The MBT-CBT proxy for the reconstruction of paleotemperatures and past soil pH is based on the distribution of branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids. The Methylation of Branched Tetraether (MBT) and the Cyclisation of Branched Tetraether (CBT) indices were developed to quantify these distributions, and significant empirical relations between these indices and annual mean air temperature (MAT) and/or soil pH were found in a large data set of soils. In this study, we extended this soil dataset to 278 globally distributed surface soils. Of these soils, 26% contains all nine brGDGTs, while in 63% of the soils the seven most common brGDGTs were detected, and the latter were selected for calibration purposes. This resulted in new transfer functions for the reconstruction of pH based on the CBT index: pH = 7.90-1.97 Â CBT (r 2 = 0.70; RMSE = 0.8; n = 176), as well as for MAT based on the CBT index and methylation index based on the seven most abundant GDGTs (defined as MBT 0 ): MAT = 0.81-5.67 Â CBT + 31.0 Â MBT 0 (r 2 = 0.59; RMSE = 5.0°C; n = 176). The new transfer function for MAT has a substantially lower correlation coefficient than the original equation (r 2 = 0.77). To investigate possible improvement of the correlation, we used our extended global surface soil dataset to statistically derive the indices that best describe the relations of brGDGT composition with MAT and soil pH. These new indices, however, resulted in only a relatively minor increase in correlation coefficients, while they cannot be explained straightforwardly by physiological mechanisms. The large scatter in the calibration cannot be fully explained by local factors or by seasonality, but MAT for soils from arid regions are generally substantially (up to 20°C) underestimated, suggesting that absolute brGDGT-based temperature records for these areas should be interpreted with caution.The applicability of the new MBT 0 -CBT calibration function was tested using previously published MBT-CBT-derived paleotemperature records covering the last deglaciation in Central Africa and East Asia, the Eocene-Oligocene boundary and the Paleocene-Eocene thermal maximum. The results show that trends remain similar in all records, but that absolute temperature estimates and the amplitude of temperature changes are lower for most records, and generally in better agreement with independent proxy data.

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Abstract-Anew route for the formation of gammacerane from tetmhymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids.

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The transition from hunter-gatherer-fisher groups to agrarian societies is arguably the most significant change in human prehistory. In the European plain there is evidence for fully developed agrarian societies by 7,500 cal. yr BP, yet a well-established agrarian society does not appear in the north until 6,000 cal. yr BP for unknown reasons. Here we show a sudden increase in summer temperature at 6,000 cal. yr BP in northern Europe using a well-dated, high resolution record of sea surface temperature (SST) from the Baltic Sea. This temperature rise resulted in hypoxic conditions across the entire Baltic sea as revealed by multiple sedimentary records and supported by marine ecosystem modeling. Comparison with summed probability distributions of radiocarbon dates from archaeological sites indicate that this temperature rise coincided with both the introduction of farming, and a dramatic population increase. The evidence supports the hypothesis that the boundary of farming rapidly extended north at 6,000 cal. yr BP because terrestrial conditions in a previously marginal region improved.

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