Characteristics of typical intermediate and semi volatile organic compounds in Shanghai during China International Import Expo event.

To ensure good air quality during the China International Import Expo (CIIE) event, stringent emission-reduction measures were implemented in Shanghai. To assess the efficacy of these measures, this study measured typical categories of intermediate/semi volatile organic compounds (I/SVOCs), including alkanes (C10-C26 n-alkanes and pristane), EPA-priority polycyclic aromatic hydrocarbons (PAHs), alkylnaphthalenes, benzothiazole (BTH) and chlorobenzenes (CBs), at an urban site of Shanghai before and during two CIIE events (2019 and 2020; non-CIIE versus CIIE). The average concentrations of alkanes and PAHs during both 2019 and 2020 CIIE events decreased by approximately 41% and 17%, respectively, compared to non-CIIE periods. However, the decline in BTH and CBs was only observed during CIIE-2019. Secondary organic aerosol (SOA) formation from alkanes, PAHs and BTH was evaluated under atmospheric conditions, revealing considerable SOA contributions from dimethylnaphthalenes and BTH. Positive matrix factorization (PMF) analysis further revealed that life-related sources, such as cooking and residential emissions, make a noticeable contribution (21.6%) in addition to the commonly concerned gasoline-vehicle sources (31.5%), diesel-related emissions (20.8%), industrial emissions (18.6%) and ship emissions (7.5%). These findings provide valuable insights into the efficacy of the implemented measures in reducing atmospheric I/SVOCs levels. Moreover, our results highlight the significance of exploring additional individual species of I/SVOCs and life-related sources for further research and policy development.

Photochemical processes transform dissolved organic matter differently depending on its initial composition.

Dissolved organic matter (DOM) is one of the most important fluxes in the global carbon cycle but its response to light exposure remains unclear at a molecular-level. The chemical response of DOM to light should vary with its molecular composition and environmental conditions while some basic hypotheses are still unclear, such as the balance between photobleaching and photo-humification and the question of oxidative properties. Here we exposed aquatic DOM from diverse freshwaters impacted by different levels of anthropogenic activity and algal exudates to environmentally-realistic light conditions. We found that photobleaching occurred in DOM with relatively high initial humic content producing low H/C molecules, whereas DOM with low initial humic content was humified. DOM pools with relatively high initial saturation and low aromaticity were prone to transform towards more unsaturated molecular formulae and high H/C molecules with a distinct decrease of bioavailability. Photo-transformation was mainly influenced by reactive intermediates, with reactive oxygen species (ROS) playing a dominant role in humification when the initial humus content of DOM was high. In contrast, for algal DOM with high protein content, it was likely that the autoxidation of excited state DOM was more important than indirect oxidation involving ROS. Our results reveal how photo-transformation patterns depend on the initial composition of DOM and provide new insights into the role of photochemical processes in biogeochemical cycling of DOM.

Scalable synthesis of N/S co-doped hard carbon microspheres as a high-performance anode material for sodium-ion batteries.

Hard carbon is a promising anode material for sodium-ion batteries (SIBs) due to its abundance. However, it exhibits low reversible capacity and slow kinetics if inappropriate microstructural features are developed during synthesis. Herein, N/S co-doped phenolic resin-based hard carbon microspheres are prepared by a scalable strategy, and the electrochemical performance is assessed both in half cells and full cells. We demonstrate that the expanded interlayer spacing, the increased active sites, and the enhanced capacitive behavior result in the enhanced reversible capacity and promoted kinetics for Na+storage. The sample with appropriate doping amount exhibits an initial charge capacity of 536.8 mAh g-1at 50 mA g-1and maintains 445.9 mAh g-1after 1000 cycles at a current density of 1 A g-1in a Na-metal half cell. Coupled with a carbon-coated Na4Fe3(PO4)2P2O7(NFPP) cathode, the full cell exhibits a capacity of 92.5 mAh g-1after 90 cycles, with a capacity retention of 91.6%. This work provides a facile and scalable method for synthesizing high-performance hard carbon anode materials for SIBs.

