Sedimentary Paleoenvironment and Organic Matter Enrichment Characteristics of Lacustrine Shahezi Shale in Songliao Basin: Insights from the Continental Scientific Drilling.

The lacustrine shale of the Shahezi Formation in the Songliao Basin has obvious organic matter enrichment characteristics and great potential for oil and gas resources. At present, the understanding of the sedimentary paleoenvironment and organic matter enrichment characteristics of the lacustrine shale of the Shahezi Formation is relatively weak. Therefore, taking the international continental scientific drilling Program (ICDP) borehole Songke-2 (SK-2) with continuous and whole Shahezi cores as the research object, combined with organic geochemistry, elemental geochemistry, and logging data, the sedimentary paleoenvironment and organic matter enrichment mechanism were studied. The results show that the organic matter of Shahezi shale is generally in the high to over mature stage. The kerogen type of organic matter is mainly II2-III. The organic matter is mainly derived from the lake basin's own algae and terrestrial higher plants. The total organic carbon (TOC) content of Shahezi shale is relatively high, and the TOC is mainly distributed between 1% and 2%. The Shahezi Formation is dominated by clay shale and siliceous shale, and experienced moderate chemical weathering during deposition. According to the analysis of organic geochemistry and elemental geochemistry data, the paleoenvironment of organic matter deposition in Shahezi shale was dominated by warm and humid climate in the early stage, and then experienced multiple cooling and arid periods. The climate type turned to semihumid-semiarid, with stable terrigenous debris input, low deposition rate, brackish water salinity and oxygen-rich-oxygen-poor water environment. The sedimentary period of Shahezi Formation is in the Cretaceous oceanic anoxic Aptian-Albian stage. During the oceanic anoxic event, the anoxic sedimentary environment and the frequent volcanic activity have an important impact on the organic matter enrichment. The oceanic anoxic event and volcanic activity are the main causes of water body hypoxia in the lake basin. The nutrients brought by volcanic activity are also one of the reasons for promoting the growth of lake basin organisms, creating good conditions for organic matter enrichment. The enrichment of organic matter in Shahezi Formation is the result of the interaction and coupling of various factors such as paleoclimate, paleoenvironment, paleoproductivity, water environment, terrestrial input, and major geological events. And, the organic matter enrichment model of Shahezi Formation shale is established.

Strengthening the argument for a large Greater India.

The Sangdanlin section in southern Tibet represents a geologic Rosetta stone to constrain the initiation of the India-Asia collision from its sedimentary and paleomagnetic records. However, geoscientists have arrived at fundamentally divergent interpretations surrounding the age of the strata and its paleomagnetic record. Here, we report paleontologic, petrographic, and paleomagnetic data from the Sangdanlin section that recognize the sequence as a thrust complex containing interlaced Barremian-Albian (Early Cretaceous) and Paleocene strata, each separated by thrust faults. Recognizing two complexly interwoven formations of distinctly different ages contradicts a continuous stratigraphic superposition. Assigning an Early Cretaceous, instead of Paleocene, age to the units collected for paleomagnetic data revises paleogeographic models thereby supporting a large (2,000 to 3,000 km) extent of Greater India, with collision initiating at 55 ± 5 Ma in the western Himalayas. A contiguous plate in the Neotethys Ocean precludes that Asia's southern margin was built through a succession of accreted terrains.

CO2-forced Late Miocene cooling and ecosystem reorganizations in East Asia.

In parallel with pronounced cooling in the oceans, vast areas of the continents experienced enhanced aridification and restructuring of vegetation and animal communities during the Late Miocene. Debate continues over whether pCO2-induced global cooling was the primary driver of this climate and ecosystem upheaval on land. Here we present an 8 to 5 Ma land surface temperatures (LST) record from East Asia derived from paleosol carbonate clumped isotopes and integrated with climate model simulations. The LST cooled by ~7 °C between 7.5 and 5.7 Ma, followed by rapid warming across the Miocene-Pliocene transition (5.5 to 5 Ma). These changes occurred synchronously with variations in alkenone and Mg/Ca-based sea surface temperatures and with hydroclimate and ecosystem shifts in East Asia, highlighting a global climate forcing mechanism. Our modeling experiments additionally demonstrate that pCO2-forced cooling would have altered moisture transfer and pathways and driven extensive aridification in East Asia. We, thus, conclude that the East Asian hydroclimate and ecosystem shift was primarily controlled by pCO2-forced global cooling between 8 and 5 Ma.

