Carbon isotopic composition of lipid biomarkers from an endoevaporitic gypsum crust microbial mat reveals cycling of mineralized organic carbon

Abstract

Microbial mats that inhabit gypsum deposits in ponds at Guerrero Negro, Baja California Sur, Mexico, developed distinct pigmented horizons that provided an opportunity to examine the fixation and flow of carbon through a trophic structure and, in conjunction with previous phylogenetic analyses, to assess the diagenetic fates of molecular δ¹³ C biosignatures. The δ¹³ C values of individual biomarker lipids, total carbon, and total organic carbon (TOC) were determined for each of the following horizons: tan-orange (TO) at the surface, green (G), purple (P), and olive-black (OB) at the bottom. δ¹³ C of individual fatty acids from intact polar lipids (IPFA) in TO were similar to δ¹³ C of dissolved inorganic carbon (DIC) in the overlying water column, indicating limited discrimination by cyanobacteria during CO₂ fixation. δ¹³ C_TOC of the underlying G was 3‰ greater than that of TO. The most δ¹³ C-depleted acetogenic lipids in the upper horizons were the cyanobacterial biomarkers C₁₇ n-alkanes and polyunsaturated fatty acids. Bishomohopanol was 4 to 7‰ enriched, relative to alkanes and intact polar fatty acids (IPFA), respectively. Acyclic C₂₀ isoprenoids were depleted by 14‰ relative to bishomohopanol. Significantly, ∆[δ¹³ C_TOC - δ¹³ C_∑IPFA ] increased from 6.9‰ in TO to 14.7‰ in OB. This major trend might indicate that ¹³ C-enriched residual organic matter accumulated at depth. The permanently anoxic P horizon was dominated by anoxygenic phototrophs and sulfate-reducing bacteria. P hosted an active sulfur-dependent microbial community. IPFA and bishomohopanol were ¹³ C-depleted relative to upper crust by 7 and 4‰, respectively, and C₂₀ isoprenoids were somewhat ¹³ C-enriched. Synthesis of alkanes in P was evidenced only by ¹³ C-depleted n-octadecane and 8-methylhexadecane. In OB, the marked increase of total inorganic carbon δ¹³ C (δ¹³ C_TIC ) of >6‰ perhaps indicated terminal mineralization. This δ¹³ C_TIC increase is consistent with degradation of the osmolyte glycine betaine by methylotrophic methanogens and loss of ¹³ C-depleted methane from the mat.

Keywords: CSIA; gypsum crust mat; intact polar fatty acid; lipid biomarker; stable carbon isotope.