The optimal frozen embryo transfer strategy for the recurrent implantation failure patient without blastocyst freezing: thawing day 3 embryos and culturing to day 5 blastocysts.

This study aimed to investigate the optimal frozen embryo transfer (FET) strategy for recurrent implantation failure (RIF) patients with three consecutive failed cleaved embryo implantations and no blastocyst preservation. This retrospective analysis was divided into three groups based on the FET strategy: thawed day 3 embryo transfer (D3 FET group); and extended culture of frozen-thawed day 3 embryos to day 5 blastocysts transfer (D3-D5 FET group); thawed blastocyst transfer (D5 FET group). Transplant cycle data were compared between the three groups. In total, 43.8% of vitrified-thawed cleavage embryos developed into blastocysts. Analysis of the three transplantation strategies showed that, compared with the D3 FET group, D3-D5 had a significantly better hCG-positivity rate and live-birth rate (P < 0.05). Pregnancy outcomes in the D3-D5 FET group and D5 FET group were similar regarding hCG-positivity rate, implantation rate, clinical pregnancy rate, and live-birth rate. Our findings propose two potentially valuable transfer strategies for patients experiencing repeated implantation failures. The D3-D5 FET approach presents a greater potential for selecting promising embryos in cases without blastocyst preservation; however, this strategy does entail the risk of cycle cancellation. Conversely, in instances where blastocyst preservation is an option, prioritizing consideration of the D5 FET strategy is recommended.

Study on potential antigenicity and functional properties of whey protein treated by high hydrostatic pressure based on structural analysis.

High hydrostatic pressure (HHP) is extensively utilized in the field of food processing due to its remarkable ability to preserve the freshness of food. The potential antigenicity of ß-lactoglobulin (ß-LG) in whey protein isolate (WPI, 3%) treated by HHP was detected by enzyme linked immunosorbent assay (ELISA) using monoclonal antibodies. Furthermore, the impact of pressure-induced structural alterations on the emulsification properties and antioxidant activity of WPI was investigated. The findings revealed that pressures exceeding 300 MPa resulted in molecular aggregation, the formation of inter-molecular disulfide bonds, and an increase in surface hydrophobicity (H0). The percentage of ß-sheet decreased along with the pressure. The results showed the increment of α-helix and ß-turn with pressure. ELISA demonstrated a significant reduction in the antigenicity of ß-LG following HHP treatment (100-600 MPa), with a slight recovery observed at 300 MPa. These spatial structural modifications led to the unfolding of the ß-LG molecule, thereby enhancing its digestibility. Moreover, HHP treatment substantially improved the antioxidant properties, with the exposure to hydrophobic amino acids contributing to increased antioxidant properties and emulsion stability.

Copper isotope evidence for sulfide fractionation and lower crustal foundering in making continental crust.

The continental crust is strongly depleted in copper compared with its building blocks-primary arc magmas-and this depletion is intrinsically associated with continental crust formation. However, the process by which Cu removal occurs remains enigmatic. Here we show, using Cu isotopes, that subduction-zone processes and mantle melting produce limited fractionation of Cu isotopes in arc magmas, and, instead, the heterogeneous Cu isotopic compositions of lower crustal rocks, which negatively correlate with Cu contents, suggest segregation or accumulation of isotopically light sulfides during intracrustal differentiation of arc magmas. This is supported by the extremely light Cu isotopic compositions of lower crustal mafic cumulates and heavy Cu isotopic compositions of differentiated magmas in thick continental arcs. Intracrustal differentiation of mantle-derived magmas and subsequent foundering of sulfide-rich mafic cumulates preferentially removes isotopically light Cu, leaving a Cu-depleted and isotopically heavy continental crust.

