The increasing significance of barium (Ba) in environmental and geologic research in recent years has led to interest in the application of the Ba isotopic composition as a tracer for natural materials with complex matrices. Most Ba isotope measurement techniques require separation of Ba from the rest of sample prior to analysis. This paper presents a method using readily available materials and disposable columns that effectively separates Ba from a range of geologic and hydrologic materials, including carbonate minerals, silicate rocks, barite, river water, and fluids with high total dissolved solids and organic content such as oil and gas brines, rapidly and without need for an additional cleanup column. The technique involves off-the-shelf columns and cation exchange resin and a two-reagent elution that uses 2.5 N HCl followed by addition of 2.0 N HNO3. We present data to show that major matrix elements from almost any natural material are separated from Ba in a single column pass, and that the method also effectively reduces or eliminates isobaric interferences from lanthanum and cerium.
Produced
waters from unconventional Marcellus Shale gas wells have
anomalously high barium (Ba) concentrations and yield some of the
isotopically heaviest Ba measured to date. Experiments were conducted
to constrain the source of Ba in these fluids and the controls on
barite (BaSO4) precipitation and dissolution in oil and
gas wells. Experiments simulating the acidizing stage evaluated the
solubility of pure barite and drilling mud in 2 M HCl at 80 °C
for periods of 2, 6, and 48 h and resulted in <0.01% barite dissolution
with no appreciable change in δ138Ba (138Ba/134Ba normalized to NIST standard 3104a). Static autoclave
experiments conducted at 66 °C and 20.7 MPa with combinations
of ground Marcellus Shale solids and/or barite-bearing drilling mud
with synthetic low-Ba fracturing fluid resulted in decreased Ba concentrations
in the fluid, with the largest decrease in the shale-only run. Fluid
δ138Ba values increased by about 0.5‰ as Ba
concentrations decreased, consistent with closed-system Rayleigh fractionation.
Flow-through experiments in Marcellus Shale core conducted for 28
days resulted in effluent Ba concentrations an order of magnitude
lower than the influent, while sulfate concentrations increased over
time. Effluent δ138Ba values increased over the first
12 days and plateaued at about 1‰ higher than the influent.
Modeling suggests a combination of the release of labile shale Ba
and barite precipitation. This work indicates that the processes of
Ba release from fluid–shale interactions and barite precipitation
in fractures and the well bore, while capable of producing high δ138Ba fluids, are unlikely to generate fluids with high-Ba
concentrations and δ138Ba values like those in Marcellus-produced
waters. We find that the release of sulfate from shale pyrite oxidation
rapidly catalyzes barite precipitation and that dissolution of drilling
mud barite or natural barite in the shale is unlikely to be the major
source of Ba in Marcellus-produced waters.
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