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High-resolution paleoclimate records from tropical continental settings are greatly needed to advance understanding of global climate dynamics. The International Continental Scientific Drilling Program (ICDP) project DeepCHALLA recovered a 214.8 m long sediment sequence from Lake Chala, a deep and permanently stratified (meromictic) crater lake in eastern equatorial Africa, covering the past ca. 250 000 years (250 kyr) of continuous lacustrine deposition since the earliest phase of lake-basin development. Lipid biomarker analyses on the sediments of Lake Chala can provide quantitative records of past variation in temperature and moisture balance from this poorly documented region. However, the degree to which climate proxies derived from aquatically produced biomarkers are affected by aspects of lake developmental history is rarely considered, even though it may critically influence their ability to consistently register a particular climate variable through time. Modern-system studies of Lake Chala revealed crucial information about the mechanisms underpinning relationships between proxies based on isoprenoid (iso-) and branched (br-) glycerol dialkyl glycerol tetraethers (GDGTs) and the targeted climate variables, but the persistence of these relationships in the past remains unclear. Here we assess the reliability of long-term climate signals registered in the sediments of Lake Chala by comparing downcore variations in GDGT distributions with major phases in lake-system evolution as reflected by independent proxies of lake depth, mixing regime and nutrient dynamics: seismic reflection data, lithology and fossil diatom assemblages. Together, these records suggest that during early lake history (before ca. 180–200 ka) the distinct mixing-related depth zones with which specific GDGT producers are associated in the modern-day lake were not yet formed, likely due to more open lake hydrology and absence of chemical water-column stratification. Consequently absolute GDGT concentrations dating to this period are relatively low, proxies sensitive to water-column stratification (e.g., branched versus isoprenoid tetraether (BIT) index) display highly irregular temporal variability, and correlations between proxies are dissimilar to expectations based on modern-system understanding. A sequence of lake-system changes between ca. 180–200 and ca. 80 ka first established and then strengthened the chemical density gradient, promoting meromictic conditions despite the overall decrease in lake depth due to the basin gradually being filled up with sediments. From ca. 180 ka onward some GDGTs and derived proxies (e.g., crenarchaeol concentration, BIT index and IR6Me) display strong ∼ 23 kyr periodicity, likely reflecting the predominantly precession-driven insolation forcing of Quaternary climate variability in low-latitude regions. Our results suggest that GDGT-based temperature and moisture-balance proxies in Lake Chala sediments reflect the climate history of eastern equatorial Africa from at least ca. 160 ka onwards, i.e., covering the complete last glacial–interglacial cycle and the penultimate glacial maximum. This work confirms the potential of lacustrine GDGTs for elucidating the climate history of tropical regions at Quaternary timescales, provided they are applied to suitably high-quality sediment archives. Additionally, their interpretation should incorporate a broader understanding of the extent to which lake-system evolution limits the extrapolation back in time of proxy-climate relationships established in the modern system.

Climate variability is typically amplified towards polar regions. The underlying causes, notably albedo and humidity changes, are challenging to accurately quantify with observations or models, thus hampering projections of future polar amplification. Polar amplification reconstructions from the ice-free early Eocene (∼56–48 Ma) can exclude ice albedo effects, but the required tropical temperature records for resolving timescales shorter than multi-million years are lacking. Here, we reconstruct early Eocene tropical sea surface temperature variability by presenting an up to ∼4 kyr resolution biomarker-based temperature record from Ocean Drilling Program (ODP) Site 959, located in the tropical Atlantic Ocean. This record shows warming across multiple orbitally paced carbon cycle perturbations, coeval with high-latitude-derived deep-ocean bottom waters, showing that these events represent transient global warming events (hyperthermals). This implies that orbital forcing caused global temperature variability through carbon cycle feedbacks. Importantly, deep-ocean temperature variability was amplified by a factor of 1.7–2.3 compared to the tropical surface ocean, corroborating available long-term estimates. This implies that fast atmospheric feedback processes controlled meridional temperature gradients on multi-million year, as well as orbital, timescales during the early Eocene. Our combined records have several other implications. First, our amplification factor is somewhat larger than the same metric in fully coupled simulations of the early Eocene (1.1–1.3), suggesting that models slightly underestimate the non-ice-related – notably hydrological – feedbacks that cause polar amplification of climate change. Second, even outside the hyperthermals, we find synchronous eccentricity-forced temperature variability in the tropics and deep ocean that represent global mean sea surface temperature variability of up to 0.7 °C, which requires significant variability in atmospheric pCO2. We hypothesize that the responsible carbon cycle feedbacks that are independent of ice, snow, and frost-related processes might play an important role in Phanerozoic orbital-scale climate variability throughout geological time, including Pleistocene glacial–interglacial climate variability.

Both marine dinoflagellate cysts and terrestrially derived pollen and spores are abundant in coastal sediments close to river mouths, making sediment records from such settings ideal to simultaneously study land–ocean climate interactions, marine productivity patterns and freshwater input over time. However, few studies consider the combined calibration of these palynological proxies in modern coastal sediments offshore from rivers, which is needed to strengthen the interpretation of paleoreconstructions. Here, we analyze the palynological content of marine surface sediments along land–sea transects off the Mississippi and Atchafalaya river mouths in the northern Gulf of Mexico (GoM) and test three palynological indices which are often employed in the paleo-domain: (i) the abundance of cysts of heterotrophic and autotrophic dinoflagellates (dinocysts) as a tracer for primary productivity (H/A ratio) and (ii) the ratio between non-bisaccate pollen and bisaccates (P/B) as well as (iii) the ratio between pollen (excluding bisaccates) and dinocysts (P/D), which are both tracers for river input and distance to the coast. Our results show that dinoflagellate cysts are most abundant on the shelf, where heterotrophic dinocyst species dominate coastal assemblages in reach of the river plume, while autotrophic taxa are more present in the oligotrophic open ocean. This is clearly reflected in decreasing H/A values further offshore. Individual dinocyst taxa also seem to inhabit specific niches along an onshore–offshore transect, linked to nutrient availability and proximity to the turbid river plume. The highest pollen concentrations are found close to the Mississippi river mouth and mostly represent a mixture of local coastal and upstream vegetation, whereas bisaccate pollen was most abundant further offshore of the Mississippi river. Multivariate redundancy analysis (RDA) performed on both pollen and dinocyst assemblages, a set of environmental parameters, and the three palynological ratios showed that net primary productivity was the most important variable influencing the dinocyst assemblages, likely as the result of nutrient input. Additionally, the RDA confirmed that the H/A ratio indeed seems to track primary productivity, while the P/B ratio results in a robust indicator for distance to the coast, and the P/D ratio better reflects river input. Together, our data confirm and further specify the suitability of these three palynological ratios in river-dominated coastal margins as proxies for (past) marine productivity and distance to the coast and river.

At present, a strong latitudinal sea-surface-temperature (SST) gradient of ∼ 16 ∘C exists across the Southern Ocean, maintained by the Antarctic Circumpolar Current (ACC) and a set of complex frontal systems. Together with the Antarctic ice masses, this system has formed one of the most important global climate regulators. The timing of the onset of the ACC system, its development towards modern-day strength and the consequences for the latitudinal SST gradient around the southern Atlantic Ocean are still uncertain. Here we present new TEX86 (TetraEther indeX of tetraethers consisting of 86 carbon atoms)-derived SST records from two sites located east of Drake Passage (south-western South Atlantic) to assist in better understanding two critical time intervals of prominent climate transitions during the Cenozoic: the late Eocene–early Oligocene (Ocean Drilling Program, ODP, Site 696) and Middle–Late Miocene (IODP Site U1536) transitions. Our results show temperate conditions (20–11 ∘C) during the first time interval, with a weaker latitudinal SST gradient (∼ 8 ∘C) across the Atlantic sector of the Southern Ocean compared to present day. We ascribe the similarity in SSTs between Sites 696 and 511 in the late Eocene–early Oligocene South Atlantic to a persistent, strong subpolar gyre circulation connecting the sites, which can only exist in the absence of a strong throughflow across the Drake Passage. Surprisingly, the southern South Atlantic record Site 696 shows comparable SSTs (∼ 12–14 ∘C) during both the earliest Oligocene oxygen isotope step (EOIS, ∼ 33.65 Ma) and the Miocene Climatic Optimum (MCO, ∼ 16.5 Ma). Apparently, maximum Oligocene Antarctic ice volume could coexist with warm ice-proximal surface ocean conditions, while at similar ocean temperatures, the Middle Miocene Antarctic ice sheet was likely reduced. Only a few Middle–Late Miocene (discontinuous) high-latitude records exist due to ice advances causing unconformities. Our low-resolution Site U1536 record of southern South Atlantic SSTs cooled to ∼ 5 ∘C during the Middle Miocene Climate Transition (MMCT, 14 Ma), making it the coldest oceanic region in the poorly recorded Antarctic realm and likely the main location for deep-water formation. The already-cold south-western South Atlantic conditions at the MMCT with relatively moderate additional cooling during the Late Miocene contrasts with the profound cooling in the lower latitudes and other sectors of the Southern Ocean due to northward expansion of the Southern Ocean frontal systems.

