Abstract. The methylation index of branched tetraethers (MBT) and cyclization ratio of branched tetraethers (CBT) based on the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGT) are useful proxies for the reconstruction of mean annual air temperature (MAT) and soil pH. Recently, a series of 6-methyl brGDGTs were identified which were previously co-eluted with 5-methyl brGDGTs. However, little is known about 6-methyl brGDGTs in the Qinghai–Tibetan Plateau (QTP), a critical region of the global climate system. Here, we analyze 30 surface soils covering a large area of the QTP, among which 6-methyl brGDGTs were the most abundant components (average 53 ± 17% of total brGDGT). The fractional abundance of 6-methyl brGDGTs showed a good correlation with soil pH, while the global MBT'5ME calibration overestimates MAT in the QTP. We therefore proposed a MBT5/6 index including both 5- and 6-methyl brGDGTs, presenting a strong correlation with MAT in QTP: MAT = −20.14 + 39.51 × MBT5/6 (n = 27, r2 = 0.82; RMSE = 1.3 °C). Another index, namely IBT (isomerization of branched tetraether), based on carbon skeleton isomerization of the 5-methyl to 6-methyl brGDGTs, is dependent on soil pH: pH = 6.77 − 1.56 × IBT (n = 27; r2 = 0.74, RMSE = 0.32). Our study suggests that changing the position of methyl group of brGDGTs may be another mechanism for some soil bacteria to adapt to the ambient pH change in addition to the well-known cyclization.

Recently, 6-methyl branched glycerol dialkyl glycerol tetraethers (brGDGTs) were separated from 5-methyl brGDGTs, which are used in brGDGT-based proxies. Here we analyzed brGDGTs in 27 soil samples along the 400 mm isoline of mean annual precipitation in China by using tandem 2D liquid chromatography. The fractional abundance of 6-methyl brGDGTs showed a positive correlation with soil pH, while that of 5-methyl brGDGTs decreased with increasing soil pH. The abundance ratio of 6-/5-methyl brGDGTs, namely the isomerization of branched tetraethers (IBT), was calculated. The correlation of IBT with pH (pH = 6.33 -1.28 × IBT; R 2 0.89; root mean squared error, RMSE, 0.24) was much stronger than that of the traditionally used cyclisation index of branched tetraethers (CBT) with pH (R 2 0.52; RMSE 0.49) and comparable with that of CBT' with pH (R 2 0.88; RMSE 0.25). Compiling all available data from 319 soil samples resulted in a global calibration: pH = 6.53 -1.55 2 × IBT (R 2 0.72; RMSE 0.65), which has a better correlation than the CBT5ME-pH proxy (R 2 0.63; RMSE 0.78), but a weaker correlation than the CBT'-pH proxy (R 2 0.85; RMSE 0.52). Our result suggests that the IBT is a promising indicator for soil pH, particularly in cases when some compounds in the CBT' index cannot be determined.

Based on satellite remote sensing image, GIS and Fragstats, this study modeled and calculated the dynamic changes of land use, land cover and landscape patterns in Guizhou Province, China, and calculated the changes of ecosystem service values (ESVs). The impacts of the evolution of landscape patterns on the ESVs were analyzed, and reasonable policy recommendations were made. The findings are as follows: (1) In the past two decades, the area of cropland and grassland has decreased; the area of water bodies, urban and rural, industrial and mining, and residential areas has increased; the area of forestland has increased first and then decreased. (2) The two major types of landscapes, cropland and grassland, are clearly being replaced by two land types, forest land and water bodies. (3) Overall, the degree of landscape aggregation and adjacency has decreased, and the landscape heterogeneity has increased. (4) The total amount of ESV in 2000, 2008, 2013 and 2017 was 2574 × 108 Yuan RMB, 2605 × 108 Yuan RMB, 2618 × 108 Yuan RMB and 2612 × 108 Yuan RMB, respectively. The changes of landscape patterns had important impacts on the ESVs. In order to solve the problems caused by the increasingly prominent changes in the landscape patterns and improve the ESVs, it is necessary to rationally plan and allocate land resources, optimize the industrial structures, and develop effective regulatory policies.

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids that are widely used as valuable paleoenvironmental proxies. The recently discovered 6-methyl brGDGTs improved the accuracy of the proxies for temperature “methylation branched tetraethers (MBT)” and soil pH “cyclization branched tetraethers (CBT)”. However, the calibration uncertainties are still substantial for brGDGT-derived proxies (e.g., 5 °C for MBT′5ME). Here we report a series of novel 7-methyl brGDGT isomers that co-eluted with the known 5- and 6-methyl brGDGTs in commonly applied normal phase high performance liquid chromatography (HPLC). Using an optimized HPLC gradient the novel 7-methyl brGDGTs could be structurally characterized and quantified. Their mean relative abundance was in the range of 6% of the total brGDGTs in Chinese and Cameroon lake sediments. The 7-methyl brGDGT IIa7 correlates with sediment pH (R2 = 0.44, root-mean-square error = 0.26 pH unit), a result that motivates the re-analysis of brGDGTs in soils and sediments to further reassess brGDGT-based proxies and to determine the source of 7-methyl brGDGTs. In addition to the 7-methyl brGDGTs, we identified two novel pentamethylated brGDGTs based on the mass spectra of its ether-cleaved hydrocarbon products

A variety of biomarkers were examined from Ocean Drilling Program Core 1202B to reconstruct temperature and phytoplankton community structures in the southern Okinawa Trough since 20 ka. Two molecular temperature proxies ( $${\rm U}_{{37}}^{{{\rm K}\prime}} $$ and TEX86) show 5°C to ~6°C warming during the glacial-interglacial transition. Prior to the Holocene, the $${\rm U}_{{37}}^{{{\rm K}\prime}} $$ -derived temperature was generally 1°C to 4°C higher than TEX86-derived temperature. This difference, however, was reduced to <1°C in the Holocene. Correspondingly, the phytoplankton biomarkers (e.g., C37:2 alkenone, brassicasterol, C30 1,15 diol, and dinosterol) indicate a shift of planktonic community structures, with coccolithophorids becoming more abundant in the Holocene at the expense of diatoms/dinoflagellates. This shift is related to the variability of nutrients, temperature, and salinity in the Okinawa Trough, likely controlled by the sea level and the intensity of the Kuroshio Current. The phytoplankton community change may have had profound implications for atmospheric CO2 fluctuations during glacial-interglacial cycles since diatoms and dinoflagellates have a higher efficiency of the biological pump than coccolithophorids.