High-precision zinc isotope measurement of chemically different geostandards by multicollector inductively coupled plasma mass spectrometry.

RATIONALE: Zinc isotopes are becoming increasingly applicable in high-temperature geochemistry, for example in crust-mantle interaction and volatilization-related processes. The published zinc isotope data for some commonly used reference materials, however, show large interlaboratory offsets. In addition, there is still limited data for zinc isotope compositions of many widely used geological reference materials. METHODS: For precise and accurate zinc isotopic ratio analysis of chemically diverse geostandards, including ultramafic to felsic igneous rocks, carbonatites, sediments and soils, an improved procedure for chemical purification of zinc was introduced in this study. The factors potentially affecting zinc isotopic ratio measurement were assessed. The accuracy and long-term reproducibility were obtained by measurements on both synthetic solutions and well-characterized geostandards. RESULTS: Purification of geologic samples with different zinc concentrations and matrix compositions yields consistent elution curves with nearly 100% recovery. Acidity and concentration mismatches and the presence of some matrix elements (e.g., Mg, Ti and Cr) have significant impacts on the precision and accuracy of zinc isotopic ratio measurement. The zinc isotope compositions of a suite of reference materials were measured using this method. CONCLUSIONS: The present study describes methods for the chemical purification of zinc and high-precision and accurate zinc isotopic ratio measurements using multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The long-term external reproducibility for δ66 Zn values is ±0.04‰ (2SD). High-quality zinc isotope data of chemically different geostandards were reported to stimulate future interlaboratory calibrations.

Preparation and Properties of a Lightweight, High-Strength, and Heat-Resistant Rigid Cross-Linked PVC Foam.

A rigid poly(vinyl chloride) foam with a cross-linked network structure was prepared by adding 3-glycidoxypropyltriethoxysilane (KH-561) into the universal formulation. The resulting foam had excellent heat resistance because of the increasing degree of cross-linking and number of Si-O bonds with a high heat resistance. The as-prepared foam was verified using Fourier-transform infrared spectroscopy (FTIR), energy-dispersive spectrometry (EDS) and foam residue (gel) analysis, which demonstrated that KH-561 was successfully grafted and cross-linked on the PVC chains. Finally, the effects of different KH-561 and NaHSO3 additions on the mechanical properties and heat resistance of the foams were studied. The results showed that the mechanical properties of the rigid cross-linked PVC foam were raised after adding a certain amount of KH-561 and NaHSO3. The residue (gel), decomposition temperature, and chemical stability of the foam significantly improved compared to the universal rigid cross-linked PVC foam (Tg = 72.2 °C). The Tg of the foam could reach 78.1 °C without any mechanical degradation. The results have important engineering application value regarding the preparation of lightweight, high-strength, heat-resistant, and rigid cross-linked PVC foam materials.

Development of three chalcopyrites and one copper metal as potential reference materials for copper isotopic analysis by LA-MC-ICP-MS.

RATIONALE: Laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) has become a powerful technique for in situ Cu isotopic analysis in natural geological samples. Cu isotopic compositions in natural chalcopyrites have been used to reveal aspects of the mineralization processes directly. However, internationally or commercially available matrix-matched chalcopyrite reference materials for mass fractionation correction or quality control purposes are still lacking for in situ Cu isotopic analysis using LA-MC-ICP-MS. METHODS: Three natural chalcopyrites 14ZJ12-1, JGZ-29 and JGZ-78, and one copper metal GBW02141 with different Cu isotopic compositions were investigated as potential microanalytical reference materials by LA-MC-ICP-MS. Ga element was used as an internal standard to correct the mass fractionation of Cu isotopes during LA-MC-ICP-MS analysis. RESULTS: A large number of Cu isotope ratio measurements using femtosecond LA-MC-ICP-MS were conducted and produced good intermediate precision of δ65 CuNIST976 (0.07-0.08‰, 2 standard deviations), demonstrating the homogeneous Cu isotopic distribution in the recommended samples. The mean δ65 CuNIST976 values of -0.21 ± 0.04‰, 0.46 ± 0.04‰, -0.06 ± 0.04‰ and 0.11 ± 0.05‰ (2 standard deviations) in 14ZJ12-1, JGZ-29, JGZ-78 and GBW02141, respectively, were obtained using solution-MC-ICP-MS in the four recommended samples. CONCLUSIONS: Here, we describe three natural chalcopyrites 14ZJ12-1, JGZ-29, JGZ-78, and one copper metal GBW02141 as the potential Cu isotopic reference materials for LA-MC-ICP-MS analysis. Our analyses demonstrate that these recommended materials have a high degree of elemental and isotopic homogeneity, indicating that they are suitable for microanalysis techniques for data quality assurance or interlaboratory calibration.