The Neogene (23.04–2.58 Ma) is characterised by progressive buildup of ice volume and climate cooling in the Antarctic and the Northern Hemisphere. Heat and moisture delivery to Antarctica is, to a large extent, regulated by the strength of meridional temperature gradients. However, the evolution of the Southern Ocean frontal systems remains scarcely studied in the Neogene. Here, we present the first long-term continuous sea surface temperature (SST) record of the subtropical front area in the Southern Ocean at Ocean Drilling Program (ODP) Site 1168 off western Tasmania. This site is, at present, located near the subtropical front (STF), as it was during the Neogene, despite a 10∘ northward tectonic drift of Tasmania. We analysed glycerol dialkyl glycerol tetraethers (GDGTs – on 433 samples) and alkenones (on 163 samples) and reconstructed the paleotemperature evolution using TEX86 and U37k′ as two independent quantitative proxies. Both proxies indicate that Site 1168 experienced a temperate ∼ 25 ∘C during the early Miocene (23–17 Ma), reaching ∼ 29 ∘C during the mid-Miocene climatic optimum. The stepwise ∼ 10 ∘C cooling (20–10 ∘C) in the mid-to-late Miocene (12.5–5.0 Ma) is larger than that observed in records from lower and higher latitudes. From the Pliocene to modern (5.3–0 Ma), STF SST first plateaus at ∼ 15 ∘C (3 Ma), then decreases to ∼ 6 ∘C (1.3 Ma), and eventually increases to the modern levels around ∼ 16 ∘C (0 Ma), with a higher variability of 5∘ compared to the Miocene. Our results imply that the latitudinal temperature gradient between the Pacific Equator and the STF during late Miocene cooling increased from 4 to 14 ∘C. Meanwhile, the SST gradient between the STF and the Antarctic margin decreased due to amplified STF cooling compared to the Antarctic margin. This implies a narrowing SST gradient in the Neogene, with contraction of warm SSTs and northward expansion of subpolar conditions.

Rivers play a key role in the global carbon cycle by transporting terrestrial organic matter (TerrOM) from land to the ocean. Upon burial in marine sediments, this TerrOM may be a significant long-term carbon sink, depending on its composition and properties. However, much remains unknown about the dispersal of different types of TerrOM in the marine realm upon fluvial discharge since the commonly used bulk organic matter (OM) parameters do not reach the required level of source- and process-specific information. Here, we analyzed bulk OM properties, lipid biomarkers (long-chain n-alkanes, sterols, long-chain diols, alkenones, branched and isoprenoid glycerol dialkyl glycerol tetraethers (brGDGTs and isoGDGTs)), pollen, and dinoflagellate cysts in marine surface sediments along two transects offshore the Mississippi–Atchafalaya River (MAR) system, as well as one along the 20 m isobath in the direction of the river plume. We use these biomarkers and palynological proxies to identify the dispersal patterns of soil–microbial organic matter (SMOM), fluvial, higher plant, and marine-produced OM in the coastal sediments of the northern Gulf of Mexico (GoM). The Branched and Isoprenoid Tetraether (BIT) index and the relative abundance of C32 1,15-diols indicative for freshwater production show high contributions of SMOM and fluvial OM near the Mississippi River (MR) mouth (BIT = 0.6, FC321,15 > 50 %), which rapidly decrease further away from the river mouth (BIT < 0.1, FC321,15 < 20 %). In contrast, concentrations of long-chain n-alkanes and pollen grains do not show this stark decrease along the path of transport, and especially n-alkanes are also found in sediments in deeper waters. Proxy indicators show that marine productivity is highest close to shore and reveal that marine producers (diatoms, dinoflagellates, coccolithophores) have different spatial distributions, indicating their preferred niches. Close to the coast, where food supply is high and waters are turbid, cysts of heterotrophic dinoflagellates dominate the assemblages. The dominance of heterotrophic taxa in shelf waters in combination with the rapid decrease in the relative contribution of TerrOM towards the deeper ocean suggest that TerrOM input may trigger a priming effect that results in its rapid decomposition upon discharge. In the open ocean far away from the river plume, autotrophic dinoflagellates dominate the assemblages, indicating more oligotrophic conditions. Our combined lipid biomarker and palynology approach reveals that different types of TerrOM have distinct dispersal patterns, suggesting that the initial composition of this particulate OM influences the burial efficiency of TerrOM on the continental margin.

Monsoonal rivers play an important role in the land-to-sea transport of soil-derived organic carbon (OC). However, spatial and temporal variation in the concentration, composition, and fate of this OC in these rivers remains poorly understood. We investigate soil-to-sea transport of soil OC by the Godavari River in India using glycerol dialkyl glycerol tetraether (GDGT) lipids in soils, river suspended particulate matter (SPM), and riverbed sediments, as well as in a marine sediment core from the Bay of Bengal. The abundance and composition of GDGTs in SPM and sediments in the Godavari River differs between the dry and wet season. In the dry season, SPM and riverbed sediments from the whole basin contain more 6-methyl branched GDGTs (brGDGTs) than the soils. In the upper basin, where mobilisation and transport of soils is limited due to deficient rainfall and damming, contributions of 6-methyl brGDGTs in SPM and riverbed sediments are relatively high year-round, suggesting that they have an aquatic source. Aquatic brGDGT production coincides with elevated values of the isoprenoid GDGT-0 / crenarchaeol ratio in SPM and riverbed sediments from the upper basin, indicating low-oxygen conditions. In the wet season, brGDGT distributions in SPM from the lower basin closely resemble those in soils, mostly from the north and east tributaries, corresponding to precipitation patterns. The brGDGT composition in SPM and sediments from the delta suggests that soil OC is only effectively transported to the Bay of Bengal in the wet season, when the river plume extends beyond the river mouth. The sediment geochemistry indicates that also the mineral particles exported by the Godavari River primarily originate from the lower basin, similar to the brGDGTs, suggesting that they are transported together. However, river depth profiles in the downstream Godavari reveal no hydrodynamic sorting effect on brGDGTs in either season, indicating that brGDGTs are not closely associated with mineral particles. The similarity of brGDGT distributions in bulk and fine-grained sediments (≤ 63 µm) further confirms the absence of selective transport mechanisms. Nevertheless, the composition of brGDGTs in a Holocene, marine sediment core near the river mouth appears substantially different from that in the modern Godavari basin, suggesting that terrestrial-derived brGDGTs are rapidly lost upon discharge into the Bay of Bengal and/or overprinted by marine in situ production. The large change in brGDGT distributions at the river–sea transition implies that this zone is key in the transfer of soil OC, as well as that of the environmental signal carried by brGDGTs from the river basin.

The large difference in the fractionation of stable carbon isotopes between C3 and C4 plants is widely used in vegetation reconstructions, where the predominance of C3 plants suggests wetter and that of C4 plants drier conditions. The stable carbon isotopic composition of organic carbon (OC) preserved in soils or sediments may be a valuable (paleo-)environmental indicator, based on the assumption that plant-derived material retains the stable carbon isotopic value of its photosynthetic pathway during transfer from plant to sediment. In this study, we investigated the bulk carbon isotopic values of C3 and C4 plants (δ13C) and of organic carbon (δ13Corg) in soils, river suspended particulate matter (SPM) and riverbed sediments to gain insight into the control of precipitation on C3 and C4 plant δ13C values and to assess changes in δ13Corg values along the plant–soil–river continuum. This information allows us to elucidate the implications of different δ13C end-members on C3 / C4 vegetation reconstructions. Our analysis was performed in the Godavari River basin, located in the core monsoon zone in peninsular India, a region that integrates the hydroclimatic and vegetation changes caused by variation in monsoonal strength. The basin has distinct wet and dry seasons and is characterised by natural gradients in soil type (from clay-rich to sandy), precipitation (∼ 500 to 1500 mm yr−1) and vegetation type (from mixed C3 / C4 to primarily C3) from the upper to the lower basin. The δ13C values of Godavari C3 plants were strongly controlled by mean annual precipitation (MAP), showing an isotopic enrichment of ∼ 2.2 ‰ from ∼ 1500 to 500 mm yr−1. Tracing δ13Corg values from plant to soils and rivers revealed that soils and riverbed sediments reflected the transition from mixed C3 and C4 vegetation in the dry upper basin to more C3 vegetation in the humid lower basin. Soil degradation and stabilisation processes and hydrodynamic sorting within the river altered the plant-derived δ13C signal. Phytoplankton dominated the δ13Corg signal carried by SPM in the dry season and year-round in the upper basin. Application of a linear mixing model showed that the %C4 plants in the different subbasins was ∼ 7 %–15 % higher using plant end-members based on measurement of the Godavari vegetation and tailored to local moisture availability than using those derived from data compilations of global vegetation. Including a correction for the 13C enrichment in Godavari C3 plants due to drought resulted in maximally 6 % lower estimated C4 plant cover. Our results from the Godavari basin underline the importance of making informed choices about the plant δ13C end-members for vegetation reconstructions, considering characteristics of the regional vegetation and environmental factors such as MAP in monsoonal regions.

