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 CO2 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 (He-3, He-4) and carbon (C-12, C-13, C-14) in 37 groundwater samples, from 24 distinct wells, collected between 20 and 60 km from Lassen Peak. Measured groundwater samples have air-corrected He-3/He-4 values between 0.19 and 7.44 RA (where RA = air He-3/He-4 = 1.39 x 10(-6)), all in excess of the radiogenic production value (similar to 0.05 RA), indicating pervasive mantle-derived helium additions to the groundwater system in the Lassen Peak region. Stable carbon isotope ratios of DIC (delta C-13) vary between 12.6 and 27.7% (vs. VPDB). Measured groundwater DIC/He-3 values fall in the range of 2.2 x 10(10) to 1.1 x 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 CO2 versus DIC derived from external (slab and mantle) carbon sources. Specifically, if we use C-14 to identify soil-derived DIC (assuming decadal-tocentennial groundwater ages and a soil CO2 C-14 activity equal to that of the atmosphere), we calculate that a hypothetical external carbon source would have an apparent delta C-13 signature between 10.3 and 59.3% (vs. Vienna Pee Dee Belemnite (VPDB)) and an apparent C/He-3 between 7.0 x 10(9) and 1.0 x 10(12). These apparent delta C-13 and C/He-3 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 nonmantle 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 delta C-13 (similar to 60%), we suggest that the second scenario is more plausible. Importantly, however, we caution that all conceptual models are dependent on assumptions about initial C-14 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 C-14 approach to deconvolving sources of DIC, we determine that the maximum passive carbon flux could be up to similar to 2.2 x 106 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 similar to 4-18% of the total Lassen geothermal CO2 degassing flux (estimated to be similar to 3.5 x 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 CO2 flux estimates (7.3-11 x 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, delta C-13 and C-14, which when interpreted together can be used to better elucidate the various sources of DIC in groundwater.