Nontarget screen and identify sulfate and sulfonate surfactants in personal care products using UHPLC-Q-Orbitrap-HRMS based on fragmentation characteristics and sulfur isotopologue pattern

Sulfate and sulfonate compounds are extensively used as anionic surfactants in personal care products (PCPs), which might pose adverse potential to human health. However, available research mostly identified certain subsets of sulfated and sulfonated surfactants based on target analysis. In this study, we developed a comprehensive nontarget strategy for identification of sulfated and sulfonated surfactants in PCPs using UHPLC-HRMS supplemented by an in-lab R script based on characteristic fragment ions and sulfur isotope patterns. A total of 20 sulfate and 12 sulfonate surfactants of confidence level 3 and above were identified in the range of alkyl chain length from C12 to C26 with 0-7 ethoxy groups and molecular weights of 200-600 Da in the PCP samples. The sulfates included 4 alkyl sulfates and 16 alkyl ether sulfates. In addition to commonly reported 4 alkyl benzene sulfonates, this study identified eight sulfonate surfactants for the first time, which were 3 alkyl sulfonates, 3 methyl ammonium sulfonates, and 2 bis-sulfonate sulfonates in the PCPs. Interestingly, 22 sulfate and sulfonate compounds were identified in the negatively labeled PCP samples which were not supposed to contain sulfate and sulfonate surfactants. The results demonstrated robustness of the developed nontarget analyzing strategy in identifying and characterizing sulfate and sulfonate surfactants and consequently providing guidance for management and regulation of chemical addition in PCPs to ensure safe use

Metal-Silicate Partitioning of Si, O, and Mg at High Pressures and High Temperatures: Implications to the Compositional Evolution of Core-Forming Metallic Melts

High-pressure and high-temperature experiments were conducted to investigate the partitioning behaviors of Si, O, and Mg between molten Fe-alloys and silicate melts in the Fe-Si-O-Mg system under conditions of 2-72 GPa and 2000-5500 K, using both laser-heated diamond anvil cells and a multi-anvil press. Combing our new experimental results with previously published data, we evaluated the effects of pressure, temperature, and metallic compositions on the partitioning behaviors of Si, O, and Mg. A set of internally consistent interaction parameters between Si, O, and Mg were obtained by the simultaneous fitting of distribution coefficients for all three elements in the Fe-Si-O-Mg system. The composition-dependent distribution coefficients were applied in calculating the compositional evolution of metallic melts during multi-stage core formation. Our results suggest that the core-forming metallic melts would contain more Si and O than previously estimated due to the attractive interactions of light elements in the metal. Compared to the geophysically constrained core composition, these findings imply the exsolution of light elements, likely in the form of SiO2, from the outer core upon cooling

Microbial recruitment and microbial ecological roles in soil nutrient cycling of Populus cathayana males and females

Soil nitrogen (N) availability influences plant production and soil nutrient cycling. However, how it influences sex-specific microbial community composition and rhizosphere nutrient cycling in dioecious plant species is poorly understood. We examined the rhizospheric bacterial and fungal community assemble and their influences on soil nutrient cycling under different N backgrounds in 30-year-old experimental stands and a soil microbial reshaping-controlled experiment. In comparison to male trees, female trees increased fungal community diversity, and the relative abundance of taxa related to nutrient availability; elevated phosphorus (P) mobilization by increasing acidic phosphatase activity and carboxylic acid release; and decreased the counts of denitrification nirS, nirK, and nosZ genes at high N supply. Males increased the nifH gene counts related to microbial N fixation at high N supply. Low N supply increased N fixation nifH gene counts in the rhizosphere of females. Males decreased bacterial and fungal diversity, increased enzymatic activities related to organic N and P mineralization, and elevated soil nitrate-nitrogen levels at low N supply. Our results indicate that sex-specific responses to N availability are associated with rhizospheric bacterial and fungal community composition and diversity and their effects on rhizospheric nutrient cycling, which may explain sex-specific resource utilization and niche differentiation

Hydrothermal pretreatment for enhanced thermochemical or biochemical conversion of pharmaceutical biowastes into fuels, fertilizers, and carbon materials

Pharmaceutical biowastes, rich in organic matter and high in moisture, are typical light industry byproducts with waste and renewable attributes. Thermochemical and biochemical conversion technologies transform these residues into value-added bioproducts, including biofuels, biofertilizers, and bio-carbon materials. Hydrothermal pretreatment effectively removes toxic substances and enhances feedstock for these processes. This review comprehensively examines its role in improving the formation of bioproducts from pharmaceutical biowastes, focusing on (i) upgrading and denitrogenating solid biofuels with better combustion performance; (ii) enhancing biodegradability and gaseous biofuel production via organic matter decomposition; (iii) enriching soluble carbon and nitrogen for liquid biofertilizer; (iv) eliminating antibiotic residues and reducing antibiotic resistance in solid biofertilizers; and (v) stabilizing carbon and nitrogen structures and optimizing pore characteristics for functionalized carbon materials. The review recommends a potential staged thermochemical approach to co-produce nitrogen-enriched liquid biofertilizers and porous carbon materials from pharmaceutical biowastes. Hydrothermal pretreatment emerges as a key technique for facilitating the migration and conversion of essential elements like carbon and nitrogen. This study reveals the potential of hydrothermal pretreatment to address the limitations of pharmaceutical biowastes and offers insights into their valorization