TEX86 is a paleothermometer based on Thaumarcheotal glycerol dialkyl glycerol tetraether (GDGT) lipids and is one of the most frequently used proxies for sea-surface temperature (SST) in warmer-than-present climates. However, GDGTs are not exclusively produced in and exported from the mixed layer, so sedimentary GDGTs may contain a depth-integrated signal that is also sensitive to local subsurface temperature variability. In addition, the correlation between TEX86 and SST is not significantly stronger than that to depth-integrated mixed-layer to subsurface temperatures. The calibration of TEX86 to SST is therefore controversial. Here we assess the influence of subsurface temperature variability on TEX86 using a downcore approach. We present a 15 Myr TEX86 record from Ocean Drilling Program Site 959 in the Gulf of Guinea and use additional proxies to elucidate the source of the recorded TEX86 variability. Relatively high GDGT[2/3] ratio values from 13.6 Ma indicate that sedimentary GDGTs were partly sourced from deeper (>200 m) waters. Moreover, late Pliocene TEX86 variability is highly sensitive to glacial–interglacial cyclicity, as is also recorded by benthic δ18O, while the variability within dinoflagellate assemblages and surface/thermocline temperature records (U37k′ and Mg/Ca) is not primarily explained by glacial–interglacial cyclicity. Combined, these observations are best explained by TEX86 sensitivity to sub-thermocline temperature variability. We conclude that TEX86 represents a depth-integrated signal that incorporates a SST and a deeper component, which is compatible with the present-day depth distribution of Thaumarchaeota and with the GDGT[2/3] distribution in core tops. The depth-integrated TEX86 record can potentially be used to infer SST variability, because subsurface temperature variability is generally tightly linked to SST variability. Using a subsurface calibration with peak calibration weight between 100 and 350 m, we estimate that east equatorial Atlantic SST cooled by ∼5 ∘C between the Late Miocene and Pleistocene. On shorter timescales, we use the TEX86 record as a proxy for South Atlantic Central Water (SACW), which originates from surface waters in the South Atlantic Gyre and mixes at depth with Antarctic Intermediate Water (AAIW). Leads and lags around the Pliocene M2 glacial (∼3.3 Ma) in our record, combined with published information, suggest that the M2 glacial was marked by SACW cooling during an austral summer insolation minimum and that decreasing CO2 levels were a feedback, not the initiator, of glacial expansion.

Sea surface temperature (SST) reconstructions based on isoprenoid glycerol dialkyl glycerol tetraether (isoGDGT) distributions from the Eocene southwest (SW) Pacific Ocean are unequivocally warmer than can be reconciled with state-of-the-art fully coupled climate models. However, the SST signal preserved in sedimentary archives can be affected by contributions of additional isoGDGT sources. Methods now exist to identify and possibly correct for overprinting effects on the isoGDGT distribution in marine sediments. Here, we use the current proxy insights to (re-)assess the reliability of the isoGDGT-based SST signal in 69 newly analyzed and 242 reanalyzed sediments at Ocean Drilling Program (ODP) Site 1172 (East Tasman Plateau, Australia) following state-of-the-art chromatographic techniques. We compare our results with paleoenvironmental and paleoclimatologic reconstructions based on dinoflagellate cysts. The resulting ∼ 130 kyr resolution Maastrichtian–Oligocene SST record based on the TetraEther indeX of tetraethers with 86 carbon atoms (TEX86) confirms previous conclusions of anomalous warmth in the early Eocene SW Pacific and remarkably cool conditions during the mid-Paleocene. Dinocyst diversity and assemblages show a strong response to the local SST evolution, supporting the robustness of the TEX86 record. Soil-derived branched GDGTs stored in the same sediments are used to reconstruct mean annual air temperature (MAAT) of the nearby land using the Methylation index of Branched Tetraethers with 5-methyl bonds (MBT'5me) proxy. MAAT is consistently lower than SST during the early Eocene, independent of the calibration chosen. General trends in SST and MAAT are similar, except for (1) an enigmatic absence of MAAT rise during the Paleocene–Eocene Thermal Maximum and Middle Eocene Climatic Optimum, and (2) a subdued middle–late Eocene MAAT cooling relative to SST. Both dinocysts and GDGT signals suggest a mid-shelf depositional environment with strong river runoff during the Paleocene–early Eocene progressively becoming more marine thereafter. This trend reflects gradual subsidence and more pronounced wet/dry seasons in the northward-drifting Australian hinterland, which may also explain the subdued middle Eocene MAAT cooling relative to that of SST. The overall correlation between dinocyst assemblages, marine biodiversity and SST changes suggests that temperature exerted a strong influence on the surface-water ecosystem. Finally, we find support for a potential temperature control on compositional changes of branched glycerol monoalkyl glycerol tetraethers (brGMGTs) in marine sediments. It is encouraging that a critical evaluation of the GDGT signals confirms that most of the generated data are reliable. However, this also implies that the high TEX86-based SSTs for the Eocene SW Pacific and the systematic offset between absolute TEX86-based SST and MBT'5me-based MAAT estimates remain without definitive explanation.

A series of papers published shortly after the Integrated Ocean Drilling Program Arctic Coring Expedition (ACEX, 2004) on Lomonosov Ridge indicated remarkably high early Eocene sea surface temperatures (SSTs; ca. 23 to 27 ∘C) and land air temperatures (ca. 17 to 25 ∘C) based on the distribution of isoprenoid and branched glycerol dialkyl glycerol tetraether (isoGDGT and brGDGT) lipids, respectively. Here, we revisit these results using recent analytical developments – which have led to improved temperature calibrations and the discovery of new temperature-sensitive glycerol monoalkyl glycerol tetraethers (GMGTs) – and currently available proxy constraints. The isoGDGT assemblages support temperature as the dominant variable controlling TEX86 values for most samples. However, contributions of isoGDGTs from land, which we characterize in detail, complicate TEX86 paleothermometry in the late Paleocene and part of the interval between the Paleocene–Eocene Thermal Maximum (PETM; ∼ 56 Ma) and the Eocene Thermal Maximum 2 (ETM2; ∼ 54 Ma). Background early Eocene SSTs generally exceeded 20 ∘C, with peak warmth during the PETM (∼ 26 ∘C) and ETM2 (∼ 27 ∘C). We find abundant branched GMGTs, likely dominantly marine in origin, and their distribution responds to environmental change. Further modern work is required to test to what extent temperature and other environmental factors determine their distribution. Published Arctic vegetation reconstructions indicate coldest-month mean continental air temperatures of 6–13 ∘C, which reinforces the question of whether TEX86-derived SSTs in the Paleogene Arctic are skewed towards the summer season. The exact meaning of TEX86 in the Paleogene Arctic thus remains a fundamental issue, and it is one that limits our assessment of the performance of fully coupled climate models under greenhouse conditions.

