Splashing is the main problem for the direct analysis of aqueous samples using LIBS since it generates serious precision and accuracy issues. This study demonstrates the direct determination of Li content in brines for the control of industrial mining processes using a portable LIBS device based on the direct laser impact on the sample, without any sample treatment, through the design of a sample injection system based on the Venturi effect. Our results demonstrated that the utilization of the 653.3 nm hydrogen line as an internal standard reduces the model calibration fitting error from 0.440 root mean square error in a standard calibration curve to 0.123 on the internal standard curve. Conversely, the development of a Venturi effect-based injection device using compressed air converts the brine into a fine mist which decrease splashing, resulting in an up to 10-fold error reduction, all without the necessity of employing an internal standard. Our results, evaluated by comparing them to the ASTM D3561-11 standard method using flame atomic absorption spectrometry, indicate that it is feasible to determine the lithium content in brine samples with an error of under 20% and a detection limit of 13 mg kg-1.