Determine both the conformation and orientation of a specific residue in α-synuclein(61-95) even in monolayer by 13C isotopic label and p-polarized multiple-angle incidence resolution spectrometry (pMAIRS).

Protein's magic function stems from its structure and various analytical techniques have been developed for it. Among proteins, membrane proteins are encoded 20-30% of genomes, whereas cause challenges for many analytical techniques. For example, lots of membrane proteins cannot form single crystal structure required by X-ray crystallography. As for NMR, the measurements were hindered by the low tumbling rates of membrane (i.e., phospholipid bilayers) where membrane proteins exist. In addition, membrane proteins usually lay parallel to the surface of phospholipid bilayers or form transmembrane structure. No matter parallel or perpendicular to phospholipid bilayers surface, membrane proteins form monolayer structure which is also difficult for X-ray and NMR to provide high-resolution results. Because NMR and X-ray crystallography are the two major analytical techniques to address protein's structure, membrane proteins only contribute 2.4% to the solved protein databank. Surface FT-IR techniques can evaluate the conformation and orientation of membrane proteins by amide I band. Specifically for α-helical peptides/proteins, the orientation of the axis is critical to decide whether proteins form transmembrane structure. Notice that the traditional FT-IR can only provide "low-resolution" results. Here, 13C isotope was introduced into the nonamyloid component (NAC), which spans residues 61-95 of α-synuclein (α-syn). Then, p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) was used to determine the orientation of a specific residue of α-helical NAC in monolayer. In general, pMAIRS is a novel technique to work complementary with X-ray and NMR to address membrane peptides/proteins structure with high resolution even in monolayer.

The Deep-Time Digital Earth program: data-driven discovery in geosciences.

Current barriers hindering data-driven discoveries in deep-time Earth (DE) include: substantial volumes of DE data are not digitized; many DE databases do not adhere to FAIR (findable, accessible, interoperable and reusable) principles; we lack a systematic knowledge graph for DE; existing DE databases are geographically heterogeneous; a significant fraction of DE data is not in open-access formats; tailored tools are needed. These challenges motivate the Deep-Time Digital Earth (DDE) program initiated by the International Union of Geological Sciences and developed in cooperation with national geological surveys, professional associations, academic institutions and scientists around the world. DDE's mission is to build on previous research to develop a systematic DE knowledge graph, a FAIR data infrastructure that links existing databases and makes dark data visible, and tailored tools for DE data, which are universally accessible. DDE aims to harmonize DE data, share global geoscience knowledge and facilitate data-driven discovery in the understanding of Earth's evolution.

Organic carbon burial is paced by a ~173-ka obliquity cycle in the middle to high latitudes.

Earth's climate system is complex and inherently nonlinear, which can induce some extraneous cycles in paleoclimatic proxies at orbital time scales. The paleoenvironmental consequences of these extraneous cycles are debated owing to their complex origin. Here, we compile high-resolution datasets of total organic carbon (TOC) and stable carbon isotope (δ13Corg) datasets to investigate organic carbon burial processes in middle to high latitudes. Our results document a robust cyclicity of ~173 thousand years (ka) in both TOC and δ13Corg The ~173-ka obliquity-related forcing signal was amplified by internal climate feedbacks of the carbon cycle under different geographic and climate conditions, which control a series of sensitive climatic processes. In addition, our new and compiled records from multiple proxies confirm the presence of the obliquity amplitude modulation (AM) cycle during the Mesozoic and Cenozoic and indicate the usefulness of the ~173-ka cycle as geochronometer and for paleoclimatic interpretation.

