ppm, respectively, by ICP-AES. Our method shows promise as a fast, reliable, water-quality monitoring tool for heavy-metal concentrations as well as for hardness.

We report an approach for selecting an internal standard to improve the precision of laser-induced breakdown spectroscopy (LIBS) analysis for determining calcium (Ca) concentration in water. The dissolved Ca²⁺ ions were pre-concentrated on filter paper by evaporating water. The filter paper was dried and analyzed using LIBS. By adding strontium chloride to sample solutions and using a Sr II line at 407.771 nm for the intensity normalization of Ca II lines at 393.366 or 396.847 nm, the analysis precision could be significantly improved. The Ca II and Sr II line intensities were mapped across the filter paper, and they showed a strong positive shot-to-shot correlation with the same spatial distribution on the filter paper surface. We applied this analysis approach for the measurement of Ca²⁺ in tap, bottled, and ground water samples. The Ca²⁺ concentrations determined using LIBS are in good agreement with those obtained from flame atomic absorption spectrometry. Finally, we suggest a homologous relation of the strongest emission lines of period 4 and 5 elements in groups IA and IIA based on their similar electronic structures. Our results indicate that the LIBS can be effectively applied for liquid analysis at the sub-parts per million level with high precision using a simple drying of liquid solutions on filter paper and the use of the correct internal standard elements with the similar valence electronic structure with respect to the analytes of interest.

Laser-induced breakdown spectroscopy (LIBS) was explored for the first time for discrimination of gallbladder (GB) polyp and GB cancer (GBC) by direct measurement of raw bile juice without pretreatment. Initially, for reproducible LIBS measurement, a laser-patterned silicon wafer (LPSW) incorporating 40 × 40 crossed trenches in an area of 1 × 1 cm² was used to spread bile juice as homogeneous as possible over the surface without substantial localization, and LiCl was employed as an internal standard. Mg, Ca, Na, and K peaks were dominant in the spectra of raw bile samples, with lower peak areas in cases of GBC. The lower elemental concentrations in GBC samples probably result from dilution of bile by a degraded water absorption ability of the thickened GB wall due to cancer and carcinogenesis. In particular, the Mg and K peak intensities were further lower and improved discrimination of GBC against normal/GB polyp. Moreover, discrimination was distinct when using the ratio of Na and K peak areas. Misbalancing of Na and K in cell metabolism induced by cancer progression was presumed to be the origin of enhanced discrimination. Overall, the LIBS-based direct bile analysis scheme is a simple and potential tool for screening of GBC.

We report a new simple method for the signal enhancement of laser-induced breakdown spectroscopy using a pulsed buffer gas jet. The signal is enhanced up to more than 10 fold by using argon gas jets, which are injected through a pulsed nozzle onto the sample area to be analyzed. By synchronizing the buffer gas pulse with the laser pulse and optimizing the spatial arrangements between the gas jet and the sample surface, we have successfully exploited the useful properties of the buffer gas in open atmosphere. The signal-enhancement mechanism in our buffer gas jet has been discussed. Also, applications to various samples (metal, glass, and paper) have been demonstrated.