Enigma of Urban Gaseous Oxygenated Organic Molecules: Precursor Type, Role of NOx, and Degree of Oxygenation.

Oxidation of volatile organic compounds (VOCs) forms oxygenated organic molecules (OOMs), which contribute to secondary pollution. Herein, we present measurement results of OOMs using chemical ionization mass spectrometry with nitrate as the reagent ion in Shanghai. Compared to those in forests and laboratory studies, OOMs detected at this urban site were of relatively lower degree of oxygenation. This was attributed to the high NOx concentrations (∼44 ppb), which overall showed a suppression on the propagation reactions. As another result, a large fraction of nitrogenous OOMs (75%) was observed, and this fraction further increased to 84% under a high NO/VOC ratio. By applying a novel framework on OOM categorization and supported by VOC measurements, 50 and 32% OOMs were attributed to aromatic and aliphatic precursors, respectively. Furthermore, aromatic OOMs are more oxygenated (effective oxygen number, nOeff = 4-6) than aliphatic ones (nOeff = 3-4), which can be partly explained by the difference in initiation mechanisms and points to possible discrimination in termination reactions. This study highlights the roles of NOx in OOM formation in urban areas, as well as the formation of nitrogenous products that might show discrimination between aromatic and aliphatic VOCs.

Extensive crystal fractionation of high-silica magmas revealed by K isotopes.

Fractional crystallization plays a critical role in generating the differentiated continental crust on Earth. However, whether efficient crystal-melt separation can occur in viscous felsic magmas remains a long-standing debate because of the difficulty in discriminating between differentiated melts and complementary cumulates. Here, we found large (~1 per mil) potassium isotopic variation in 54 strongly peraluminous high-silica (silicon dioxide >70 weight %) leucogranites from the Himalayan orogen, with potassium isotopes correlated with trace elemental proxies (e.g., strontium, rubidium/strontium, and europium anomaly) for plagioclase crystallization. Quantitative modeling requires up to ~60 to 90% fractional crystallization to account for the progressively light potassium isotopic composition of the fractionated leucogranites, while plagioclase accumulation results in enrichment of heavy potassium isotopes in cumulate leucogranites. Our findings strongly support fractional crystallization of high-silica magmas and highlight the great potential of potassium isotopes in studying felsic magma differentiation.

Finite Element Analysis of Elastoplastic Elements in the Iwan Model of Bolted Joints.

The Iwan model is composed of elastoplastic elements and is widely used to represent the stiffness degradation of bolted joints under mixed-mode loading (normal and tangential loading). The latest static methods of parameter identification established the relationship between the elastoplastic elements and the contact pressure under normal loading. Under mixed-mode loading, the parameters of the Iwan model are dynamic for the evolution of contact conditions. Therefore, static parameter identification methods are not suitable for the dynamic Iwan model. A new technique was proposed to identify the parameters of the elastoplastic elements in this paper. Firstly, several different finite element models were established. The influence of the contact method and the thread structure were analyzed, and a reliable and efficient bolted-joint modeling method was proposed. Secondly, the evolution of contact conditions was studied. The dynamic elliptical contact model and the ellipticity discrete method were proposed. Finally, the residual stiffness of the Iwan model was analyzed to establish the mapping between the residual stiffness and the bending of the screw. The results can provide a technique for identifying the parameters of the dynamic Iwan model.

