Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

Neogene burial of organic carbon in the global ocean.

Organic carbon buried in marine sediment serves as a net sink for atmospheric carbon dioxide and a source of oxygen1,2. The rate of organic carbon burial through geologic history is conventionally established by using the mass balance between inorganic and organic carbon, each with distinct carbon isotopic values (δ13C)3,4. This method is complicated by large uncertainties, however, and has not been tested with organic carbon accumulation data5,6. Here we report a 'bottom-up' approach for calculating the rate of organic carbon burial that is independent from mass balance calculations. We use data from 81 globally distributed sites to establish the history of organic carbon burial during the Neogene (roughly 23-3 Ma). Our results show larger spatiotemporal variability of organic carbon burial than previously estimated7-9. Globally, the burial rate is high towards the early Miocene and Pliocene and lowest during the mid-Miocene, with the latter period characterized by the lowest ratio of organic-to-carbonate burial rates. This is in contrast to earlier work that interpreted enriched carbonate 13C values of the mid-Miocene as massive organic carbon burial (that is, the Monterey Hypothesis)10,11. Suppressed organic carbon burial during the warm mid-Miocene is probably related to temperature-dependent bacterial degradation of organic matter12,13, suggesting that the organic carbon cycle acted as positive feedback of past global warming.

The PhanSST global database of Phanerozoic sea surface temperature proxy data.

Paleotemperature proxy data form the cornerstone of paleoclimate research and are integral to understanding the evolution of the Earth system across the Phanerozoic Eon. Here, we present PhanSST, a database containing over 150,000 data points from five proxy systems that can be used to estimate past sea surface temperature. The geochemical data have a near-global spatial distribution and temporally span most of the Phanerozoic. Each proxy value is associated with consistent and queryable metadata fields, including information about the location, age, and taxonomy of the organism from which the data derive. To promote transparency and reproducibility, we include all available published data, regardless of interpreted preservation state or vital effects. However, we also provide expert-assigned diagenetic assessments, ecological and environmental flags, and other proxy-specific fields, which facilitate informed and responsible reuse of the database. The data are quality control checked and the foraminiferal taxonomy has been updated. PhanSST will serve as a valuable resource to the paleoclimate community and has myriad applications, including evolutionary, geochemical, diagenetic, and proxy calibration studies.

Oceanic nutrient rise and the late Miocene inception of Pacific oxygen-deficient zones.

The modern Pacific Ocean hosts the largest oxygen-deficient zones (ODZs), where oxygen concentrations are so low that nitrate is used to respire organic matter. The history of the ODZs may offer key insights into ocean deoxygenation under future global warming. In a 12-My record from the southeastern Pacific, we observe a >10‰ increase in foraminifera-bound nitrogen isotopes (15N/14N) since the late Miocene (8 to 9 Mya), indicating large ODZs expansion. Coinciding with this change, we find a major increase in the nutrient content of the ocean, reconstructed from phosphorus and iron measurements of hydrothermal sediments at the same site. Whereas global warming studies cast seawater oxygen concentrations as mainly dependent on climate and ocean circulation, our findings indicate that modern ODZs are underpinned by historically high concentrations of seawater phosphate.

Persistent high latitude amplification of the Pacific Ocean over the past 10 million years.

While high latitude amplification is seen in modern observations, paleoclimate records, and climate modeling, better constraints on the magnitude and pattern of amplification would provide insights into the mechanisms that drive it, which remain actively debated. Here we present multi-proxy multi-site paleotemperature records over the last 10 million years from the Western Pacific Warm Pool (WPWP) - the warmest endmember of the global ocean that is uniquely important in the global radiative feedback change. These sea surface temperature records, based on lipid biomarkers and seawater Mg/Ca-adjusted foraminiferal Mg/Ca, unequivocally show warmer WPWP in the past, and a secular cooling over the last 10 million years. Compiling these data with existing records reveals a persistent, nearly stationary, extratropical response pattern in the Pacific in which high latitude (~50°N) temperatures increase by ~2.4° for each degree of WPWP warming. This relative warming pattern is also evident in model outputs of millennium-long climate simulations with quadrupling atmospheric CO2, therefore providing a strong constraint on the future equilibrium response of the Earth System.

Archaeal lipids trace ecology and evolution of marine ammonia-oxidizing archaea.

