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Fluids associated with the San Andreas and companion faults in central and south-central California have high 3 He/ 4 He ratios. The lack of correlation between helium isotopes and fluid chemistry or local geology requires that fluids enter the fault system from the mantle. Mantle fluids passing through the ductile lower crust must enter the brittle fault zone at or near lithostatic pressures; estimates of fluid flux based on helium isotopes suggest that they may thus contribute directly to fault-weakening high-fluid pressures at seismogenic depths.

Approximately 300 kg/day of food-grade CO 2 was injected through a perforated pipe placed horizontally 2-2.3 m deep during July 9-August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO 2 . As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1-6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO 2 injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO 2 injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO 2 leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO 2 intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0-5.6), alkalinity (400-1,330 mg/l as HCO 3 ), and electrical conductance (600-1,800 lS/cm) following CO 2 injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90-240 mg/l), Mg (25-70 mg/l), Fe (5-1,200 ppb), and Mn (5-1,400 ppb) following CO 2 injection. These chemical changes could provide early detection of CO 2 leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorptionion exchange resulting from lowered pH values following CO 2 injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO 2 injection. CO 2 injection, however, is responsible for detection of BTEX (e.g. benzene, 0-0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.