Hydrogen and Carbon Stable Isotopic Compositions and Concentrations of Methane in Cave Air of Cueva de Villa Luz, Tabasco, Mexico

Wednesday, 17 December 2014
Kevin Webster1, Laura Rosales Lagarde2, Peter E Sauer1, Arndt Schimmelmann1, Jay T Lennon1 and Penelope Jane Boston3, (1)Indiana University, Bloomington, IN, United States, (2)UNLV, Las Vegas, NV, United States, (3)New Mexico Tech, Socorro, NM, United States
Cueva de Villa Luz (CVL) is a unique biogeochemical environment where microbial consortia are supported by hydrogen sulfide (H2S) leading to sulfuric acid speleogenesis (SAS) which is thought to have generated the porosity and permeability of several petroleum reservoirs. Possible sources of the sulfur (S) include the Chichón Volcano and petroleum basins in the area. A better understanding of the source of the H2S in CVL may help predict where else SAS may have occurred. Analysis of methane (CH4) in CVL may provide a proxy to assess the source of S entering CVL.

We obtained 13 air samples in 1-L Tedlar® bags from varying locations in CVL to assess the role of CH4 in sulfide-rich karst systems. CH4 and carbon dioxide (CO2) concentrations were measured by gas-chromatography. The stable isotopic ratios of carbon and hydrogen were measured on a stable isotope-ratio mass-spectrometer.

CH4 in the air of CVL ranged from 1.88 ± 0.10 ppmv to 3.7 ± 0.2 ppmv. CO2 concentrations ranged from 400 ± 20 ppmv to 920 ± 50 ppmv. For comparison, the CH4 and CO2 concentrations in the outside atmosphere were 1.96 ± 0.10 ppmv and 430 ± 20 ppmv respectively. CH4 and CO2 were positively correlated in CVL (R2 = 0.91, CH4 = [0.0035 ± 0.0007] CO2 + [0.4 ± 0.4], p >0.01). The highest concentrations were near springs. Keeling-style analysis showed that the CH4 samples from CVL plot along a two-end member mixing model and suggest that CH4 is outgassing from spring water with isotopic compositions δ13CCH4 = -24 ± 3 ‰ and δ2HCH4 = -40 ± 40 ‰. CO2 did not plot along a two end member mixing model.

The proposed δ13C of CH4 entering from springs does not closely match the δ13CCH4 values from hydrocarbon basins in the area. This is likely due to oxidative loss of CH4 as it ascends to CVL which may be partly driven by anaerobic methanotrophy coupled to sulfate reduction. Analysis of the spring water chemistry coupled to biogeochemical modeling may help quantify the amount of methanotrophy occurring in the subsurface.