The Paradox Basin in the Colorado Plateau (USA) has some of the most iconic records of paleofluid flow, including sandstone bleaching and ore mineralization, and hydrocarbon, CO2, and He reservoirs, yet the sources of fluids responsible for these extensive fluid-rock reactions are highly debated. This study, for the first time, characterizes fluids within the basin to constrain the sources and emergent behavior of paleofluid flow resulting in the iconic rock records. Major ion and isotopic (δ18Owater; δDwater; δ18OSO4; δ34SSO4; δ34SH2S; 87Sr/86Sr) signatures of formation waters were used to evaluate the distribution and sources of fluids and water-rock interactions by comparison with the rock record. There are two sources of salinity in basinal fluids: (1) diagenetically altered highly evaporated paleo-seawater-derived brines associated with the Pennsylvanian Paradox Formation evaporites; and (2) dissolution of evaporites by topographically driven meteoric circulation. Fresh to brackish groundwater in the shallow Cretaceous Burro Canyon Formation contains low Cu and high SO4 concentrations and shows oxidation of sulfides by meteoric water, while U concentrations are higher than within other formation waters. Deeper brines in the Pennsylvanian Honaker Trail Formation were derived from evaporated paleo-seawater mixed with meteoric water that oxidized sulfides and dissolved gypsum and have high 87Sr/86Sr indicating interaction with radiogenic siliciclastic minerals. Upward migration of reduced (hydrocarbon- and H2S-bearing) saline fluids from the Pennsylvanian Paradox Formation along faults likely bleached sandstones in shallower sediments and provided a reduced trap for later Cu and U deposition. The distribution of existing fluids in the Paradox Basin provides important constraints to understand the rock record over geological time.

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Rationale: Noble gases are widely used as physically based climate proxies, notably in dissolved water samples as tracers of past recharge temperature in groundwater and air-sea gas exchange processes in seawater. Recent advances in measuring largevolume samples of dissolved noble gas isotopic ratios at high precision have expanded the range of climate parameters that can be interpreted. Methods:We build on prior methods for measuring noble gas stable isotopes at high precision with a new large-volume equilibration (LVE) method wherein sample gases are equilibrated in the sample flask between the dissolved phase and the headspace.The original dissolved gas composition is determined by measuring the headspace gases and correcting for the equilibrium dissolved gas content of the discarded water using known solubilities and fractionation factors. We evaluate the accuracy and precision of this method with air-equilibrated water standards of known noble gas composition.Results: Replicate air-equilibrated water standards and field measurements demonstrate that the LVE method achieves comparable precision to prior methods, with major advantages of measuring the Ne content as a constraint on excess air and allowing for long-term sample storage. Isotope ratios measured with the LVE method in replicate samples were consistent between two laboratories, and LVE elemental noble gas abundances agreed closely with replicate samples measured using established copper-tube methods and static noble gas mass spectrometry. Conclusions:The new LVE method enables reconstruction of past water table depths at ±1 m precision along with excess air, recharge temperature, and age and hydrogeochemical indicators. It has wide application to investigating climate signals and physical gas exchange processes in groundwater and seawater. | INTRODUCTIONNoble gases are valuable physical tracers of past climate and gas exchange processes due to their chemical and biological inertness, and their presence in various terrestrial, marine, and polar climate archives. In groundwater and ice cores, noble gases are a wellestablished tool to reconstruct paleotemperatures at the time of recharge or air-bubble closure in ice based on their temperaturedependent solubilities. [1][2][3] In seawater, noble gas measurements help distinguish physical processes of air-sea gas exchange from biogeochemical ones. 4,5 Dissolved noble gases in groundwater or seawater are typically sampled in 10-50-ml copper tubes for measurement of elemental abundances via static mass spectrometry (herein, the CT method). 6 Recently, high-precision measurements of dissolved argon (Ar), krypton (Kr), and xenon (Xe) stable isotope ratios-alongside their elemental concentrations-have allowed for reconstructions of additional paleoclimatic parameters beyond traditional

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