A python code for automatic construction of Fischer plots using proxy data.

Fischer plots are widely used in paleoenvironmental research as graphic representations of sea- and lake-level changes through mapping linearly corrected variation of accumulative cycle thickness over cycle number or stratum depth. Some kinds of paleoenvironmental proxy data (especially subsurface data, such as natural gamma-ray logging data), which preserve continuous cyclic signals and have been largely collected, are potential materials for constructing Fischer Plots. However, it is laborious to count the cycles preserved in these proxy data manually and map Fischer plots with these cycles. In this paper, we introduce an original open-source Python code "PyFISCHERPLOT" for constructing Fischer Plots in batches utilizing paleoenvironmental proxy data series. The principle of constructing Fischer plots based on proxy data, the data processing and usage of the PyFISCHERPLOT code and the application cases of the code are presented. The code is compared with existing methods for constructing Fischer plots.

Revised chronology of central Tibet uplift (Lunpola Basin).

Knowledge of the topographic evolution of the Tibetan Plateau is essential for understanding its construction and its influences on climate, environment, and biodiversity. Previous elevations estimated from stable isotope records from the Lunpola Basin in central Tibet, which indicate a high plateau since at least 35 Ma, are challenged by recent discoveries of low-elevation tropical fossils apparently deposited at 25.5 Ma. Here, we use magnetostratigraphic and radiochronologic dating to revise the chronology of elevation estimates from the Lunpola Basin. The updated ages reconcile previous results and indicate that the elevations of central Tibet were generally low (<2.3 km) at 39.5 Ma and high (3.5 to 4.5 km) at ~26 Ma. This supports the existence in the Eocene of low-elevation longitudinally oriented narrow regions until their uplift in the early Miocene, with potential implications for the growth mechanisms of the Tibetan Plateau, Asian atmospheric circulation, surface processes, and biotic evolution.

Multifractal characterization of the Coniacian-Santonian OAE3 in lacustrine and marine deposits based on spectral gamma ray logs.

Limited to the Atlantic and its surrounding basins, the expression of the Coniacian-Santonian oceanic anoxic event (OAE3) was discovered in the non-marine Cretaceous Songliao Basin, Eastern Asia not long ago. In this study, based on spectral gamma ray logs data recorded in three basins, the self-similarity of the OAE3 was studied through the analysis of the scaling properties of thorium-potassium and thorium-uranium distributions both in marine and terrestrial environments using the multifractal detrending fluctuation analysis. The results indicate that, in both marine and terrestrial systems, the OAE3 intervals are characterized by their multifractal nature due to long-range correlation. However, the multifractal features of the studied OAE3 intervals are different in the three basins, although some common trends were observed. By comparing the degree of multifractality of the OAE3 deposits with the clay minerals and the redox conditions, it appears that the changes of the multifractal features are controlled by local changes such as clay mineralogy and redox conditions in both milieus under different sedimentation patterns. At all sites, the left side shortened spectrum of the thorium-potassium distribution suggests the presence of local fluctuations with minor amplitudes during the OAE3. Furthermore, the shortened singularity spectrum of the thorium-uranium distribution reflects the existence of small-scale fluctuations with large amplitudes at marine sites while in the non-marine Songliao Basin, the thorium-uranium distribution suggests the presence of local fluctuations with small amplitudes during the OAE3. Therefore, a more local behavior of the event is considered although the regional character is not neglected.

Conformation change of α-synuclein(61－95) at the air-water interface and quantitative measurement of the tilt angle of the axis of its α-helix by multiple angle incidence resolution spectroscopy.

