Applications of laser-induced breakdown spectroscopy for geochemical and environmental analysis: A comprehensive review

This chapter reviews proximal soil sensing (PSS). Our intent is for it to be a source of up-to-date information on PSS, the technologies that are currently available and their use for measuring soil properties. We first define PSS and discuss the sampling dilemma. Using the range of frequencies in the electromagnetic spectrum as a framework, we describe a large range of technologies that can be used for PSS, including electrochemical and mechanical sensors, telemetry, geographic positioning and elevation, multisensor platforms, and core measuring and down-borehole sensors. Because soil properties can be measured with different proximal soil sensors, we provide examples of the alternative techniques that are available for measuring soil properties. We also indicate the developmental stage of technologies for PSS and the current approximate cost of commercial sensors. Our discussion focuses on the development of PSS over the past 30 years and on its current state. Finally, we provide a short list of general considerations for future work and suggest that we need research and development to: (i) improve soil sampling designs for PSS, (ii) define the most suitable technique or combination of techniques for measuring key soil properties, (iii) better understand the interactions between soil and sensor signals, (iv) derive theoretical sensor calibrations, (v) understand the basis for local versus global sensor calibrations, (vi) improve signal processing, analysis, and reconstruction techniques, (vii) derive and improve methods for sensor data fusion, and (viii) explore the many and varied soil, agricultural, and environmental applications where proximal soil sensors could be used. PSS provides soil scientists with an effective approach to learn more about soils. Proximal soil sensors allow rapid and inexpensive collection of precise, quantitative, high-resolution data, which can be used to better understand soil spatial and temporal variability. We hope that this review raises awareness about PSS to further its research and development and to encourage the use of proximal soil sensors in different applications. PSS can help provide sustainable solutions to the global issues that we face: food, water, and energy security and climate change.

Proximal Soil Sensing: An Effective Approach for Soil Measurements in Space and Time

Laser-induced breakdown spectroscopy (LIBS) has been applied to the analysis of three chromium-doped soils. Two chemometric techniques, principal components analysis (PCA) and neural networks analysis (NNA), were used to discriminate the soils on the basis of their LIBS spectra. An excellent rate of correct classification was achieved and a better ability of neural networks to cope with real-world, noisy spectra was demonstrated. Neural networks were then used for measuring chromium concentration in one of the soils. We performed a detailed optimization of the inputs of the network so as to improve its predictive performances and we studied the effect of the presence of matrix-specific information in the inputs examined. Finally the inputs of the network—the spectral intensities—were replaced by the line areas. This provided the best results with a prediction accuracy and precision of about 5% in the determination of chromium concentration and a significant reduction of the data, too.

Qualitative and quantitative investigation of chromium-polluted soils by laser-induced breakdown spectroscopy combined with neural networks analysis.

Spectroscopy is emerging as a technique that can expand the envelope of modern oceanographic sensors. The selectivity of spectroscopic techniques enables a single instrument to measure multiple components of the marine environment and can form the basis for versatile tools to perform in situ geochemical analysis. We have developed a deep-sea laser-induced breakdown spectrometer (ChemiCam) and successfully deployed the instrument from a remotely operated vehicle (ROV) to perform in situ multi-element analysis of both seawater and mineral deposits at depths of over 1000 m. The instrument consists of a long-nanosecond duration pulse-laser, a spectrometer and a high-speed camera. Power supply, instrument control and signal telemetry are provided through a ROV tether. The instrument has two modes of operation. In the first mode, the laser is focused directly into seawater and spectroscopic measurements of seawater composition are performed. In the second mode, a fiber-optic cable assembly is used to make spectroscopic measurements of mineral deposits. In this mode the laser is fired through a 4 m long fiber-optic cable and is focused onto the target’s surface using an optical head and a linear stage that can be held by a ROV manipulator. In this paper, we describe the instrument and the methods developed to process its measurements. Exemplary measurements of both seawater and mineral deposits made during deployments of the device at an active hydrothermal vent field in the Okinawa trough are presented. Through integration with platforms such as underwater vehicles, drilling systems and subsea observatories, it is hoped that this technology can contribute to more efficient scientific surveys of the deep-sea environment.

Development of a deep-sea laser-induced breakdown spectrometer for in situ multi-element chemical analysis

Proximal soil sensing

A direct push, FO-LIBS sensor probe for real-time, in-situ measurement of metals in soils has been built and its capabilities demonstrated at three sites. The response of the FO-LIBS sensor is affected by the soil matrix conditions of grain size, composition, and water content. For each site, uncontaminated soil was collected and spiked with known quantities of the metal under investigation. These calibration standards were used to generate a site-specific calibration curve, which compensates for variations in soil matrix conditions of grain size, composition, porosity, etc. To compensate for moisture content, extra laser pulses are used to volatilize the water, higher power densities and/or shortened acquisition delay times are used. The LIBS experiment inherently exhibits poor precision since it is a point measurement. When multiple spectra are taken of a single, homogenized soil sample, there is a significant amount of variability in the peak intensities. There is no internal standard available to corr...

Theriault Ga

Papers

Field demonstrations of a direct push FO-LIBS metal sensor.