Tectonic activity as a significant source of crustal tetrafluoromethane emissions to the atmosphere: Observations in groundwaters along the San Andreas Fault

- Groundwater CF4 concentrations are elevated from crustal emissions.
- Weathering of alluvium insufficient to account for groundwater CF4 concentrations.
- Additional deep crustal CF4 added by a high flux through San Andreas Fault System.
- Tectonic CF4 emissions are an important source of CF4 to the Earth's surface.
- Paleoatmospheric CF4 may record changes in crustal weathering and tectonic activity.

Tetrafluoromethane (CF4) concentrations were measured in 14 groundwater samples from the Cuyama Valley, Mil Potrero and Cuddy Valley aquifers along the Big Bend section of the San Andreas Fault System (SAFS) in California to assess whether tectonic activity in this region is a significant source of crustal CF4 to the atmosphere. Dissolved CF4 concentrations in all groundwater samples but one were elevated with respect to estimated recharge concentrations including entrainment of excess air during recharge (Cre; ∼30 fmol kg−1 H2O), indicating subsurface addition of CF4 to these groundwaters. Groundwaters in the Cuyama Valley contain small CF4 excesses (0.1-9 times Cre), which may be attributed to an in situ release from weathering and a minor addition of deep crustal CF4 introduced to the shallow groundwater through nearby faults. CF4 excesses in groundwaters within 200 m of the SAFS are larger (10-980 times Cre) and indicate the presence of a deep crustal flux of CF4 that is likely associated with the physical alteration of silicate minerals in the shear zone of the SAFS. Extrapolating CF4 flux rates observed in this study to the full extent of the SAFS (1300 km × 20-100 km) suggests that the SAFS potentially emits (0.3-1)×10−1 kg CF4 yr−1 to the Earth's surface. For comparison, the chemical weathering of ∼7.5×104 km2 of granitic rock in California is estimated to release (0.019-3.2)×10−1 kg CF4 yr−1. Tectonic activity is likely an important, and potentially the dominant, driver of natural emissions of CF4 to the atmosphere. Variations in preindustrial atmospheric CF4 as observed in paleo-archives such as ice cores may therefore represent changes in both continental weathering and tectonic activity, including changes driven by variations in continental ice cover during glacial-interglacial transitions.