Authigenic components in marine sediments are important archives for past environment reconstructions. However, defining reliable age constraints and assessing the effects of post-depositional overprints in Precambrian sequences are challenging. We demonstrate a new laser-based analytical approach that has the potential to rapidly and accurately evaluate the depositional and alteration histories of Proterozoic shales. Our study employs a novel application of in situ Rb-Sr dating coupled with simultaneous trace-element analysis using reaction-cell laser ablation–inductively coupled plasma–tandem mass spectrometry (LA-ICPMS/MS). We present results from shales sourced from two wells in the Proterozoic McArthur Basin, northern Australia. These rocks have been widely used by previous studies as a key section for ancient biogeochemical and paleo-redox reconstructions. Shales from well UR5 yielded initial 87Sr/86Sr ratios, Rb-Sr ages, and rare earth element plus yttrium (REEY) patterns similar to those of a dolerite sampled from the same core. We propose that the UR5 samples chronicle hydrothermal alteration instigated by the dolerite intrusion. In contrast, a correlative shale from well UR6 yielded an age consistent with the expected depositional age (1577 ± 56 Ma) with REEY and initial 87Sr/86Sr ratios similar to ca. 1.5 Ga seawater. We suggest that this sample records the minimum depositional age and early marine diagenetic history for this unit. This new technique can date Proterozoic shales quickly, cheaply, and with minimum sample preparation. Importantly, ages are triaged to differentiate between those recording primary marine versus secondary processes. This novel approach provides a potentially powerful tool for dating and fingerprinting the vast array of ancient marine shales for further studies of Earth systems through deep time.

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Abstract. Recent developments in tandem laser ablation mass spectrometer technology have demonstrated the capacity for separating parent and daughter isotopes of the same mass online. As a result, beta-decay chronometers can now be applied to the geological archive in situ as opposed to through traditional whole-rock digestions. One novel application of this technique is the in situ Rb–Sr dating of Proterozoic shales that are dominated by authigenic clays such as illite. This method can provide a depositional window for shales by differentiating signatures of early diagenetic processes versus late-stage secondary alteration. However, the hydrothermal sensitivity of the Rb–Sr isotopic system across geological timescales in shale-hosted clay minerals is not well understood. As such, we dated the Mesoproterozoic Velkerri Formation from the Altree 2 well in the Beetaloo Sub-basin (greater McArthur Basin), northern Australia, using this approach. We then constrained the thermal history of these units using common hydrocarbon maturity indicators and modelled effects of contact heating due to the intrusion of the Derim Derim Dolerite. In situ Rb–Sr dating of mature, oil-prone shales in the diagenetic zone from the Velkerri Formation yielded ages of 1448 ± 81, 1434 ± 19, and 1421 ± 139 Ma. These results agree with previous Re–Os dating of the unit and are interpreted as recording the timing of an early diagenetic event soon after deposition. Conversely, overmature, gas-prone shales in the anchizone sourced from deeper within the borehole were dated at 1322 ± 93 and 1336 ± 40 Ma. These ages are younger than the expected depositional window for the Velkerri Formation. Instead, they are consistent with the age of the Derim Derim Dolerite mafic intrusion intersected 800 m below the Velkerri Formation. Thermal modelling suggests that a single intrusion of 75 m thickness would have been capable of producing a significant hydrothermal perturbation radiating from the sill top. The intrusion width proposed by this model is consistent with similar Derim Derim Dolerite sill thicknesses found elsewhere in the McArthur Basin. The extent of the hydrothermal aureole induced by this intrusion coincides with the window in which kerogen from the Velkerri Formation becomes overmature. As a result, the mafic intrusion intersected here is interpreted to have caused kerogen in these shales to enter the gas window, induced fluids that mobilize trace elements, and reset the Rb–Sr chronometer. Consequently, we propose that the Rb–Sr chronometer in shales may be sensitive to temperatures of ca. 120 ∘C in hydrothermal reactions but can withstand temperatures of more than 190 ∘C in thermal systems not dominated by fluids. Importantly, this study demonstrates a framework for the combined use of in situ Rb–Sr dating and kerogen maturation indicators to help reveal the thermochronological history of Proterozoic sedimentary basins. As such, this approach can be a powerful tool for identifying the hydrocarbon potential of source rocks in similar geological settings.

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