Ring Index Research Articles

Glycerol dialkyl glycerol tetraether signatures in tropical mesotidal estuary sediments of Qua Iboe River, Gulf of Guinea

The continuous supply of land derived organic carbon by rivers is significant to the ocean carbon cycle. In river-estuary systems, the composition and distribution of sedimentary organic matter (OM) can provide detailed information on the balance of land-derived inputs and in situ productivity. This insight is significant for an improved understanding of anthropogenic activity and the changing climate. In the Gulf of Guinea (GoG), high rainfall, coupled with flooding and a warmer climate have direct impacts on OM distributions. Glycerol dialkyl glycerol tetraethers (GDGTs) have been used extensively to investigate OM. In this study, we focused on the widespread occurrence of isoprenoid GDGTs (isoGDGTs), branched GDGTs (brGDGTs), H-tetraethers (H-isoGDGTs and H-brGDGTs), hydroxyl GDGTs (OH-GDGTs), isoGDGT isomers, methylated isoGDGTs (Me-GDGTs), butanetriol and pentanetriol tetraethers (BDGTs and PDGTs), in short sediment cores collected from the inner and outer Qua Iboe River Estuary, located in the GoG. We further determined total organic carbon (Corg), total nitrogen (TN), long chain hydrocarbons (LCA; C27–C33n-alkanes), dinosterol, brassicasterol and phytol, to estimate OM sources, flooding activity, OM degradation, to reconstruct pH and to determine past tropical temperatures. The distribution patterns of GDGTs, use of principal component analysis (PCA), heatmap hierarchical cluster analysis, correlation models, the ratios of isoGDGTs/brGDGTs, ring index (RI), brGDGT-IIIa/IIa, branched and isoprenoid tetraether (BIT), Corg/TN and terrestrial-marine biomarker ratio (TMBR) were all sensitive for indicating terrestrial vs marine OM contributions to the total OM of the tropical estuarine sediments. Marine OM persisted from subsurface to bottom sediment layers (8–38 cm) in the outer estuary site, while a mixed OM source was observed in inner estuary sediments. The Cren/Cren’ ratio >58.5 (up to 83.8), pointed to a predominance of Thaumarchaeota group I.1a microbes. The Methane Index (MI) and isoGDGT-0/Cren ratio indicated significant imprints of a non-methanotrophic archaeal community. A positive linearity of total BDGTs and PDGTs plotted against MI and isoGDGT-0/Cren suggested that these compounds are produced by the same group of the non-methanogenic archaeal community in this tropical estuary. Thus, Methanomassiliicoccus luminyensis is not the only source of BDGTs and PDGTs in the marine environment. Further, the calculated CBT5me derived pH reflected in situ measured sediment pH (6.3). TEX86H-derived sea surface temperature (SST), within error, reflected water column temperature. Calculated brGDGT mean annual air temperatures (MAATs) reflected average annual atmospheric temperatures. Ring index OH-GDGTs temperature proxies (RI-OH SSTsummer and RI-OHꞌ SST) reflected mean dry season (November to February) temperatures. A newly derived MAAT proxy, calculated from H-brGDGT, also reflected the tropical annual air temperature (23–28 °C). Altogether, as expected, the OM sources are traced largely to both terrestrial and marine inputs. The terrestrial OM was deposited by excess flooding and surface runoff occasioned by torrential monsoon rains in recent years, triggered by climate change, while mesotidal currents introduced marine OM into the Qua Iboe River Estuary system. This study further contributes to our understanding of OM distributions in warmer climate conditions.

