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USGS2021

The triple argon isotope composition of groundwater on ten-thousand-year timescales

Understanding the age and movement of groundwater is important for predicting the vulnerability of wells to contamination, constraining flow models that inform sustainable groundwater management, and interpreting geochemical signals that reflect past climate. Due to both the ubiquity of groundwater with order ten-thousand-year residence times and its importance for climate reconstruction of the last glacial period, there is a strong need for improving geochemical dating tools on this timescale. Whereas 14 C of dissolved inorganic carbon and dissolved 4 He are common age tracers for Late Pleistocene groundwater, each is limited by systematic uncertainties related to aquifer composition and lithology, and the extent of water-rock interaction. In principle, radiogenic 40 Ar in groundwater acquired from decay of 40 K in aquifer minerals should be insensitive to some processes that impact 14 C and 4 He and thus represent a useful, complementary age tracer. In practice, however, detection of significant radiogenic 40 Ar signals in groundwater has been limited to a small number of studies of extremely old groundwater (>100 ka). Here we present the first high-precision (<1‰) measurements of triple Ar isotopes ( 40 Ar, 38 Ar, 36 Ar) in groundwater. We introduce a model that distinguishes radiogenic 40 Ar from atmospheric 40 Ar by using the non-radiogenic Ar isotopes ( 36 Ar, 38 Ar) to correct for mass-dependent fractionation. Using this model, we investigate variability in radiogenic 40 Ar excess (Δ 40 Ar) across 58 groundwater samples collected from 36 wells throughout California (USA). We find that Δ 40 Ar ranges from ~0‰ (the expected minimum value) to +4.2‰ across three study areas near Fresno, San Diego, and the western Mojave Desert. Based on measurements from a network of 23 scientific monitoring wells in San Diego, we find evidence for a strong dependence of Δ 40 Ar on aquifer lithology. We suggest that Δ 40 Ar is fundamentally controlled by the weathering of old K-bearing minerals and thus reflects both the degree of groundwater-rock interaction, which is related to groundwater age, and the integrated flow through different geological formations. Future studies of Late Pleistocene groundwater may benefit from high-precision triple Ar isotope measurements as a new tool to better interpret 14 C- and 4 He-based constraints on groundwater age and flow.

Chemical Geology↗

USGS2021

Helium-carbon systematics of groundwaters in the Lassen Peak Region

Carbon dioxide emissions from active subaerial volcanoes represent 20–50% of the annual global volcanic CO 2 flux (Barry et al., 2014). Passive degassing of carbon from the flanks of volcanoes, and the associated accumulation of dissolved inorganic carbon (DIC) within nearby groundwater, also represents a potentially important, yet poorly constrained flux of carbon to the surface (Werner et al., 2019). Here we investigate sources and sinks of DIC in groundwaters in the Lassen Peak region of California. Specifically, we report and interpret the relative abundance and isotopic composition of helium ( 3 He, 4 He) and carbon ( 12 C, 13 C, 14 C) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected 3 He/ 4 He values between 0.19 and 7.44 R A (where R A = air 3 He/ 4 He = 1.39 × 10 −6 ), all in excess of the radiogenic production value (~0.05 R A ), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (δ 13 C) vary between −12.6 and − 27.7‰ (vs. VPDB). Measured groundwater DIC/ 3 He values fall in the range of 2.2 × 10 10 to 1.1 × 10 12 . Using helium and carbon isotope data, we explore several conceptual models to estimate surface carbon contributions and to differentiate between DIC derived from soil CO 2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use 14 C to identify soil-derived DIC (assuming decadal-to-centennial groundwater ages and a soil CO 2 14 C activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent δ 13 C signature between −10.3 and − 59.3‰ (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/ 3 He between 7.0 × 10 9 and 1.0 × 10 12 . These apparent δ 13 C and C/ 3 He values are substantially isotopically lighter than and greater than canonical MORB values, respectively. We suggest that >95% of any external (non-soil-derived) DIC in groundwater must thus be non-mantle in origin (i.e., slab derived or assimilated organic carbon). We further investigate possible sources of external DIC to groundwater using two idealized conceptual approaches: a pure (unfractionated) source mixing model (after Sano and Marty, 1995) and a scenario that invokes fractionation due to calcite precipitation. Because the former model requires carbon contributions from an organic source component with unrealistically low δ 13 C (~ − 60‰), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial 14 C activity. Thus, we cannot rule out the possibility that the true fraction of non-surface-derived DIC in these samples is lower or negligible, despite the pervasive mantle-derived He isotope signatures throughout the region. Following the 14 C approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to ~2.2 × 10 6 kg/yr, which is lower than previous magmatic carbon flux estimates from the Lassen region (Rose and Davisson, 1996). We find that the passive dissolved carbon flux could represent a maximum of ~4–18% of the total Lassen geothermal CO 2 degassing flux (estimated to be ~3.5 × 10 7 kg/yr Rose and Davisson, 1996; Gerlach et al., 2008), which is still more than an order of magnitude smaller than soil gas CO 2 flux estimates (7.3–11 × 10 7 kg/yr) for nearby volcanoes (Sorey et al., 1998; Gerlach et al., 1999; Evans et al., 2002; Werner et al., 2014 ). We conclude that passive dissolved carbon fluxes should be combined with geothermal fluxes and soil gas fluxes to obtain a complete picture of volcanic carbon emissions globally. Our approach highlights the utility of measuring helium isotopes in concert with the full suite of noble gas abundances, tritium, δ 13 C and 14 C, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.

California↗

USGS2021

Groundwater residence time estimates obscured by anthropogenic carbonate

Groundwater is an important source of drinking and irrigation water. Dating groundwater informs its vulnerability to contamination and aids in calibrating flow models. Here, we report measurements of multiple age tracers ( 14 C, 3 H, 39 Ar, and 85 Kr) and parameters relevant to dissolved inorganic carbon (DIC) from 17 wells in California’s San Joaquin Valley (SJV), an agricultural region that is heavily reliant on groundwater. We find evidence for a major mid-20th century shift in groundwater DIC input from mostly closed- to mostly open-system carbonate dissolution, which we suggest is driven by input of anthropogenic carbonate soil amendments. Crucially, enhanced open-system dissolution, in which DIC equilibrates with soil CO 2 , fundamentally affects the initial 14 C activity of recently recharged groundwater. Conventional 14 C dating of deeper SJV groundwater, assuming an open system, substantially overestimates residence time and thereby underestimates susceptibility to modern contamination. Because carbonate soil amendments are ubiquitous, other groundwater-reliant agricultural regions may be similarly affected.

California↗