科研成果

The practical importance of coherent forecasts in hierarchical forecasting has inspired many studies on forecast reconciliation. Under this approach, so-called base forecasts are produced for every series in the hierarchy and are subsequently adjusted to be coherent in a second reconciliation step. Reconciliation methods have been shown to improve forecast accuracy, but will, in general, adjust the base forecast of every series. However, in an operational context, it is sometimes necessary or beneficial to keep forecasts of some variables unchanged after forecast reconciliation. In this paper, we formulate reconciliation methodology that keeps forecasts of a pre-specified subset of variables unchanged or "immutable". In contrast to existing approaches, these immutable forecasts need not all come from the same level of a hierarchy, and our method can also be applied to grouped hierarchies. We prove that our approach preserves unbiasedness in base forecasts. Our method can also account for correlations between base forecasting errors and ensure non-negativity of forecasts. We also perform empirical experiments, including an application to sales of a large scale online retailer, to assess the impacts of our proposed methodology.

Organic peroxides (POs) are organic molecules with one or more peroxide (−O–O−) functional groups. POs are commonly regarded as chemically labile termination products from gas-phase radical chemistry and therefore serve as temporary reservoirs for oxidative radicals (HOx and ROx) in the atmosphere. Owing to their ubiquity, active gas-particle partitioning behavior, and reactivity, POs are key reactive intermediates in atmospheric multiphase processes determining the life cycle (formation, growth, and aging), climate, and health impacts of aerosol. However, there remain substantial gaps in the origin, molecular diversity, and fate of POs due to their complex nature and dynamic behavior. Here, we summarize the current understanding on atmospheric POs, with a focus on their identification and quantification, state-of-the-art analytical developments, molecular-level formation mechanisms, multiphase chemical transformation pathways, as well as environmental and health impacts. We find that interactions with SO2 and transition metal ions are generally the fast PO transformation pathways in atmospheric liquid water, with lifetimes estimated to be minutes to hours, while hydrolysis is particularly important for α-substituted hydroperoxides. Meanwhile, photolysis and thermolysis are likely minor sinks for POs. These multiphase PO transformation pathways are distinctly different from their gas-phase fates, such as photolysis and reaction with OH radicals, which highlights the need to understand the multiphase partitioning of POs. By summarizing the current advances and remaining challenges for the investigation of POs, we propose future research priorities regarding their origin, fate, and impacts in the atmosphere.

Organosulfur compounds (OSCs) are important components of fine particulate matter (PM2.5); however, little information is available on OSCs in urban regions due to their chemical complexity, especially for novel species such as aromatic sulfonates. To supplement the detection technique and systematically identify OSCs, in this study we developed a nontargeted approach based on gas chromatography and high-resolution mass spectrometry (GC-HRMS) to screen OSCs in PM2.5 of urban Beijing and provide field evidence for their source and formation mechanism. 76 OSCs were found through mass difference of sulfur isotopes and characteristic sulfur-containing fragments. 6 species were confirmed as aromatic sulfonates by authentic standards. 32 OSCs showed higher levels in the heating season, presumably because of the intensive emission, especially from coal combustion. While certain species, with 2-sulfobenzoic acid as the representative, were 2.6-times higher in the non-heating season than in the heating season. Such species were significantly correlated with ozone and aerosol liquid water content (r = 0.2–0.8, p < 0.05), implying an oxidation-involved aqueous-phase formation in the atmosphere. In addition, with an average proportion of ∼95 % of the total sulfobenzoic acids, the predominance of the 2-substitution product over its isomers of 3- or 4-sulfobenzoic acid suggests a more plausible mechanism of radical-initiated reaction of phthalic acid followed by sulfonation, with atmospheric reactivity indicated by ozone and temperature as the determining factor. This study provided not only a nontargeted approach for OSCs in ambient PM2.5, but also field evidence on their secondary formation proposed in previous simulation studies.