Lake sediments are important archives of continental climate history, and their lipid biomarker content can be exploited to reconstruct paleoenvironmental conditions. Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids widely used in paleoclimate studies to reconstruct past temperature. However, major gaps still exist in our understanding of the environmental controls on in situ (i.e. aquatic) production in lake systems. In Lake Chala, a permanently stratified tropical crater lake in East Africa, we determined the concentrations and fractional abundances of individual brGDGTs along depth profiles of suspended particulate matter collected monthly from September 2013 to January 2015 and in settling particles collected monthly at 35 m water depth from August 2010 to January 2015 and compared these brGDGT distributions with those in surficial lake bottom sediments and catchment soils. We find that brGDGTs are primarily produced within the water column and that their concentrations and distributions vary greatly with depth and over time. Comparison with concentration–depth profiles of the monthly distribution and abundance of bacterial taxa, based on 16S rRNA gene amplicon sequencing and quantification, indicates that Acidobacteria are likely not the main producers of brGDGTs in Lake Chala. Shallowing of the oxic–anoxic boundary during seasonal episodes of strong water column stratification promoted production of specific brGDGTs in the anoxic zone. BrGDGT distributions in the water column do not consistently relate with temperature, pH, or dissolved-oxygen concentration but do respond to transitions between episodes of strong stratification and deep (but partial) lake mixing, as does the aquatic bacterial community. Hence, the general link between brGDGT distributions and temperature in brGDGT-based paleothermometry is more likely driven by a change in bacterial community composition than by membrane adaptation of specific members of the bacterial community to changing environmental conditions. Although temperature is not the principal driver of distributional changes in aquatic brGDGTs in this system, at least not during the 17-month study period, abundance-weighted and time-integrated averages of brGDGT fractional abundance in the 53-month time series of settling particles reveal systematic variability over longer timescales that indirectly relates to temperature. Thus, although we do not as yet fully understand the drivers of modern-day brGDGT fluxes and distributions in Lake Chala, our data do support the application of brGDGT paleothermometry to time-integrated archives such as sediments. Highlights. BrGDGTs in the tropical African lake Chala are produced in situ. Acidobacteria are not the dominant source of aquatic brGDGTs. Stratification and mixing drive aquatic brGDGT production and their signature.

Global climate cooled from the early Eocene hothouse (∼52–50 Ma) to the latest Eocene (∼34 Ma). At the same time, the tectonic evolution of the Southern Ocean was characterized by the opening and deepening of circum-Antarctic gateways, which affected both surface- and deep-ocean circulation. The Tasmanian Gateway played a key role in regulating ocean throughflow between Australia and Antarctica. Southern Ocean surface currents through and around the Tasmanian Gateway have left recognizable tracers in the spatiotemporal distribution of plankton fossils, including organic-walled dinoflagellate cysts. This spatiotemporal distribution depends on both the physicochemical properties of the water masses and the path of surface-ocean currents. The extent to which climate and tectonics have influenced the distribution and composition of surface currents and thus fossil assemblages has, however, remained unclear. In particular, the contribution of climate change to oceanographic changes, superimposed on long-term and gradual changes induced by tectonics, is still poorly understood. To disentangle the effects of tectonism and climate in the southwest Pacific Ocean, we target a climatic deviation from the long-term Eocene cooling trend: the Middle Eocene Climatic Optimum (MECO; ∼40 Ma). This 500 kyr phase of global warming was unrelated to regional tectonism, and thus provides a test case to investigate the ocean's physicochemical response to climate change alone. We reconstruct changes in surface-water circulation and temperature in and around the Tasmanian Gateway during the MECO through new palynological and organic geochemical records from the central Tasmanian Gateway (Ocean Drilling Program Site 1170), the Otway Basin (southeastern Australia), and the Hampden Beach section (New Zealand). Our results confirm that dinocyst communities track specific surface-ocean currents, yet the variability within the communities can be driven by superimposed temperature change. Together with published results from the east of the Tasmanian Gateway, our new results suggest a shift in surface-ocean circulation during the peak of MECO warmth. Simultaneous with high sea-surface temperatures in the Tasmanian Gateway area, pollen assemblages indicate warm temperate rainforests with paratropical elements along the southeastern margin of Australia. Finally, based on new age constraints, we suggest that a regional southeast Australian transgression might have been coincident with the MECO.

A range of future climate scenarios are projected for high atmospheric CO2 concentrations, given uncertainties over future human actions as well as potential environmental and climatic feedbacks. The geological record offers an opportunity to understand climate system response to a range of forcings and feedbacks which operate over multiple temporal and spatial scales. Here, we examine a single interglacial during the late Pliocene (KM5c, ca. 3.205±0.01 Ma) when atmospheric CO2 exceeded pre-industrial concentrations, but were similar to today and to the lowest emission scenarios for this century. As orbital forcing and continental configurations were almost identical to today, we are able to focus on equilibrium climate system response to modern and near-future CO2. Using proxy data from 32 sites, we demonstrate that global mean sea-surface temperatures were warmer than pre-industrial values, by ∼2.3 ∘C for the combined proxy data (foraminifera Mg∕Ca and alkenones), or by ∼3.2–3.4 ∘C (alkenones only). Compared to the pre-industrial period, reduced meridional gradients and enhanced warming in the North Atlantic are consistently reconstructed. There is broad agreement between data and models at the global scale, with regional differences reflecting ocean circulation and/or proxy signals. An uneven distribution of proxy data in time and space does, however, add uncertainty to our anomaly calculations. The reconstructed global mean sea-surface temperature anomaly for KM5c is warmer than all but three of the PlioMIP2 model outputs, and the reconstructed North Atlantic data tend to align with the warmest KM5c model values. Our results demonstrate that even under low-CO2 emission scenarios, surface ocean warming may be expected to exceed model projections and will be accentuated in the higher latitudes.

Soils represent the largest reservoir of organic carbon (OC) on land. Upon mobilization, this OC is either returned to the atmosphere as carbon dioxide (CO2) or transported and ultimately locked into (marine) sediments, where it will act as a long-term sink of atmospheric CO2. These fluxes of soil OC are, however, difficult to evaluate, mostly due to the lack of a soil-specific tracer. In this study, a suite of branched glycerol dialkyl glycerol tetraethers (brGDGTs), which are membrane lipids of soil bacteria, is tested as specific tracers for soil OC from source (soils under arable land, ley, grassland, and woodland) to sink (Loe Pool sediments) in a small catchment located in southwest England (i.e. Carminowe Creek draining into Loe Pool). The analysis of brGDGTs in catchment soils reveals that their distribution is not significantly different across different land use types (p>0.05) and thus does not allow land-use-specific soil contributions to Loe Pool sediments to be traced. Furthermore, the significantly higher contribution of 6-methyl brGDGT isomers in creek sediments (isomerization ratio (IR) = 0.48±0.10, mean ± standard deviation (SD); p) compared to that in catchment soils (IR = 0.28±0.11) indicates that the initial soil signal is substantially altered by brGDGT produced in situ. Similarly, the riverine brGDGT signal appears to be overwritten by lacustrine brGDGTs in the lake sedimentary record, indicated by remarkably lower methylation of branched tetraethers (MBT5ME′=0.46±0.02 in creek bed sediments and 0.38±0.01 in lake core sediments; p) and a higher degree of cyclization (DC = 0.23±0.02 in creek bed sediments and 0.32±0.08 in lake core sediments). Thus, in this small catchment, brGDGTs do not allow us to trace soil OC transport. Nevertheless, the downcore changes in the degree of cyclization and the abundance of isoprenoid GDGTs produced by methanogens in the Loe Pool sediment do reflect local environmental conditions over the past 100 years and have recorded the eutrophication history of the lake.

The mid-Piacenzian Warm Period (mPWP; 3264–3025 ka) represents the most recent interval in Earth's history where atmospheric CO2 levels were similar to today. The reconstruction of sea surface temperatures (SSTs) and climate modelling studies has shown that global temperatures were 2–4 ∘C warmer than present. However, detailed reconstructions of marginal seas and/or coastal zones, linking the coastal and continental climate evolution, are lacking. This is in part due to the absence of precise age models for coastal sedimentary successions, as they are generally formed by dynamic depositional systems with varying sediment and freshwater inputs. Here, we present a multi-proxy record of Pliocene climate change in the coastal southern North Sea basin (SNSB) based on the sedimentary record from borehole Hank, the Netherlands. The marginal marine setting of the Hank borehole during the late Pliocene provides an excellent opportunity to correlate marine and terrestrial signals due to continental sediment input mainly derived from the proto-Rhine–Meuse River. We improve the existing low-resolution palynology-based age model for the Hank borehole using stable oxygen and carbon isotope (δ18O and δ13C) measurements of the endobenthic foraminifera species Cassidulina laevigata, integrated with biochrono- and seismostratigraphy. Identification of hiatuses and freshwater effects in the record allows us to isolate glacial–interglacial climate signals in order to tune the endobenthic oxygen stable isotope record to a global benthic δ18O stack. This results in a tuned age framework for the SNSB for the late Pliocene (∼3190–2770 ka). Our multi-proxy climate reconstruction for the interval which covers part of the mPWP (∼3190–3000 ka) shows a strong agreement between lipid biomarker and palynology-based terrestrial temperature proxies, which suggest a stable climate, 1–2 ∘C warmer than present. In the marine realm, however, biomarker-based SSTs show a large range of variation (10 ∘C). Nevertheless, the fluctuation is comparable to other SST records from the North Atlantic and Nordic Seas, suggesting that a common factor, possibly ocean circulation, exerted a strong influence over SSTs in the North Atlantic and the North Sea at this time.

