Fully automated microfluidic mixing aided in-line detection of trace level oil field tracers

Abstract

Recent development in oil field tracer technologies has been focused on implementations that increase oil recovery through optimized algorithms for production, aided by the addition of high fidelity interwell tracer data that improve reservoir history match. Prerequisites for successful tracer campaigns in oil reservoirs at a large scale not only include low-cost tracer materials with a rich palette of uniquely identifiable tracers, but also high sensitivity, easy-to-use trace-level detection and analysis methodologies. A fully automated in-line separation and detection protocol can simultaneously address challenges in throughput (speed and efficiencies) and accuracy (minimization of error-prone steps) of multi-tracer detection. Our previously reported tracer materials consist of barcoded variants of the dipicolinic acid (DPA) molecules that sensitize the emission of lanthanide ions. We have capitalized on the time-gated optical luminescence detectability of this sensitizer-lanthanide ion complex to reject background oil fluorescence, achieving high detection sensitivity in particularly complex oil field produced brine matrix. However, automation of the detection and analysis process has been hindered by opposing requirements in the integration of chromatography instrumentation (separation resolution) with in-line mixing (dispersion due to increase in residence time), and high sensitivity spectrofluorimetry (long integration time). We overcome this major barrier to implementing an in-line detection design under flow conditions by utilizing a microfluidic mixing chip which offers a high degree of mixing in a very short fluidic path length for the in-flow chelation of lanthanide ion to the chromatographically resolved tracer variants, and a flow-cell fluorescence detector at the output of the high-performance liquid chromatography (HPLC). In this study, we demonstrated the rapid in-line detection of a mixture of three different DPA-based barcoded tracers at ultra-trace level. An automated solid phase extraction (SPE) pre-concentration stage is added to the input of the HPLC, further lowering the detection limit down to a level of 100 pM (pico molar) of tracer molecules. As developed, the complete automated system offers unprecedented sensitivity of detection and accelerated oil field tracer analysis that approaches “near real-time” speed.