Archaeal membrane lipids are widely used for paleotemperature reconstructions, yet these molecular fossils also bear rich information about ecology and evolution of marine ammonia-oxidizing archaea (AOA). Here we identified thermal and nonthermal behaviors of archaeal glycerol dialkyl glycerol tetraethers (GDGTs) by comparing the GDGT-based temperature index (TEX86) to the ratio of GDGTs with two and three cyclopentane rings (GDGT-2/GDGT-3). Thermal-dependent biosynthesis should increase TEX86 and decrease GDGT-2/GDGT-3 when the ambient temperature increases. This presumed temperature-dependent (PTD) trend is observed in GDGTs derived from cultures of thermophilic and mesophilic AOA. The distribution of GDGTs in suspended particulate matter (SPM) and sediments collected from above the pycnocline-shallow water samples-also follows the PTD trend. These similar GDGT distributions between AOA cultures and shallow water environmental samples reflect shallow ecotypes of marine AOA. While there are currently no cultures of deep AOA clades, GDGTs derived from deep water SPM and marine sediment samples exhibit nonthermal behavior deviating from the PTD trend. The presence of deep AOA increases the GDGT-2/GDGT-3 ratio and distorts the temperature-controlled correlation between GDGT-2/GDGT-3 and TEX86. We then used Gaussian mixture models to statistically characterize these diagnostic patterns of modern AOA ecology from paleo-GDGT records to infer the evolution of marine AOA from the Mid-Mesozoic to the present. Long-term GDGT-2/GDGT-3 trends suggest a suppression of today's deep water marine AOA during the Mesozoic-early Cenozoic greenhouse climates. Our analysis provides invaluable insights into the evolutionary timeline and the expansion of AOA niches associated with major oceanographic and climate changes.

Exploration of walnut components and their association with health effects.

Traditionally, walnuts have occupied an imperative position in the functional food market with consistently recognized nutritious and functional properties. In the past years, the lipid profile of walnuts has brought much scientific attention via linking a cascade of biological attributes and health-promoting effects. Over time, researchers have focused on diversified composition (polyphenols and vitamins) of different parts of walnut (flower, pellicle, and kernel) and emphasized their physiological significance. Consequently, a plethora of reports has emerged on the potential role of walnut consumption against a series of diseases including cancer, gut dysbiosis, cardiovascular, and neurodegenerative diseases. Therefore, we accumulated the updated data on composition and classification, extraction methods, and utilization of different parts of walnuts as well as associated beneficial effects under in vivo and clinical studies. Altogether, this review summarized the ameliorative effects of a walnut-enriched diet in chronic diseases which can be designated to the synergistic or individual effects of walnut components mainly through anti-oxidative and anti-inflammatory role.

Past climates inform our future.

As the world warms, there is a profound need to improve projections of climate change. Although the latest Earth system models offer an unprecedented number of features, fundamental uncertainties continue to cloud our view of the future. Past climates provide the only opportunity to observe how the Earth system responds to high carbon dioxide, underlining a fundamental role for paleoclimatology in constraining future climate change. Here, we review the relevancy of paleoclimate information for climate prediction and discuss the prospects for emerging methodologies to further insights gained from past climates. Advances in proxy methods and interpretations pave the way for the use of past climates for model evaluation-a practice that we argue should be widely adopted.

Comparison of phenolic compounds extracted from Diaphragma juglandis fructus, walnut pellicle, and flowers of Juglans regia using methanol, ultrasonic wave, and enzyme assisted-extraction.

The phenols in Diaphragma juglandis fructus (DJF), walnut pellicle (WP), and flowers of Juglans regia (FJR) from walnut were extracted using three methods (methanolic condensation reflux extraction, ultrasonic wave extraction, and enzyme assisted-extraction), and phenolics and antioxidant capacities of different extractions were compared. Overall, 50 phenolics were identified by HPLC-MS/MS with 41 compounds in DJF, 32 in WP, and 29 in FJR. It was observed that tannins in WP was higher than those in DJF and FJR. As for PCA, more than 70% of the variance was explained with the obvious comparison between the phenolic constituents. The phenolics in walnut contributed to remarkable antioxidant effect, with the highest effect observed in WP. This study presents the analysis and comparison of the phenols can be further extended for the development of functional walnut instant foods.

Comparative study of chemical compositions and antioxidant activities of Zhizi fruit extracts from different regions.

The fruits of Gardenia jasminoides Ellis are folk medicines in China and their major components are geniposide and water soluble pigment crocins. This study compared the chemical profiles and free radical scavenging activities of two Zhizi species from five provinces of China, including Jiangxi, Anhui, Hunan, Sichuan and Henan. The results showed that Jiangxi Zhizi contained higher levels of volatiles (71.84%), crocins (20.38 mg/g), geniposide (31.36 mg/g) and flavonoids (84.42 µg quercetin/mg) than four other Zhizi fruits; whereas Hunan Zhizi provided higher total phenolics (33.81 µg catechin/mg) and ABTS/DPPH radical scavenging activities. These findings implied that Jiangxi Zhizi would be suitable for extraction of gardenia yellow and geniposide, as well as preparation of essential oil. This information may provide valuable guidance for application of Zhizi fruits to biomedicine industry in China.

Low CO2 levels of the entire Pleistocene epoch.

Quantifying ancient atmospheric pCO2 provides valuable insights into the interplay between greenhouse gases and global climate. Beyond the 800-ky history uncovered by ice cores, discrepancies in both the trend and magnitude of pCO2 changes remain among different proxy-derived results. The traditional paleosol pCO2 paleobarometer suffers from largely unconstrained soil-respired CO2 concentration (S(z)). Using finely disseminated carbonates precipitated in paleosols from the Chinese Loess Plateau, here we identified that their S(z) can be quantitatively constrained by soil magnetic susceptibility. Based on this approach, we reconstructed pCO2 during 2.6-0.9 Ma, which documents overall low pCO2 levels (<300 ppm) comparable with ice core records, indicating that the Earth system has operated under late Pleistocene pCO2 levels for an extended period. The pCO2 levels do not show statistically significant differences across the mid-Pleistocene Transition (ca. 1.2-0.8 Ma), suggesting that CO2 is probably not the driver of this important climate change event.