The scarcity of continuous, terrestrial, palaeoenvironmental records in eastern South Africa leaves the evolution of late Quaternary climate and its driving mechanisms uncertain. Here we use a ∼7 m long core from Mfabeni peatland (KwaZulu-Natal, South Africa) to reconstruct climate variability for the last 32 000 years (cal ka BP). We infer past vegetation and hydrological variability using stable carbon (δ13Cwax) and hydrogen isotopes (δDwax) of plant-wax n-alkanes and use Paq to reconstruct water table changes. Our results indicate that late Quaternary climate in eastern South Africa did not respond directly to orbital forcing or to changes in sea-surface temperatures (SSTs) in the western Indian Ocean. We attribute the arid conditions evidenced at Mfabeni during the Last Glacial Maximum (LGM) to low SSTs and an equatorward displacement of (i) the Southern Hemisphere westerlies, (ii) the subtropical high-pressure cell, and (iii) the South Indian Ocean Convergence Zone (SIOCZ), which we infer was linked to increased Antarctic sea-ice extent. The northerly location of the high-pressure cell and the SIOCZ inhibited moisture advection inland and pushed the rain-bearing cloud band north of Mfabeni, respectively. The increased humidity at Mfabeni between 19 and 14 cal kyr BP likely resulted from a southward retreat of the westerlies, the high-pressure cell, and the SIOCZ, consistent with a decrease in Antarctic sea-ice extent. Between 14 and 5 cal kyr BP, when the westerlies, the high-pressure cell, and the SIOCZ were in their southernmost position, local insolation became the dominant control, leading to stronger atmospheric convection and an enhanced tropical easterly monsoon. Generally drier conditions persisted during the past ca. 5 cal ka BP, probably resulting from an equatorward return of the westerlies, the high-pressure cell, and the SIOCZ. Higher SSTs and heightened El Niño–Southern Oscillation (ENSO) activity may have played a role in enhancing climatic variability during the past ca. 5 cal ka BP. Our findings highlight the influence of the latitudinal position of the westerlies, the high-pressure cell, and the SIOCZ in driving climatological and environmental changes in eastern South Africa.

As Arctic warming continues and permafrost thaws, more soil and sedimentary organic matter (OM) will be decomposed in northern high latitudes. Still, uncertainties remain in the quality of the OM and the size of the organic carbon (OC) pools stored in different deposit types of permafrost landscapes. This study presents OM data from deep permafrost and lake deposits on the Baldwin Peninsula which is located in the southern portion of the continuous permafrost zone in west Alaska. Sediment samples from yedoma and drained thermokarst lake basin (DTLB) deposits as well as thermokarst lake sediments were analyzed for cryostratigraphical and biogeochemical parameters and their lipid biomarker composition to identify the belowground OC pool size and OM quality of ice-rich permafrost on the Baldwin Peninsula. We provide the first detailed characterization of yedoma deposits on Baldwin Peninsula. We show that three-quarters of soil OC in the frozen deposits of the study region (total of 68 Mt) is stored in DTLB deposits (52 Mt) and one-quarter in the frozen yedoma deposits (16 Mt). The lake sediments contain a relatively small OC pool (4 Mt), but have the highest volumetric OC content (93 kg m−3) compared to the DTLB (35 kg m−3) and yedoma deposits (8 kg m−3), largely due to differences in the ground ice content. The biomarker analysis indicates that the OM in both yedoma and DTLB deposits is mainly of terrestrial origin. Nevertheless, the relatively high carbon preference index of plant leaf waxes in combination with a lack of a degradation trend with depth in the yedoma deposits indicates that OM stored in yedoma is less degraded than that stored in DTLB deposits. This suggests that OM in yedoma has a higher potential for decomposition upon thaw, despite the relatively small size of this pool. These findings show that the use of lipid biomarker analysis is valuable in the assessment of the potential future greenhouse gas emissions from thawing permafrost, especially because this area, close to the discontinuous permafrost boundary, is projected to thaw substantially within the 21st century.

The volume of the Antarctic continental ice sheet(s) varied substantially during the Oligocene and Miocene ( ∼ 34–5 Ma) from smaller to substantially larger than today, both on million-year and on orbital timescales. However, reproduction through physical modeling of a dynamic response of the ice sheets to climate forcing remains problematic, suggesting the existence of complex feedback mechanisms between the cryosphere, ocean, and atmosphere systems. There is therefore an urgent need to improve the models for better predictions of these systems, including resulting potential future sea level change. To assess the interactions between the cryosphere, ocean, and atmosphere, knowledge of ancient sea surface conditions close to the Antarctic margin is essential. Here, we present a new TEX86-based sea surface water paleotemperature record measured on Oligocene sediments from Integrated Ocean Drilling Program (IODP) Site U1356, offshore Wilkes Land, East Antarctica. The new data are presented along with previously published Miocene temperatures from the same site. Together the data cover the interval between ∼ 34 and ∼ 11 Ma and encompasses two hiatuses. This record allows us to accurately reconstruct the magnitude of sea surface temperature (SST) variability and trends on both million-year and glacial–interglacial timescales. On average, TEX86 values indicate SSTs ranging between 10 and 21 °C during the Oligocene and Miocene, which is on the upper end of the few existing reconstructions from other high-latitude Southern Ocean sites. SST maxima occur around 30.5, 25, and 17 Ma. Our record suggests generally warm to temperate ocean offshore Wilkes Land. Based on lithological alternations detected in the sedimentary record, which are assigned to glacial–interglacial deposits, a SST variability of 1.5–3.1 °C at glacial–interglacial timescales can be established. This variability is slightly larger than that of deep-sea temperatures recorded in Mg ∕ Ca data. Our reconstructed Oligocene temperature variability has implications for Oligocene ice volume estimates based on benthic δ18O records. If the long-term and orbital-scale SST variability at Site U1356 mirrors that of the nearby region of deep-water formation, we argue that a substantial portion of the variability and trends contained in long-term δ18O records can be explained by variability in Southern high-latitude temperature and that the Antarctic ice volume may have been less dynamic than previously thought. Importantly, our temperature record suggests that Oligocene–Miocene Antarctic ice sheets were generally of smaller size compared to today.

Long-chain diols (LCDs) occur widespread in marine environments and also in lakes and rivers. Transport of LCDs from rivers may impact the distribution of LCDs in coastal environments, however relatively little is known about the distribution and biological sources of LCDs in river systems. In this study, we investigated the distribution of LCDs in suspended particulate matter (SPM) of three river systems (Godavari, Danube, and Rhine) in relation with precipitation, temperature, and source catchments. The dominant long-chain diol is the C32 1,15-diol followed by the C30 1,15-diol in all studied river systems. In regions influenced by marine waters, such as delta systems, the fractional abundance of the C30 1,15-diol is substantially higher than in the river itself, suggesting different LCD producers in marine and freshwater environments. A change in the LCD distribution along the downstream transects of the rivers studied was not observed. However, an effect of river flow is observed; i.e., the concentration of the C32 1,15-diol is higher in stagnant waters such as reservoirs and during seasons with river low stands. A seasonal change in the LCD distribution was observed in the Rhine, likely due to a change in the producers. Eukaryotic diversity analysis by 18S rRNA gene sequencing of SPM from the Rhine showed extremely low abundances of sequences (i.e., < 0.32 % of total reads) related to known algal LCD producers. Furthermore, incubation of the river water with 13C-labeled bicarbonate did not result in 13C incorporation into LCDs. This indicates that the LCDs present are mainly of fossil origin in the fast-flowing part of the Rhine. Overall, our results suggest that the LCD producers in rivers predominantly reside in lakes or side ponds that are part of the river system.