Influence of bottom seawater oxygen on archaeal tetraether lipids in sediments: Implications for archaeal lipid-based proxies

Glycerol dibiphytanyl glycerol tetraethers (GDGTs) are important archaeal membrane lipids that widely occur in marine water columns and sediments. Based on its sensitivity to temperature, the paleotemperature index TEX86 was developed and extensively studied. However, GDGTs in sediments are not only affected by their external sources, but also by internal biochemical processes. The effect of bottom water redox conditions on GDGT composition and TEX86 in the surface sediments remains unclear. In this study, field investigations in the eastern China marginal seas were conducted to trace the responses of sedimentary GDGTs to bottom dissolved oxygen (DO). Our results showed that the TEX86 was independent of the DO level. However, the decrease in DO was accompanied by an increase in GDGT Ring Index (RI) and relative abundance of crenarchaeol (Cren) in contrast to the decrease pattern for GDGT-0, suggesting that DO has important effects on the composition of GDGTs but shows limited impact on TEX86 in the study area. These changes were probably driven by archaeal adaptation, shift of community structure and degradation of GDGTs. In addition, strong relationships between DO and RI and between DO and GDGT abundances (i.e., %GDGT-0, GDGT-0/Cren) indicate that these parameters can be used as potential redox proxies for bottom water, especially in relatively stable stratified waters. Further studies coupled with archaeal community are needed to cover more areas to constrain their applicability and driving mechanisms.

Simultaneous extraction and chromatographic separation of n-alkanes and alkenones from glycerol dialkyl glycerol tetraethers via selective Accelerated Solvent Extraction

A method is described for simultaneous extraction and chromatographic separation of saturated hydrocarbons (n-alkanes) and unsaturated long-chain ketones (alkenones) from glycerol dialkyl glycerol tetraethers (GDGTs) using selective accelerated solvent extraction (ASE). We show that the method can be used to successfully separate n-alkanes and alkenones from GDGTs in marine sediment samples and n-alkanes from GDGTs in lake sediments and soil samples. A comparison of our method with analysis of samples purified using classical silica column chromatography demonstrates that the new method does not affect the alkenone unsaturation index (U37K'), the TetraEther indeX (TEX86), the Methane Index (MI), the Ring Index (RI), the branched-GDGT-based paleotemperature and soil pH indices, the Branched and Isoprenoid Tetraether (BIT) index, the n-alkane average chain length (ACL) or the carbon preference index (CPI). The new procedure results in higher sample recoveries for n-alkanes and more precise U37K' estimates at low concentrations, and contributes to reduced analyst laboratory time.

Seasonality of archaeal lipid flux and GDGT-based thermometry in sinking particles of high-latitude oceans: Fram Strait (79° N) and Antarctic Polar Front (50° S)

Abstract. The relative abundance of individual archaeal membrane lipids, namely of glycerol dialkyl glycerol tetraethers (GDGTs) with different numbers of cyclopentane rings, varies with temperature, which enables their use as a paleotemperature proxy index. The first GDGT-based index in marine sediments called TEX86 is believed to reflect mean annual sea surface temperature (maSST). The TEX86L is an alternative temperature proxy for “low-temperature” regions (<15 ∘C), where the original TEX86 proxy calibration shows a larger scatter. However, TEX86L-derived temperatures still display anomalous estimates in polar regions. In order to elucidate the potential cause of the disagreement between the TEX86L estimate and SST, we analyzed GDGT fluxes and TEX86L-derived temperatures in sinking particles collected with time-series sediment traps in high-northern- and high-southern-latitude regions. At 1296 m depth in the eastern Fram Strait (79∘ N), a combination of various transporting mechanisms for GDGTs might result in seasonally different sinking velocities for particles carrying these lipids, resulting in strong variability in the TEX86L signal. The similarity of flux-weighted TEX86L temperatures from sinking particles and surface sediments implies an export of GDGTs without alteration in the Fram Strait. The estimated temperatures correspond to temperatures in water depths of 30–80 m, where nitrification might occur, indicating the favorable depth habitat of Thaumarchaeota. In the Antarctic Polar Front of the Atlantic sector (50∘ S), TEX86L-derived temperatures displayed warm and cold biases compared to satellite-derived SSTs at 614 m depth, and its flux-weighted mean signal differs from the deep signal at 3196 m. TEX86L-derived temperatures at 3196 m depth and the surface sediment showed up to 7 ∘C warmer temperatures relative to satellite-derived SST. Such a warm anomaly might be caused by GDGT contributions from Euryarchaeota, which are known to dominate archaeal communities in the circumpolar deep water of the Antarctic Polar Front. The other reason might be that a linear calibration is not appropriate for this frontal region. Of the newly suggested SST proxies based on hydroxylated GDGTs (OH-GDGTs), only those with OH-GDGT–0 and crenarchaeol or the ring index (RI) of OH-GDGTs yield realistic temperature estimates in our study regions, suggesting that OH-GDGTs could be applied as a potential temperature proxy in high-latitude oceans.