Fate of Oxygenated Volatile Organic Compounds in the Yangtze River Delta Region: Source Contributions and Impacts on the Atmospheric Oxidation Capacity.

The Community Multiscale Air Quality model (CMAQv5.2) was implemented to investigate the sources and sinks of oxygenated volatile organic compounds (OVOCs) during a high O3 and high PM2.5 season in the Yangtze River Delta (YRD) region, based on constraints from observations. The model tends to overpredict non-oxygenated VOCs and underpredict OVOCs, which has been improved with adjusted emissions of all VOCs. The OVOCs in the YRD are dominated by ketones, aldehydes, and alcohols. Ketones and aldehydes mainly originate from direct emissions and secondary formation in the northern YRD, and primarily originate from secondary formation in the southern part influenced by biogenic emissions. The concentration of secondary organic aerosols (SOA) produced by OVOCs is 0.5-1.5 µg/m3, with 40-80% originated from organic nitrates, 20-70% originated from dicarbonyls, and 0-20% originated from isoprene epoxydiols. The influences of OVOCs on the atmospheric oxidation capacity are dominated by the OH• pathway during the day (∼350%) and by the NO3• pathway at night (∼150%). Consequently, O3 is enhanced by 30-70% in the YRD. Aerosols are also enhanced by 50-140%, 20-80%, and ∼20% for SOA, nitrate, and sulfate, respectively.

An online method for monitoring atmospheric intermediate volatile organic compounds with a thermal desorption-gas chromatography/mass spectrometry.

As one of important precursors of secondary organic aerosol (SOA), intermediate volatile organic compounds (IVOCs) have attracted much attention in recent years. Most of the previous studies however largely focused on characteristics of IVOCs from different emission sources, while data from field observations to study their temporal variations was limited for lacking the sufficient time resolution monitoring data. In this study, an online thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed to generate monitor data with a three-hour time resolution for gaseous atmospheric IVOCs. The method used two multi-sorbent traps that alternated for conducting sample collection and sample analysis. Compounds of C12C22 n-alkanes and 2-4 ring PAHs were chosen as surrogates to evaluate the performance of this method. Regression coefficients of external calibration curves were greater than 0.93 and 0.96 for all individual n-alkanes and PAHs, respectively. Average relative standard deviation (RSD) values among replicate samples spiked at 3 ng for each individual standard were 9% ± 5%. The detection limits of this method for individual n-alkanes and PAHs were 3.1-16.2 ng/m3 and 1.0-2.7 ng/m3, respectively. Atmospheric IVOCs were continuously monitored from September 28 to 30 and October 22 to November 9 in 2018, in an urban area of Shanghai. Besides targeted n-alkanes and PAHs, unspeciated complex mixtures (UCM) of IVOCs as well as total-IVOCs concentrations in the atmosphere were also determined. Measured concentrations and compositions of gaseous IVOCs in the atmosphere in this study were comparable to other similar studies.

Linking deep CO2 outgassing to cratonic destruction.

Outgassing of carbon dioxide from the Earth's interior regulates the surface climate through deep time. Here we examine the role of cratonic destruction in mantle CO2 outgassing via collating and presenting new data for Paleozoic kimberlites, Mesozoic basaltic rocks and their mantle xenoliths from the eastern North China Craton (NCC), which underwent extensive destruction in the early Cretaceous. High Ca/Al and low Ti/Eu and δ 26Mg are widely observed in lamprophyres and mantle xenoliths, which demonstrates that the cratonic lithospheric mantle (CLM) was pervasively metasomatized by recycled carbonates. Raman analysis of bubble-bearing melt inclusions shows that redox melting of the C-rich CLM produced carbonated silicate melts with high CO2 content. The enormous quantities of CO2 in these magmas, together with substantial CO2 degassing from the carbonated melt-CLM reaction and crustal heating, indicate that destruction of the eastern NCC resulted in rapid and extensive mantle CO2 emission, which partly contributed to the early Cretaceous greenhouse climate episode.