The modern-day Godavari River transports large amounts of sediment (170 Tg per year) and terrestrial organic carbon (OCterr; 1.5 Tg per year) from peninsular India to the Bay of Bengal. The flux and nature of OCterr is considered to have varied in response to past climate and human forcing. In order to delineate the provenance and nature of organic matter (OM) exported by the fluvial system and establish links to sedimentary records accumulating on its adjacent continental margin, the stable and radiogenic isotopic composition of bulk OC, abundance and distribution of long-chain fatty acids (LCFAs), sedimentological properties (e.g. grain size, mineral surface area, etc.) of fluvial (riverbed and riverbank) sediments and soils from the Godavari basin were analysed and these characteristics were compared to those of a sediment core retrieved from the continental slope depocenter. Results show that river sediments from the upper catchment exhibit higher total organic carbon (TOC) contents than those from the lower part of the basin. The general relationship between TOC and sedimentological parameters (i.e. mineral surface area and grain size) of the sediments suggests that sediment mineralogy, largely driven by provenance, plays an important role in the stabilization of OM during transport along the river axis, and in the preservation of OM exported by the Godavari to the Bay of Bengal. The stable carbon isotopic (δ13C) characteristics of river sediments and soils indicate that the upper mainstream and its tributaries drain catchments exhibiting more 13C enriched carbon than the lower stream, resulting from the regional vegetation gradient and/or net balance between the upper (C4-dominated plants) and lower (C3-dominated plants) catchments. The radiocarbon contents of organic carbon (Δ14COC) in deep soils and eroding riverbanks suggests these are likely sources of old or pre-aged carbon to the Godavari River that increasingly dominates the late Holocene portion of the offshore sedimentary record. While changes in water flow and sediment transport resulting from recent dam construction have drastically impacted the flux, loci, and composition of OC exported from the modern Godavari basin, complicating reconciliation of modern-day river basin geochemistry with that recorded in continental margin sediments, such investigations provide important insights into climatic and anthropogenic controls on OC cycling and burial.

We assess the disputed phase relations between forcing and climatic response in the early Pleistocene with a spliced Gelasian (∼ 2.6–1.8 Ma) multi-proxy record from the southern North Sea basin. The cored sections couple climate evolution on both land and sea during the intensification of Northern Hemisphere glaciation (NHG) in NW Europe, providing the first well-constrained stratigraphic sequence of the classic terrestrial Praetiglian stage. Terrestrial signals were derived from the Eridanos paleoriver, a major fluvial system that contributed a large amount of freshwater to the northeast Atlantic. Due to its latitudinal position, the Eridanos catchment was likely affected by early Pleistocene NHG, leading to intermittent shutdown and reactivation of river flow and sediment transport. Here we apply organic geochemistry, palynology, carbonate isotope geochemistry, and seismostratigraphy to document both vegetation changes in the Eridanos catchment and regional surface water conditions and relate them to early Pleistocene glacial–interglacial cycles and relative sea level changes. Paleomagnetic and palynological data provide a solid integrated timeframe that ties the obliquity cycles, expressed in the borehole geophysical logs, to Marine Isotope Stages (MIS) 103 to 92, independently confirmed by a local benthic oxygen isotope record. Marine and terrestrial palynological and organic geochemical records provide high-resolution reconstructions of relative terrestrial and sea surface temperature (TT and SST), vegetation, relative sea level, and coastal influence.During the prominent cold stages MIS 98 and 96, as well as 94, the record indicates increased non-arboreal vegetation, low SST and TT, and low relative sea level. During the warm stages MIS 99, 97, and 95 we infer increased stratification of the water column together with a higher percentage of arboreal vegetation, high SST, and relative sea level maxima. The early Pleistocene distinct warm–cold alterations are synchronous between land and sea, but lead the relative sea level change by 3000–8000 years. The record provides evidence for a dominantly Northern Hemisphere-driven cooling that leads the glacial buildup and varies on the obliquity timescale. Southward migration of Arctic surface water masses during glacials, indicated by cool-water dinoflagellate cyst assemblages, is furthermore relevant for the discussion on the relation between the intensity of the Atlantic meridional overturning circulation and ice sheet growth.

We have performed incubation experiments in order to examine the behaviour of soil-derived branched glycerol dialkyl glycerol tetraether (brGDGT) membrane lipids upon entering an aquatic environment and to evaluate the processes that potentially take place during their fluvial transport from land to sea. We incubated a soil from the Rakaia River catchment on the South Island of New Zealand using Rakaia River water and ocean water collected near the river mouth as inocula for a period of up to 152 days. The concentrations, as well as the relative distribution of brGDGTs derived from intact polar ("living"; IPL) lipids and core ("fossil"; CL) lipids remained unaltered over the course of the experiment. Although the stability of the brGDGTs may be a consequence of the higher than natural soil : water ratio used in the laboratory experiment, the substantial increase (27–72%) in the total pool of isoprenoid GDGTs (isoGDGTs) in all incubation setups, including the control using distilled water, indicates that entering an aquatic environment does influence the behaviour of soil-derived GDGTs. However, the availability of water appears to be more important than its properties. As a consequence of increasing isoGDGT concentrations, a decrease in Branched and Isoprenoid Tetraether (BIT) index values – a proxy for the relative input of fluvially discharged soil material into a marine system – became evident after an incubation period of 30 days, with a maximum final decrease of 0.88 to 0.74 in the experiment with river water. The relative distribution within the isoGDGT pool shows changes with time, suggesting that isoGDGT producers may either have different rates of membrane adaptation or production/degradation, or that preferential release from the soil matrix or a shift in source organism(s) may take place. While the apparent stability of soil brGDGTs during this incubation experiment reinforces their potential as tracers for land–sea transport of soil organic carbon and their use in paleoclimate reconstructions, the distributional differences between GDGTs in river water and nearby soil, as well as in river and ocean water, indicate that further research is needed to pinpoint the sources of GDGTs that are ultimately discharged to the oceans and are subsequently archived in continental margin sediments.

δ18O values of pedogenic minerals forming from soil water are commonly used to reconstruct paleoelevation. To circumvent some of the disadvantages of this method, soil n-alkane δD values were recently proposed as a new tool to reconstruct elevation changes, after showing that soil n-alkane δD values track the altitude effect on precipitation δD variations (r2=0.73 along Mt. Gongga, China). To verify the suitability of soil n-alkane δD values as a paleoelevation proxy we measured the δD of soil n-alkanes along Mt. Kilimanjaro (Tanzania). At midslope, soil n-alkane δD values are possibly influenced by the present precipitation belt, causing D-depletion in precipitation, and hence in the soil n-alkanes. Consequently, soil n-alkane δD values do not linearly relate with altitude (r2=0.03), suggesting that, in this case, they can not serve as an unambiguous proxy to infer past elevation changes. In contrast, it was recently shown that the MBT/CBT temperature proxy, which is based on the distribution of branched glycerol dialkyl glycerol tetraether (GDGT) membrane lipids, is linearly related with MAT, and thus altitude (r2=0.77), at Mt. Kilimanjaro. This suggests that this proxy may be more suitable for paleoelevation reconstruction for this region. However, application of the MBT/CBT proxy on the altitude gradient along Mt. Gongga showed that, although the MBT/CBT-derived temperature lapse rate (−5.9°C/1000 m) resembles the measured temperature lapse rate (−6.0°C/1000 m), there is a relatively large degree of scatter (r2=0.55). Our results thus show that both proxies can be subject to relatively large uncertainties in their assessment of past elevation changes, but that a combination of the soil n-alkane δD and MBT/CBT proxies can likely result in a more reliable assessment of paleoelevation.

The northern margin of the Ligurian Basin shows notable seismicity at the Alpine front, including frequent magnitude 4 events. Seismicity decreases offshore towards the Basin centre and Corsica, revealing a diffuse distribution of low-magnitude earthquakes. We analyse data of the amphibious AlpArray seismic network with focus on the offshore component, the AlpArray ocean bottom seismometer (OBS) network, consisting of 24 broadband OBSs deployed for 8 months, to reveal the seismicity and depth distribution of micro-earthquakes beneath the Ligurian Sea. Two clusters occurred between ∼ 10 km to ∼ 16 km depth below the sea surface, within the lower crust and uppermost mantle. Thrust faulting focal mechanisms indicate compression and an inversion of the Ligurian Basin, which is an abandoned Oligocene–Miocene rift basin. The basin inversion is suggested to be related to the Africa–Europe plate convergence. The locations and focal mechanisms of seismicity suggest reactivation of pre-existing rift-related structures. Slightly different striking directions of presumed rift-related faults in the basin centre compared to faults further east and hence away from the rift basin may reflect the counter-clockwise rotation of the Corsica–Sardinia block. High mantle S-wave velocities and a low Vp/Vs ratio support the hypothesis of strengthening of crust and uppermost mantle during the Oligocene–Miocene rifting-related extension and thinning of continental crust.

