Changes in formation gas composition and isotope content as indicators of unsaturated-zone chemical reactions related to recharge events

The constituent composition and carbon and oxygen isotopes for CO2 in unsaturated-zone gases have been utilized to provide an independent means of determining what chemical reactions occurred during an extended artificial recharge experiment on the High Plains of Texas. Gas samples were collected from a sample point at a depth of 16 metres beneath a waterspreading basin to see what effect recharging water had on the unsaturated-zone atmosphere. Two different systems, one open and one closed, were sampled during this study. The 13C, 18O, Psub(CO2), and N/Ar data for gas collected during a 1975 experiment show the influence of unsaturated-zone gases being displaced by recharging waters, the trend towards equilibration with dissolved atmospheric gases as the sampling point is submerged by rising waters, the onset of a reducing environment and, following the termination of recharge, the slow recovery of the gas composition to pre-recharge conditions. The 13C content of the CO2 in the gases varied from -18.06% for the pre-recharge formation gas, to -10.01% for gases approaching equilibrium with dissolved atmospheric gases, to -38.01% for a CO2 produced from methane generated in a reducing evironment. The log Psub(CO2) for the above samples varied from -2.10 to -3.02 to -4.18 atmospheres, respectively. Recovery to pre-recharge unsaturated-zone atmospheric conditions took many months following the termination of recharge. (author)