Various techniques have been developed to determine protein's structure to understand how proteins work.  Compared with X-ray crystallography requiring proteins to form single crystal structure and NMR which usually needs long time measurement, surface FT-IR techniques are able to quickly determine the tilt angle (the key information to determine whether the α-helix is transmembrane) of peptides/proteins in a monolayer at the interface (e.g. membranes). Specifically, for α-helical peptides/proteins in membrane, the tilt angle of the axis is one of the key information. In this paper, Multiple Angle Incidence Resolution Spectroscopy (MAIRS), a recently developed surface FTIR technique, was applied for the first time to quantitatively determine the tilt angle of the axis of α-helical model peptide related to α-synuclein (α-syn). α-Syn is a 140-amino-acid presynaptic protein whose aggregation is the hallmark of Parkinson's disease (PD). It is difficult for α-syn to form a single crystal structure and the primary structure of α-syn constitutes three domains: the N-terminus containing residues 1-60; the nonamyloid component (NAC) which spans residues 61-95 and is highly prone to aggregation; and C-terminus with residues 96-140. Here, the NAC part (i.e., α-syn(61-95)) responsible for the aggregation was found to change its unstructured conformation in aqueous solution to α-helix at the air-water interface by circular dichroism and MAIRS. In addition, the instinct power of MAIRS to quantitatively measure the tilt angle of the axis of α-helical α-syn(61-95) in monolayer was fully exhibited. Therefore, MAIRS is a potential supplemental technique to X-ray crystallography and NMR to determine the structure of membrane peptides/proteins.

Substrates for Paraoxonase.

BACKGROUND: Paraoxonase (PON) is a family of calcium-dependent hydrolases, which is related to many diseases. Elucidation of PON physiological roles, active center and all applications in medical fields are dependent on its substrates. OBJECTIVE: The reports about PON substrates scattered in a long span of period are collected to afford clue for drug design, diagnosis of PON status and other academic purposes. METHOD: PON substrates from 133 references are classified and compared. Structurally, PON substrates are generally classified as organic phosphorous esters, lactones and arylesters. Some phosphoramidates, organophosphorous obidoximes, aryl carboxylic acid amides and special fatty alcohol esters as PON substrates are also included. RESULTS: The electron nature, steric hindrance and hydrophilicity of substrate substituents affecting the PON catalytic ability, binding ability and specificities are discussed. Drugs, prodrugs and naturally endogenous molecules in life processes activated or inactivate by PON are reviewed. Interestingly, some organophosphate and lactone substrates are preferably hydrolyzed by one of the PON1R192Q allozymes, and such a substrate is generally essential for differentiating the three PON1192R phenotypes by using a dual-substrate method. Intricately, some chiral substrates are hydrolyzed by PON stereoselectively. CONCLUSION: As more substrates are synthesized and characterized, more facts about PON structure and catalytic properties (including PON active center and catalytic mechanism) will be revealed, and therefore the use of PON as a drug target or as an accurate disease marker will be achieved.

The onset of widespread marine red beds and the evolution of ferruginous oceans.

Banded iron formations were a prevalent feature of marine sedimentation ~3.8-1.8 billion years ago and they provide key evidence for ferruginous oceans. The disappearance of banded iron formations at ~1.8 billion years ago was traditionally taken as evidence for the demise of ferruginous oceans, but recent geochemical studies show that ferruginous conditions persisted throughout the later Precambrian, and were even a feature of Phanerozoic ocean anoxic events. Here, to reconcile these observations, we track the evolution of oceanic Fe-concentrations by considering the temporal record of banded iron formations and marine red beds. We find that marine red beds are a prominent feature of the sedimentary record since the middle Ediacaran (~580 million years ago). Geochemical analyses and thermodynamic modelling reveal that marine red beds formed when deep-ocean Fe-concentrations were > 4 nM. By contrast, banded iron formations formed when Fe-concentrations were much higher (> 50 µM). Thus, the first widespread development of marine red beds constrains the timing of deep-ocean oxygenation.The evolution of oceanic redox state in the past is poorly known. Here, the authors present a temporal record of banded iron formations and marine red beds, which indicate deep-ocean oxygenation occurred in the middle Ediacaran, coinciding with the onset of widespread marine red beds.

The (13)C amide I band is still sensitive to conformation change when the regular amide I band cannot be distinguished at the typical position in H2O.