Numerous proxy reconstructions have provided general insight into late Quaternary East Asian Monsoon variability. However, challenges persist in precisely assessing absolute temperature impacts on proxy variations. Here, we use two independent paleothermometers, based on bacterial membrane lipids and clumped isotopes of snail shells, in the same section of the western Chinese Loess Plateau to establish a robust land surface temperature record spanning the past approximately 21,000 years. Our independent temperature records consistently reveal (i) similar land surface temperatures between the Last Glacial Maximum and late Holocene and (ii) a gradual cooling Holocene, which contrasts with the climate model predictions. We propose that changes in soil moisture availability over the deglaciation modulates the land surface temperature recorded by the proxies. A land surface energy partitioning model confirms this mechanism, suggesting that effects of soil moisture availability should be properly considered when comparing proxy records with climate model outputs.

Rationale: Embedding resins are widely used to fix carbonates for high-precision sample preparation and high-resolution sampling. However, these embedding materials are difficult to remove after sample preparation and are known to affect the accuracy of carbonate stable isotope analyses. Nevertheless, their impact on clumped isotope analysis, which is particularly sensitive to contamination artifacts, has so far not been tested. The observation that running resin-containing samples decreased the reproducibility of clumped isotope values for internal laboratory carbonate standards and increased the external standard deviation (SD 0.061-0.088‰) compared to the long-term observations (0.034‰), prompted us to set up an experiment to test the influence of resin addition on instrument performance., Methods: Here we analyzed the stable and clumped isotope composition of a pure calcium carbonate standard (ETH-4) mixed with three types of embedding resins in 2:1 and 1:1 proportions. Our aim was to assess how resin addition affects isotope analyses., Results: We found that none of the stable isotopic values were significantly different. The δ 13 C values were -10.22 ± 0.07‰ (mean ± SD) for pure ETH-4, while the δ 13 C values of ETH-4 mixed with embedding resins in 2:1 and 1:1 proportions were -10.21 ± 0.06‰ and -10.18 ± 0.06‰, respectively (p > 0.05). The δ 18 O values were -18.82 ± 0.11‰ for pure ETH-4 versus -18.81 ± 0.09‰ and -18.82 ± 0.08‰ for 2:1 and 1:1 ETH-4:resin mixtures, respectively (p > 0.05). Given the large uncertainty in our results, we did not find significant differences between different mixtures in the carbonate clumped isotope values (Δ 47 ), with 0.458 ± 0.107‰, 0.464 ± 0.086‰, and 0.417 ± 0.089‰ in pure ETH-4 and ETH-4 with 2:1 and 1:1 resin mixtures, respectively (p > 0.05). However, a resin-related bias in the results might be masked by the large uncertainty. The measured ETH-4 values in our study are similar to the InterCarb values (δ 13 C = -10.20‰, δ 18 O = -18.81‰, Δ 47  = 0.450‰, InterCarb-Carbon Dioxide Equilibrium Scale). However, the external SD of Δ 47 in sessions measuring ETH-4 with resins is higher than in sessions without deliberate resin addition for the same measuring period., Conclusions: We find that the potential contamination from the resin addition leads to a larger variability for Δ 47 values in sessions measuring ETH-4 including resins. We therefore recommend purification of embedded samples using a contamination trap with Porapak prior to analysis, if possible, or avoiding resins during sample preparation and workup, as well as monitoring the measurement quality during and after sessions with samples containing embedding resins., (© 2023 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.)

Anthropogenic climate change is predicted to severely impact the global hydrological cycle 1 , particularly in tropical regions where agriculture-based economies depend on monsoon rainfall 2 . In the Horn of Africa, more frequent drought conditions in recent decades 3,4 contrast with climate models projecting precipitation to increase with rising temperature 5 . Here we use organic geochemical climate-proxy data from the sediment record of Lake Chala (Kenya and Tanzania) to probe the stability of the link between hydroclimate and temperature over approximately the past 75,000 years, hence encompassing a sufficiently wide range of temperatures to test the 'dry gets drier, wet gets wetter' paradigm 6 of anthropogenic climate change in the time domain. We show that the positive relationship between effective moisture and temperature in easternmost Africa during the cooler last glacial period shifted to negative around the onset of the Holocene 11,700 years ago, when the atmospheric carbon dioxide concentration exceeded 250 parts per million and mean annual temperature approached modern-day values. Thus, at that time, the budget between monsoonal precipitation and continental evaporation 7 crossed a tipping point such that the positive influence of temperature on evaporation became greater than its positive influence on precipitation. Our results imply that under continued anthropogenic warming, the Horn of Africa will probably experience further drying, and they highlight the need for improved simulation of both dynamic and thermodynamic processes in the tropical hydrological cycle., (© 2023. The Author(s).)

Quantitative reconstructions of hydrological change during ancient greenhouse warming events provide valuable insight into warmer-than-modern hydrological cycles but are limited by paleoclimate proxy uncertainties. We present sea surface temperature (SST) records and seawater oxygen isotope (δ 18 O sw ) estimates for the Middle Eocene Climatic Optimum (MECO), using coupled carbonate clumped isotope (Δ 47 ) and oxygen isotope (δ 18 O c ) data of well-preserved planktonic foraminifera from the North Atlantic Newfoundland Drifts. These indicate a transient ~3°C warming across the MECO, with absolute temperatures generally in accordance with trace element (Mg/Ca)-based SSTs but lower than biomarker-based SSTs for the same interval. We find a transient ~0.5‰ shift toward higher δ 18 O sw , which implies increased salinity in the North Atlantic subtropical gyre and potentially a poleward expansion of its northern boundary in response to greenhouse warming. These observations provide constraints on dynamic ocean response to warming events, which are consistent with theory and model simulations predicting an enhanced hydrological cycle under global warming.

Some lipid-biomarker-based sea surface temperature (SST) proxies applied in the modern Mediterranean Sea exhibit large offsets from expected values, generating uncertainties in climate reconstructions. Lateral transport of proxy carriers along ocean currents prior to burial can contribute to this offset between reconstructed and expected SSTs. We perform virtual particle tracking experiments to simulate transport prior to and during sinking and derive a quantitative estimate of transport bias for alkenones and glycerol dibiphytanyl glycerol tetraethers (GDGTs), which form the basis of the U K' 37 and TEX 86 paleothermometers, respectively. We use a simple 30-day surface advection scenario and sinking speeds appropriate for the export of various proxy carriers (6, 12, 25, 50, 100, 250, 500, and 1000 md -1 ). For the assessed scenarios, lateral transport bias is generally small (always <0.85°C) within the Mediterranean Sea and does not substantially contribute to uncertainties in U K' 37 - or TEX 86 -based SSTs., (© 2022. The Authors.)

The end-Permian mass extinction event (∼252 Mya) is associated with one of the largest global carbon cycle perturbations in the Phanerozoic and is thought to be triggered by the Siberian Traps volcanism. Sizable carbon isotope excursions (CIEs) have been found at numerous sites around the world, suggesting massive quantities of 13 C-depleted CO 2 input into the ocean and atmosphere system. The exact magnitude and cause of the CIEs, the pace of CO 2 emission, and the total quantity of CO 2 , however, remain poorly known. Here, we quantify the CO 2 emission in an Earth system model based on new compound-specific carbon isotope records from the Finnmark Platform and an astronomically tuned age model. By quantitatively comparing the modeled surface ocean pH and boron isotope pH proxy, a massive (∼36,000 Gt C) and rapid emission (∼5 Gt C yr -1 ) of largely volcanic CO 2 source (∼-15%) is necessary to drive the observed pattern of CIE, the abrupt decline in surface ocean pH, and the extreme global temperature increase. This suggests that the massive amount of greenhouse gases may have pushed the Earth system toward a critical tipping point, beyond which extreme changes in ocean pH and temperature led to irreversible mass extinction. The comparatively amplified CIE observed in higher plant leaf waxes suggests that the surface waters of the Finnmark Platform were likely out of equilibrium with the initial massive centennial-scale release of carbon from the massive Siberian Traps volcanism, supporting the rapidity of carbon injection. Our modeling work reveals that carbon emission pulses are accompanied by organic carbon burial, facilitated by widespread ocean anoxia., Competing Interests: The authors declare no competing interest., (Copyright © 2021 the Author(s). Published by PNAS.)