Probing recycled carbonate in the lower mantle.

Whether surficial carbonates can be carried into the Earth's lower mantle is key to global deep carbon cycles but remains poorly understood. New clues from magnesium and zinc isotopic systematics on rocks from deep-rooted mantle plumes are presented and discussed in this Perspective.

From "Human-to-Human" to "Human-to-Non-human" - Influence Factors of Artificial Intelligence-Enabled Consumer Value Co-creation Behavior.

The emergence of artificial intelligence (AI) has changed traditional methods of value co-creation. Diverging from traditional methods, this study discusses the influencing factors of AI-supported consumer value co-creation from the perspective of human-to-non-human interactions. This study adopts the stimulus-organism-response framework with consumer engagement (CE) as the intermediary to explore the impact of consumers' personal subjective factors, community factors, and perceptions of AI technology on their value co-creating behaviors. Data were collected from 528 respondents from the Huawei Huafen Club, Xiaomi BBS, Apple China Virtual Brand, Micromobile Phone, and Lenovo communities. SPSS Amos software was used for statistical analysis, revealing that perceived personalization, autonomy, community identity, trust in AI, and self-efficacy are motivational factors that have significant effects on consumer value co-creation behaviors, in which CE plays a significant intermediary role. Our study contributes to the literature on consumer value co-creation supported by AI technology. We also offer important insights for developers of AI-enabled products and service managers.

Field Detection of Highly Oxygenated Organic Molecules in Shanghai by Chemical Ionization-Orbitrap.

Secondary organic aerosol, formed through atmospheric oxidation processes, plays an important role in affecting climate and human health. In this study, we conducted a comprehensive campaign in the megacity of Shanghai during the 2019 International Import Expo (EXPO), with the first deployment of a chemical ionization─Orbitrap mass spectrometer for ambient measurements. With the ultrahigh mass resolving power of the Orbitrap mass analyzer (up to 140,000 Th/Th) and capability in dealing with massive spectral data sets by positive matrix factorization, we were able to identify the major gas-phase oxidation processes leading to the formation of oxygenated organic molecules (OOM) in Shanghai. Nine main factors from three independent sub-range analysis were identified. More than 90% of OOM are of anthropogenic origin and >60% are nitrogen-containing molecules, mainly dominated by the RO2 + NO and/or NO3 chemistry. The emission control during the EXPO showed that even though the restriction was effectual in significantly lowering the primary pollutants (20-70% decrease), the secondary oxidation products responded less effectively (14% decrease), or even increased (50 to >200%) due to the enhancement of ozone and the lowered condensation sink, indicating the importance of a stricter multi-pollutant coordinated strategy in primary and secondary pollution mitigation.

Felsic volcanism as a factor driving the end-Permian mass extinction.

The Siberian Traps large igneous province (STLIP) is commonly invoked as the primary driver of global environmental changes that triggered the end-Permian mass extinction (EPME). Here, we explore the contributions of coeval felsic volcanism to end-Permian environmental changes. We report evidence of extreme Cu enrichment in the EPME interval in South China. The enrichment is associated with an increase in the light Cu isotope, melt inclusions rich in copper and sulfides, and Hg concentration spikes. The Cu and Hg elemental and isotopic signatures can be linked to S-rich vapor produced by felsic volcanism. We use these previously unknown geochemical data to estimate volcanic SO2 injections and argue that this volcanism would have produced several degrees of rapid cooling before or coincident with the more protracted global warming. Large-scale eruptions near the South China block synchronous with the EPME strengthen the case that the STLIP may not have been the sole trigger.