New tracers identify hydraulic fracturing fluids and accidental releases from oil and gas operations.

Identifying the geochemical fingerprints of fluids that return to the surface after high volume hydraulic fracturing of unconventional oil and gas reservoirs has important applications for assessing hydrocarbon resource recovery, environmental impacts, and wastewater treatment and disposal. Here, we report for the first time, novel diagnostic elemental and isotopic signatures (B/Cl, Li/Cl, δ11B, and δ7Li) useful for characterizing hydraulic fracturing flowback fluids (HFFF) and distinguishing sources of HFFF in the environment. Data from 39 HFFFs and produced water samples show that B/Cl (>0.001), Li/Cl (>0.002), δ11B (25-31‰) and δ7Li (6-10‰) compositions of HFFF from the Marcellus and Fayetteville black shale formations were distinct in most cases from produced waters sampled from conventional oil and gas wells. We posit that boron isotope geochemistry can be used to quantify small fractions (∼0.1%) of HFFF in contaminated fresh water and likely be applied universally to trace HFFF in other basins. The novel environmental application of this diagnostic isotopic tool is validated by examining the composition of effluent discharge from an oil and gas brine treatment facility in Pennsylvania and an accidental spill site in West Virginia. We hypothesize that the boron and lithium are mobilized from exchangeable sites on clay minerals in the shale formations during the hydraulic fracturing process, resulting in the relative enrichment of boron and lithium in HFFF.

Monitoring reverse osmosis treated wastewater recharge into a coastal aquifer by environmental isotopes (B, Li, O, H).

Artificial recharge (AR) is gaining importance as a management tool in water stressed regions. The need to prove recovery performance requires new monitoring tools for AR systems. A novel combination of environmental isotope tracers (B, Li, O, H stable isotopes) was tested for the monitoring of AR of tertiary treated, desalinated domestic wastewater into a coastal dune aquifer in Flanders, Belgium. No significant isotope fractionation was observed for the treatment process, which includes low pH RO desalination. The wastewater, after infiltration through ponds and before recovery through pumping wells is characterized by low molar Cl/B ratios (3.3 to 5.2), compared to 130 to 1020 in the wider study area, delta(11)B values close to 0% per hundred, rather homogeneous delta(7)Li values (10.3 +/- 1.7% per hundred), and a 18O and 2H enrichment with respect to ambient groundwater due to evaporation in the infiltration ponds. This confers to the AR component a unique isotopic and geochemical fingerprint. Immediately downstream of the pumping wells and in the deeper part of the aquifer no evidence of AR wastewater could be found, indicating a high recovery efficiency. In the wider area and in the deeper part of the aquifer, isotopes evidence mixing of coastal rain and a fresh paleo-groundwater component with residual seawater as well as interaction with the aquifer material. Combining several isotope tracers provides independent constraints on groundwater flow and mixing proportions as a complement to hydrodynamic modeling and geochemical studies.