Evaluating Production of Cyclopentyl Tetraethers by Marine Group II Euryarchaeota in the Pearl River Estuary and Coastal South China Sea: Potential Impact on the TEX86 Paleothermometer.

TEX86 [TetraEther indeX of glycerol dialkyl glycerol tetraethers (GDGTs) with 86 carbon atoms] has been widely applied to reconstruct (paleo-) sea surface temperature. Marine Group I (MG-I) Thaumarchaeota were thought to be the primary source of GDGTs constituting the TEX86 formula; however, recent research has suggested that Marine Group II (MG-II) Euryarchaeota may also contribute significantly to the GDGT pool in the ocean. Little is known regarding the potential impact of MG-II Euryarchaeota-derived GDGTs on TEX86 values recorded in marine sediments. In this study, we assessed the relationship between distributions of GDGTs and MG-II Euryarchaeota and evaluated its potential effect on the TEX86 proxy. Lipid and DNA analyses were performed on suspended particulate matter and surface sediments collected along a salinity gradient from the lower Pearl River (river water) and its estuary (mixing water) to the coastal South China Sea (SCS, seawater). TEX86-derived temperatures from the water column and surface sediments were significantly correlated and both were lower than satellite-based temperatures. The ring index (RI) values in these environments were higher than predicted from the calculated TEX86-RI correlation, indicating that the GDGT pool in the water column of the PR estuary and coastal SCS comprises relatively more cyclopentane rings, which thereby altered TEX86 values. Furthermore, the abundance of MG-II Euryarchaeota 16S rRNA gene in the mixing water was two to three orders of magnitude higher than those observed in the river or seawater. Significant linear correlations were observed between the gene abundance ratio of MG-II Euryarchaeota to total archaea and the fractional abundance of GDGTs with cyclopentane rings. Collectively, these results suggest that MG-II Euryarchaeota likely produce a large proportion of GDGTs with 1–4 cyclopentane moieties, which may bias TEX86 values in the water column and sediments. As such, valid interpretation of TEX86 values in the sediment record, particularly in coastal oceans, should consider the contribution from MG-II Euryarchaeota.

Ring Index: A new strategy to evaluate the integrity of TEX86 paleothermometry

AbstractThe TEX86 (tetraether index of 86 carbon atoms) sea surface temperature proxy has been increasingly applied in the reconstruction of Mesozoic and Cenozoic ocean temperatures. However, the archaeal lipids that compose TEX86 indices, glycerol dialkyl glycerol tetraethers (GDGTs), can derive from water column production, terrestrial sources, and/or within sediments. TEX86‐sea surface temperature estimates can also be influenced by non‐temperature factors, such as growth phase and nutrient levels. Here we show that the weighted average of cyclopentane moieties, known as the Ring Index (RI), can be used to determine if TEX86 temperature estimates are influenced by non‐thermal factors and/or deviate from modern analogues. We demonstrate that RI and TEX86 indices from the published global core top data set and mesocosm cultures are significantly correlated, as predicted through the influence of temperature on lipid biochemistry. We further show that when RI and TEX86 indices in modern or ancient records deviate from the modern global TEX86‐RI relationship, GDGT distributions are not solely controlled by environmental temperature and/or TEX86‐based temperature reconstructions are questionable.