Age-dating and assumptions testing of 226Ra and 228Ra decay series applied to barite chimneys and mud volcanoes in deepwater Gulf of Mexico

Abstract

A chronological framework of ocean-based methane emissions is a prerequisite to identify the factors controlling the flux and duration of gas venting into the atmosphere.Here we report the results of a study of ubiquitous barite chimneys and barite-bearing mud volcanoes documented in association with methane seeps and gas hydrates at mid-bathyal depths in the Gulf of Mexico.The barites exhibit anomalously high 226Ra and 228Ra activities, orphans in the 238U/232Th decay chains, and are well suited for the application of 210Pb/226Ra and 228Th/228Ra dating methods. In order to account for the interference of impurities with the accuracy of the dates, gamma counts from paired raw and purified aliquots were evaluated. Chimneys yield a mean 228Th/228Ra age of 1.60 ± 0.25 yr (n = 16) and consistently younger 210Pb/226Ra ages. The biased 210Pb/226Ra ages are attributed to poor 210Pb counting efficiency, young chimneys with little 210Pb ingrowth and possibly an open system. Rapid vertical growth rates of 11.4 and 12.8 cm/yr established from 228Th/228Ra ages are comparable to barite chimney estimates from hydrothermal settings.In general mud volcanoes are distinguished from the chimneys by absence of 228Ra and 228Th and high 210Pb/226Ra ratios, occasionally >1 in the raw subsamples. A positive relation between 210Pb/226Ra and the amount of pyrite in the samples supports the contention that PbS, co-precipitated with pyrite in H2S-rich pore fluids, acts as the principal scavenger of external 210Pb resulting from decay of 222Rn in the pore fluids. The mud volcanoes 210Pb/226Ra assays yield consistent ages with a mean of 17.4 ± 1.8 yr (n = 9) after removal of the pyrite. The general absence of 228Ra and 228Th in the mud volcanoes, contrasting to their abundance in the chimneys, is attributed to the age difference between the barite geomorphic forms.The (228Ra/226Ra)o initial activities in the chimneys, representing the ratios in the fluids at the time of barite deposition, exhibit statistically distinct values of 1.084 ± 0.015 (n = 28) and 0.752 ± 0.023 (n = 4) at the two sampling sites separated by a 265 km stretch. These (228Ra/226Ra)o values match the range of oil-field brine values from deep siliciclastic reservoirs in the US Gulf Coast. The fluids maximum migration time from the source to the seafloor is estimated to be <20 yr on the basis of 228Ra presence in the chimneys. The assessment based on the radiometric ages supports the notion that barite deposition in the Gulf of Mexico is a relatively recent event.