Application of laser-induced breakdown spectroscopyfor detection of elements in flowback water samplesfrom shale gas wells

Laser-induced breakdown spectroscopy (LIBS) was applied to rapidly detect elements in flowback water samples from shale gas wells in Oklahoma. Two types of LIBS systems (aerosolization and collection on a substrate) were used. The LIBS with an aerosolization system provided rapid determination of elements in flowback water, but moisture present in the chamber and variation in the water droplet size could make quantification difficult. In the substrate collection system, a comparison among substrate types showed that a hydrophilic cellulose filter gave the most homogeneous sample distribution after drying and provided the best performance. The elements in flowback water samples were also determined by inductively coupled plasma–optical emission spectroscopy (ICP-OES). ICP-OES data showed spatial variations for the elements among the different wells. Among the elements, K showed the highest variation (relative standard ${\rm deviation} = {62.8}\% $deviation=62.8%) and Mg the lowest (relative standard ${\rm deviation} = {39.1}\% $deviation=39.1%). Good correlations (${ r} = {0.98 - 0.99}$r=0.98−0.99) were observed between Ca, K, Mg, and Na LIBS peak areas determined using the cellulose filter and their mass concentrations (ppm) measured by ICP-OES for aqueous solutions. The limits of detection for Ca, K, Mg, and Na by LIBS were 122 ppm, 68 ppm, 36 ppm, and 142 ppm, respectively. Both the LIBS and ICP-OES data showed that element concentrations in the flowback water samples were in the order of Na, Ca, Mg, and K from highest to lowest. Our data suggest that the LIBS technique could rapidly detect elements in flowback water samples on site. However, accurate quantification of elements present in low concentrations in water samples is limited.