The attenuated total reflection technique was utilized to obtain FTIR spectra of (13)C-labeled peptides with a sequence of (AAAAK)4AAAAY in H2O. The regular amide I band was not at the typical position as reported in globular proteins, whereas the (13)C amide I band was still sensitive to conformation change.

Isotope-edited FTIR in H2O: determination of the conformation of specific residues in a model α-helix peptide by 13C labeled carbonyls.

Isotope-edited FTIR spectroscopy has been shown to be able to determine peptide's structure in the residue level in D2O, which is not a physiological solvent. Here, attenuated total reflection technique was utilized to successfully apply isotope-edited FTIR spectroscopy in H2O to determine the conformation of specific residues in a model peptide.

Smooth surface roughness of silanized CdSe(ZnS) quantum dots.

The interparticle distance of CdSe(ZnS) quantum dots was accurately controlled by polymerization at the air-water interface which provided an increased homogeneity of the Langmuir-Blodgett film leading to a surface smoothness comparable to mica. The choice of a silane derivative is based on the fact that silicon is semiconductor, and the compound CdSe being the core of the quantum dot is also semiconductor. The combination of the two semiconductors could bring some unusual conduction properties as a polymeric silanized network. But first, it is most important to characterize the smoothness of the surface, which might be correlated to the formation of "trap" states, i.e. the photo-excited electron can fall, or the photo-excited hole can "float". One will focus our research strategy, as a pilot study, to characterize the surface of the new polymeric material.

Conversion of natively unstructured α-synuclein to its α-helical conformation significantly attenuates production of reactive oxygen species.

The intracellular α-synuclein (α-syn) protein, whose conformational change and aggregation have been closely linked to the pathology of Parkingson's disease (PD), is highly populated at the presynaptic termini and remains there in the α-helical conformation. In this study, circular dichroism confirmed that natively unstructured α-syn in aqueous solution was transformed to its α-helical conformation upon addition of trifluoroethanol (TFE). Electrochemical and UV-visible spectroscopic experiments reveal that both Cu (I) and Cu (II) are stabilized, with the former being stabilized by about two orders of magnitude. Compared to unstructured α-syn (Binolfi et al., J. Am. Chem. Soc. 133 (2011) 194-196), α-helical α-syn stabilizes Cu (I) by more than three orders of magnitude. Through the measurements of H(2)O(2) and hydroxyl radicals (OH) in solutions containing different forms of Cu (II) (free and complexed by unstructured or α-helical α-syn), we demonstrate that the significantly enhanced Cu (I) binding affinity helps inhibit the production of highly toxic reactive oxygen species, especially the hydroxyl radicals. Our study provides strong evidence that, as a possible means to prevent neuronal cell damage, conversion of the natively unstructured α-syn to its α-helical conformation in vivo could significantly attenuate the copper-modulated ROS production.

The effect of continuous Zn (II) exposure on the organic degradation capability and soluble microbial products (SMP) of activated sludge.

This study describes the change of organic degradation capability and soluble microbial products (SMP) generated in activated sludge under continuous exposure to Zn (II) in a sequencing batch reactor (SBR). In 338 days of operation, the added Zn (II) concentrations were gradually increased from 50 to 100, 200, 400 to 600 and 800 mg/L. Results showed that after adaptation, the activated sludge could endure 400mg/L Zn (II) without showing evident reduction in organic degradation ability (92±1% of chemical oxygen demand (COD) removal in stable state). However, when 600 and 800 mg/L Zn (II) were applied, the effluent water quality significantly deteriorated. Meanwhile, under increasing Zn (II) concentrations, the SMP content in the activated sludge, together with its main biochemical constituents, first increased slightly below 400mg/L of Zn (II), then rose sharply under 600 and 800 mg/L Zn (II). Furthermore, a close correlation was found between SMP content and effluent soluble COD in both the Experimental Reactor and Control Reactor. In addition, the Zn (II) concentrations in the effluent and SMP extraction liquid were further analyzed and discussed to reveal the role that SMP constituents played in defense and resistance to the toxicity of Zn (II).