Enhanced nutrient input and warming have led to the development of low oxygen (hypoxia) in coastal waters globally. For many coastal areas, insight into redox conditions prior to human impact is lacking. Here, we reconstructed bottom water redox conditions and sea surface temperatures (SSTs) for the coastal Stockholm Archipelago over the past 3000 yr. Elevated sedimentary concentrations of molybdenum indicate (seasonal) hypoxia between 1000 b.c.e. and 1500 c.e. Biomarker-based (TEX 86 ) SST reconstructions indicate that the recovery from hypoxia after 1500 c.e. coincided with a period of significant cooling (∼ 2°C), while human activity in the study area, deduced from trends in sedimentary lead and existing paleobotanical and archeological records, had significantly increased. A strong increase in sedimentary lead and zinc, related to more intense human activity in the 18 th and 19 th century, and the onset of modern warming precede the return of hypoxia in the Stockholm Archipelago. We conclude that climatic cooling played an important role in the recovery from natural hypoxia after 1500 c.e., but that eutrophication and warming, related to modern human activity, led to the return of hypoxia in the 20 th century. Our findings imply that ongoing global warming may exacerbate hypoxia in the coastal zone of the Baltic Sea., Competing Interests: None declared., (© 2020 The Authors. Limnology and Oceanography published by Wiley Periodicals LLC on behalf of Association for the Sciences of Limnology and Oceanography.)

Several studies indicate that North Atlantic Deep Water (NADW) formation might have initiated during the globally warm Eocene (56-34 Ma). However, constraints on Eocene surface ocean conditions in source regions presently conducive to deep water formation are sparse. Here we test whether ocean conditions of the middle Eocene Labrador Sea might have allowed for deep water formation by applying (organic) geochemical and palynological techniques, on sediments from Ocean Drilling Program (ODP) Site 647. We reconstruct a long-term sea surface temperature (SST) drop from ~30°C to ~27°C between 41.5 to 38.5 Ma, based on TEX 86 . Superimposed on this trend, we record ~2°C warming in SST associated with the Middle Eocene Climatic Optimum (MECO; ~40 Ma), which is the northernmost MECO record as yet, and another, likely regional, warming phase at ~41.1 Ma, associated with low-latitude planktic foraminifera and dinoflagellate cyst incursions. Dinoflagellate cyst assemblages together with planktonic foraminiferal stable oxygen isotope ratios overall indicate low surface water salinities and strong stratification. Benthic foraminifer stable carbon and oxygen isotope ratios differ from global deep ocean values by 1-2‰ and 2-4‰, respectively, indicating geographic basin isolation. Our multiproxy reconstructions depict a consistent picture of relatively warm and fresh but also highly variable surface ocean conditions in the middle Eocene Labrador Sea. These conditions were unlikely conducive to deep water formation. This implies either NADW did not yet form during the middle Eocene or it formed in a different source region and subsequently bypassed the southern Labrador Sea., (©2020. The Authors.)

Earthworms co-determine whether soil, as the largest terrestrial carbon reservoir, acts as source or sink for photosynthetically fixed CO 2 . However, conclusive evidence for their role in stabilising or destabilising soil carbon has not been fully established. Here, we demonstrate that earthworms function like biochemical reactors by converting labile plant compounds into microbial necromass in stabilised carbon pools without altering bulk measures, such as the total carbon content. We show that much of this microbial carbon is not associated with mineral surfaces and emphasise the functional importance of particulate organic matter for long-term carbon sequestration. Our findings suggest that while earthworms do not necessarily affect soil organic carbon stocks, they do increase the resilience of soil carbon to natural and anthropogenic disturbances. Our results have implications for climate change mitigation and challenge the assumption that mineral-associated organic matter is the only relevant pool for soil carbon sequestration., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2019.)

Current climate change may induce positive carbon cycle feedbacks that amplify anthropogenic warming on time scales of centuries to millennia. Similar feedbacks might have been active during a phase of carbon cycle perturbation and global warming, termed the Paleocene-Eocene Thermal Maximum (PETM, 56 million years ago). The PETM may help constrain these feedbacks and their sensitivity to warming. We present new high-resolution carbon isotope and sea surface temperature data from Ocean Drilling Program Site 959 in the Equatorial Atlantic. With these and existing data from the New Jersey Shelf and Maud Rise, Southern Ocean, we quantify the lead-lag relation between PETM warming and the carbon input that caused the carbon isotope excursion (CIE). We show ~2 °C of global warming preceded the CIE by millennia, strongly implicating CO 2 -driven warming triggered a positive carbon cycle feedback. We further compile new and published barium (Ba) records encompassing continental shelf, slope, and deep ocean settings. Based on this compilation, we calculate that average Ba burial rates approximately tripled during the PETM, which may require an additional source of Ba to the ocean. Although the precipitation pathway is not well constrained, dissolved Ba stored in sulfate-depleted pore waters below methane hydrates could represent an additional source. We speculate the most complete explanation for early warming and rise in Ba supply is that hydrate dissociation acted as a positive feedback and caused the CIE. These results imply hydrates are more temperature sensitive than previously considered, and may warrant reconsideration of the political assignment of 2 °C warming as a safe future scenario.

Palaeoclimate reconstructions of periods with warm climates and high atmospheric CO 2 concentrations are crucial for developing better projections of future climate change. Deep-ocean 1,2 and high-latitude 3 palaeotemperature proxies demonstrate that the Eocene epoch (56 to 34 million years ago) encompasses the warmest interval of the past 66 million years, followed by cooling towards the eventual establishment of ice caps on Antarctica. Eocene polar warmth is well established, so the main obstacle in quantifying the evolution of key climate parameters, such as global average temperature change and its polar amplification, is the lack of continuous high-quality tropical temperature reconstructions. Here we present a continuous Eocene equatorial sea surface temperature record, based on biomarker palaeothermometry applied on Atlantic Ocean sediments. We combine this record with the sparse existing data 4-6 to construct a 26-million-year multi-proxy, multi-site stack of Eocene tropical climate evolution. We find that tropical and deep-ocean temperatures changed in parallel, under the influence of both long-term climate trends and short-lived events. This is consistent with the hypothesis that greenhouse gas forcing 7,8 , rather than changes in ocean circulation 9,10 , was the main driver of Eocene climate. Moreover, we observe a strong linear relationship between tropical and deep-ocean temperatures, which implies a constant polar amplification factor throughout the generally ice-free Eocene. Quantitative comparison with fully coupled climate model simulations indicates that global average temperatures were about 29, 26, 23 and 19 degrees Celsius in the early, early middle, late middle and late Eocene, respectively, compared to the preindustrial temperature of 14.4 degrees Celsius. Finally, combining proxy- and model-based temperature estimates with available CO 2 reconstructions 8 yields estimates of an Eocene Earth system sensitivity of 0.9 to 2.3 kelvin per watt per square metre at 68 per cent probability, consistent with the high end of previous estimates 11 .

The geological record contains evidence for numerous pronounced perturbations in the global carbon cycle, some of which are associated with mass extinction. In the Carnian (Late Triassic), evidence from sedimentology and fossil pollen points to a significant change in climate, resulting in biotic turnover, during a time termed the 'Carnian Pluvial Episode' (CPE). Evidence from the marine realm suggests a causal relationship between the CPE, a global 'wet' period, and the injection of light carbon into the atmosphere. Here we provide the first evidence from a terrestrial stratigraphic succession of at least five significant negative C-isotope excursions (CIE)'s through the CPE recorded in both bulk organic carbon and compound specific plant leaf waxes. Furthermore, construction of a floating astronomical timescale for 1.09 Ma of the Late Triassic, based on the recognition of 405 ka eccentricity cycles in elemental abundance and gamma ray (GR) data, allows for the estimation of a duration for the isotope excursion(s). Source mixing calculations reveal that the observed substantial shift(s) in δ 13 C was most likely caused by a combination of volcanic emissions, subsequent warming and the dissociation of methane clathrates.

The first step of nitrification is catalysed by both ammonia-oxidizing bacteria (AOB) and archaea (AOA), but physicochemical controls on the relative abundance and function of these two groups are not yet fully understood, especially in freshwater environments. This study investigated ammonia-oxidizing populations in nitrifying rotating biological contactors (RBCs) from a municipal wastewater treatment plant. Individual RBC stages are arranged in series, with nitrification at each stage creating an ammonia gradient along the flowpath. This RBC system provides a valuable experimental system for testing the hypothesis that ammonia concentration determines the relative abundance of AOA and AOB. The results demonstrate that AOA increased as ammonium decreased across the RBC flowpath, as indicated by qPCR for thaumarchaeal amoA and 16S rRNA genes, and core lipid (CL) and intact polar lipid (IPL) crenarchaeol abundances. Overall, there was a negative logarithmic relationship (R(2) =0.51) between ammonium concentration and the relative abundance of AOA amoA genes. A single AOA population was detected in the RBC biofilms; this phylotype shared low amoA and 16S rRNA gene homology with existing AOA cultures and enrichments. These results provide evidence that ammonia availability influences the relative abundances of AOA and AOB, and that AOA are abundant in some municipal wastewater treatment systems., (© 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.)