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.

Response to Comment on "A 12-million-year temperature history of the tropical Pacific Ocean".

Contrary to our conclusions, Ravelo et al. argue that our TEX86-based sea surface temperature (SST) records do not conflict with the supposition of "permanent El Niño-like" conditions during the early Pliocene. We show that the way Ravelo et al. treat the existing temperature data perpetuates an inaccurate impression of cooler Pacific warm-pool SSTs and low equatorial temperature gradients in the past.

A 12-million-year temperature history of the tropical Pacific Ocean.

The appearance of permanent El Niño-like conditions prior to 3 million years ago is founded on sea-surface temperature (SST) reconstructions that show invariant Pacific warm pool temperatures and negligible equatorial zonal temperature gradients. However, only a few SST records are available, and these are potentially compromised by changes in seawater chemistry, diagenesis, and calibration limitations. For this study, we establish new biomarker-SST records and show that the Pacific warm pool was ~4°C warmer 12 million years ago. Both the warm pool and cold tongue slowly cooled toward modern conditions while maintaining a zonal temperature gradient of ~3°C in the late Miocene, which increased during the Plio-Pleistocene. Our results contrast with previous temperature reconstructions that support the supposition of a permanent El Niño-like state.

A 40-million-year history of atmospheric CO(2).

The alkenone-pCO2 methodology has been used to reconstruct the partial pressure of ancient atmospheric carbon dioxide (pCO2) for the past 45 million years of Earth's history (Middle Eocene to Pleistocene epochs). The present long-term CO2 record is a composite of data from multiple ocean localities that express a wide range of oceanographic and algal growth conditions that potentially bias CO2 results. In this study, we present a pCO2 record spanning the past 40 million years from a single marine locality, Ocean Drilling Program Site 925 located in the western equatorial Atlantic Ocean. The trends and absolute values of our new CO2 record site are broadly consistent with previously published multi-site alkenone-CO2 results. However, new pCO2 estimates for the Middle Miocene are notably higher than published records, with average pCO2 concentrations in the range of 400-500 ppm. Our results are generally consistent with recent pCO2 estimates based on boron isotope-pH data and stomatal index records, and suggest that CO2 levels were highest during a period of global warmth associated with the Middle Miocene Climatic Optimum (17-14 million years ago, Ma), followed by a decline in CO2 during the Middle Miocene Climate Transition (approx. 14 Ma). Several relationships remain contrary to expectations. For example, benthic foraminiferal δ(18)O records suggest a period of deglaciation and/or high-latitude warming during the latest Oligocene (27-23 Ma) that, based on our results, occurred concurrently with a long-term decrease in CO2 levels. Additionally, a large positive δ(18)O excursion near the Oligocene-Miocene boundary (the Mi-1 event, approx. 23 Ma), assumed to represent a period of glacial advance and retreat on Antarctica, is difficult to explain by our CO2 record alone given what is known of Antarctic ice sheet history and the strong hysteresis of the East Antarctic Ice Sheet once it has grown to continental dimensions. We also demonstrate that in the Neogene with low CO2 levels, algal carbon concentrating mechanisms and spontaneous biocarbonate-CO2 conversions are likely to play a more important role in algal carbon fixation, which provides a potential bias to the alkenone-pCO2 method.

Temperature and pH controls on glycerol dibiphytanyl glycerol tetraether lipid composition in the hyperthermophilic crenarchaeon Acidilobus sulfurireducens.

Cyclization in glycerol dibiphytanyl glycerol tetraethers (GDGTs) results in internal cyclopentane moieties which are believed to confer thermal stability to crenarchaeal membranes. While the average number of rings per GDGT lipid (ring index) is positively correlated with temperature in many temperate environments, poor correlations are often observed in geothermal environments, suggesting that additional parameters may influence GDGT core lipid composition in these systems. However, the physical and chemical parameters likely to influence GDGT cyclization which are often difficult to decouple in geothermal systems, making it challenging to assess their influence on lipid composition. In the present study, the influence of temperature (range 65-81°C), pH (range 3.0-5.0), and ionic strength (range 10.1-55.7 mM) on GDGT core lipid composition was examined in the hyperthermoacidophile Acidilobus sulfurireducens, a crenarchaeon originally isolated from a geothermal spring in Yellowstone National Park, Wyoming. When cultivated under defined laboratory conditions, the composition of individual and total GDGTs varied significantly with temperature and to a lesser extent with the pH of the growth medium. Ionic strength over the range of values tested did not influence GDGT composition. The GDGT core lipid ring index was positively correlated with temperature and negatively correlated with pH, suggesting that A. sulfurireducens responds to increasing temperature and acidity by increasing the number of cyclopentyl rings in GDGT core membrane lipids.