Atomic Insights into the Heterogeneous Crystallization of Manganese (Oxyhydr)oxides on Typical Iron (Oxyhydr)oxides: from Adsorption to Oxidation to Crystallization

Heterogeneous crystallization of manganese (oxyhydr)oxides (MnO x ) on iron (oxyhydr)oxides (FeO x ) is crucial for the biogeochemical cycling of Mn, yet atomic-level insights into this process are important but relatively limited. Herein, we revealed the distinct adsorption, oxidation, and crystallization mechanisms of Mn on hematite (Hem), ferrihydrite (Fhy), and goethite (Gth). Gth exhibited highest ability in Mn(II) removal and oxidation, followed by Hem and Fhy. Manganite and hausmannite were the main MnO x products with distinct proportions, and morphologies cross the systems. MnO x growth mechanisms involve surface-induced nucleation, crystallization by particle attachment (CPA), and self-catalyzed growth. On Fhy, self-catalyzed growth was dominant; for Gth, surface-induced nucleation was prevalent, supplemented by CPA; and Hem combined all three mechanisms. These distinct mechanisms led to nanoparticles primarily of hausmannite on Gth and nanowires of manganite and hausmannite on Hem and Fhy, with those on Hem displaying lower aspect ratios. Differences in MnO x structure and morphology were attributed to Mn(II)-FeO x complexation, FeO x electronic band structure, and crystal structure mismatch between MnO x and FeO x , which respectively influenced the direct and indirect electron transfer and heterogeneous nucleation efficiency. This work advances our understanding of MnO x crystallization on FeO x at the nanoscale, explaining the diverse morphology and structure of MnO x in different environments

Molybdenum isotopes demonstrate that multistage upgrading is required to generate heavy rare earth element-enriched carbonatites

Carbonatites with heavy rare earth element (HREE) enrichment are a rare and intriguing prospect for economic geology research, due to the growing global demand for HREEs in various industries. However, debate persists over the mechanism responsible for HREE enrichment in carbonatites, with the mantle source, magmatic-hydrothermal evolution, or a combination of these factors proposed to be responsible. This study examines three adjacent Late Triassic carbonatites (from the Huanglongpu, Huayangchuan, and Jialu carbonatite dike systems) in the Lesser Qinling of Central China and uses Mo isotope systematics to provide unique insights into the HREE enrichment process of these magmas. All three carbonatites exhibit elevated total REE (Sigma REE) concentrations (up to 4600 ppm), along with significant HREE enrichment (Sigma HREE/Sigma REE = 0.1-0.4). Notably, Jialu carbonatite stands out for having the highest total HREE concentrations (>= 360 ppm) and Sigma HREE/Sigma REE ratios (0.2-0.4). Regardless of their variable degrees of HREE enrichment, the three carbonatites display similar Sr-Nd-Pb isotope signatures, which indicates a shared enriched mantle source. The Huanglongpu and Huayangchuan carbonatites mostly display significantly lighter delta Mo-98/95 (-1.71 parts per thousand to -0.15 parts per thousand) values than the depleted mantle, which indicates an origin from an enriched mantle influenced by recycled pelagic clays and Fe-Mn nodules. Both types of marine sediments are enriched in REEs and would have undergone initial HREE enrichment during slab dehydration and metamorphism, resulting in an HREE-enriched mantle source region. In contrast, Jialu carbonatite possesses significantly heavier delta Mo-98/95 (0.13 parts per thousand-1.89 parts per thousand), which is indicative of the subsequent influence of hydrothermal processes. Additional evidence of this hydrothermal influence at Jialu is preserved in calcite crystal fluid inclusions, elevated delta O-18 (8.71 parts per thousand-10.72 parts per thousand), non-charge-and-radius-controlled (CHARAC) Y/Ho ratios (36-41), and low Sr concentrations (<4800 ppm). Secondary upgrading of HREEs at Jialu occurred due to preferential complexation and transportation during hydrothermal exsolution. This study demonstrates that maximum HREE enrichment in carbonatites is achieved through a two-stage process that involves both a refertilized mantle source and late-stage hydrothermal exsolution

Mercury evidence for volcanism driving environmental changes during the protracted Late Ordovician mass extinction and early Silurian recovery

Volcanism has been proposed as the trigger for the environmental perturbations and associated mass extinction during the Ordovician-Silurian (O-S) transition. However, the timing, duration, and intensity of volcanic eruptions during this critical period and their relationships to environmental perturbations and biotic changes remain unresolved. In this study, we use mercury (Hg) concentrations and isotopes from marine sediments in South China to reconstruct the evolution of volcanism from the Late Ordovician to early Silurian. Our results show that strong Hg enrichment coupled with generally near-zero to slightly positive Delta 199Hg values occurred before, during, and after the classically defined Late Ordovician Mass Extinction (LOME), suggesting a significant influx of volcanogenic Hg. The Hg enrichment intervals coincided with global warming, oceanic anoxia, and negative excursions in carbon and sulfur isotopes, suggesting that volcanism drove the environmental perturbations during the O-S transition. The coincidence of Hg enrichment with extinction horizons supports the hypothesis that volcanism may have contributed to LOME. Our study also suggests that volcanism persisted for approximately 3 million years after mass extinction and may have delayed the recovery of marine ecosystems during early Silurian

Mid-Late Holocene coral calcification dynamics: deciphering climatic and environmental effects

Over the past four decades, a marked decrease in coral calcification has occurred across the world's tropical reefs, closely linked to climate change and the impact of human activity. However, how natural and human-induced factors influence coral calcification remains unclear due to limited understanding of the geological past. This study addresses this gap by investigating the calcification parameters of 82 Porites corals from the northern South China Sea, with growth periods covering distinct climatic epochs during the Mid-Late Holocene, including the Holocene Climate Optimum, 4.2 ka BP event, Medieval Climate Anomaly, Little Ice Age and Current Warm Period. Our findings show a gradual increase in coral skeletal density towards the present, and varied linear extension and calcification rates between warm and cold phases and between pre- and post-industrial periods. This suggests that temperature plays a pivotal role in controlling coral calcification, with contingent influences from volcanic activity and solar radiation. Notably, the linear extension and calcification rates were significantly reduced during the Current Warm Period, suggesting a surpassing impact of contemporary human activities over the natural variability on coral calcification. This raises concerns about the future prospects of coral reefs in the face of ongoing climate change and increasing impact of human activity

Formation and evolution of environmentally persistent free radicals in charcoal and soot generated from biomass materials

Environmentally persistent free radicals (EPFRs) are emerging pollutants that are highly reactive and toxic, posing potential health risks. Biomass burning is a significant source of EPFRs, but there has been a notable gap in research regarding the EPFRs present in charcoal and soot produced from the same combustion process. Our study detected EPFRs in both charcoal and soot, but there were significant differences in their characteristics. The EPFR concentrations in charcoal were much higher than that in soot, by approximately 2-4 orders of magnitude, suggesting that charcoal may be more chemically reactive. Differences in the formation mechanisms between charcoal and soot were found to result in variations in the characteristics of EPFRs observed in each material. Furthermore, the ability of EPFRs to generate reactive oxygen species (ROS) differed considerably between charcoal and soot. Charcoal exhibited a strong ability to produce ROS, including O-1(2) and center dot OH radicals, and the abundances of O-1(2) was further enhanced (similar to 1.2-2.1 times) after illumination. In contrast, only the O-1(2) radical was found in soot produced at 300 degrees C. These findings enhanced our understanding of the environmental impact and potential toxicity of EPFRs, offering valuable insights for evaluating the risks associated with wildfires and agricultural burning

Controlling factors and geological applications of the drimane-skeleton compound content and composition of crude oils in complex petroleum systems: New insights from the Western Pearl River Mouth Basin, South China Sea

Crude oils generally contain drimane-skeleton compounds, but the uncertainty of the main factors controlling drimane distributions limits their effective geological applications, especially in complex petroleum systems. In this study, the drimane-skeleton compound composition and the relative content of each drimane-skeleton compound to C 30 hopane (CDSC) were systematically studied for crude oils in different structural regions of the Western Pearl River Mouth (WPRM) Basin, South China Sea. The results show that the C DSC of crude oil is mainly controlled by its organic sources. Higher C DSC values in crude oil indicates a greater contribution from terrigenous organic matter to their source rocks. For crude oils from source rocks with similar biotic inputs, the C DSC values are controlled mainly by the depositional environment. Higher C DSC values in crude oil correspond to higher concentrations of clay minerals and lower salinities. In addition, the drimane-skeleton compound composition of crude oil is largely controlled by its maturity. The ratios of drimane to homodrimane (Dr/HDr), total rearranged drimane to total drimane and homodrimane (TRDr/TDr), and 8-rearranged drimane to 9-rearranged drimane (8RDr/9RDr) synchronously increase with increasing maturity. These ratios can effectively characterize the maturity of various types of crude oils. The maturity range characterized by the drimane maturity parameters is greater than that characterized by conventional maturity parameters. Correlation diagrams based on drimane parameters and other organic geochemical parameters can be used to classify crude oils and reveal their sources and origins, which has great application potential in complex petroliferous basins, especially in deep and ultra-deep petroleum systems with abundant light oil/condensate