Vacuum ultraviolet (VUV) based advanced oxidation processes (AOPs) recently attracted widespread interests. However, the role of UV185 in VUV is only considered to be generating a series of active species, while the effect of photoexcitation has long been overlooked. In this work, the role of UV185 induced high-energy excited state for the dephosphorization of organophosphorus pesticides was studied using malathion as a model. Results showed malathion degradation was highly related to radical yield, while its dephosphorization was not. It was UV185 rather than UV254 or radical yield that was responsible for malathion dephosphorization by VUV/persulfate. DFT calculation results demonstrated that the polarity of P-S bond was further increased during UV185 excitation, favoring dephosphorization while UV254 did not. The conclusion was further supported by degradation path identification. Moreover, despite the fact that anions (Cl-, SO42- and NO3-) considerably affected radical yield, only Cl- and NO3- with high molar extinction coefficient at 185 nm significantly affected dephosphorization. This study shed light on the crucial role of excited states in VUV based AOPs and provided a new idea for the development of mineralization technology of organophosphorus pesticides.

Tungsten oxide nanowires (WO3−x) with rich oxygen vacancies (OVs) were fabricated through a facile hydrothermal method, which had both high adsorptive capability and photocatalytic activity. 95.1% of total U(VI) (C0 = 10 mg/L) was removed by WO3−x at pH 5, and 79.9% was transformed to U(IV) to achieve reductive immobilization after photocatalysis under simulated solar light. Band structure and optical characterizations indicated WO3−x had narrower band gap energy, but higher charger carrier separation and transfer rates compared with conventional WO3. Density functional theory (DFT) calculations further demonstrate the spin polarization state electrons of W 5d in WO3−x due to the construction of OVs, thus greatly inhibiting recombination of electron-hole pairs. In addition, the electron density increases in WO3−x and the photogenerated e– in the conduction band of WO3−x has higher reduction ability than WO3, leading to more efficient electron transfer from WO3−x to UO22+ after photo-excitation for U(VI) reduction.

Global hydrofluorocarbon (HFC) cumulative emissions will bemore than 20 Gt CO2-equiv during 2020−2060 and have a non-negligible impacton global warming even in full compliance with the Kigali Amendment (KA).Fluorochemical manufacturers (including multinationals) in China haveaccounted for about 70% of global HFC production since 2015, of which about60% is emitted outside China. This study built an integrated model (i.e., DECAF)to estimate both territorial and exported emissions of China under three scenariosand assess the corresponding climate effects as well as abatement costs. Achievingnear-zero territorial emissions by 2060 could avoid 23 ± 4 Gt CO2-equiv ofcumulative territorial emissions (compared to the 2019 Baseline scenario) during2020−2060 at an average abatement cost of 9 ± 6 USD/t CO2-equiv. Under thenear-zero emission (including territorial and abroad) pathway, radiative forcingfrom HFCs will peak in 2037 (60 ± 6 mW/m2) with a 33% peak reduction and 8years in advance compared to the path regulated by the KA, and the radiative forcing by 2060 will be lower than that in 2019. Accelerated phase-out of HFC production in China could provide a possibility for rapid global HFC abatement and achieve greater climate benefits.

The propagation of antibiotic-resistant bacteria (ARB) greatly endangers the ecological safety and human health. This study employed pyrite (FeS2, naturally abundant mineral) for periodate (PI) activation to disinfect ARB. FeS2/PI system could disinfect 1 × 107 CFU mL−1 of kanamycin-resistant E.coli below the limit of detection in 20 min. Efficient ARB inactivation performance was achieved in pH from 3 to 9, ionic strength from 0 to 300 mM, with HA (0.1–10 mg L−1) in suspension, and in real water samples including tap water, river water and sewage. FeS2/PI system could also efficiently disinfect gentamycin-resistant E.coli and Gram-positive B. subtilis. The generated reactive species including Fe(IV), ·O2– and ·OH would attack cell membrane and overwhelmed intracellular defense system. The intracellular kanamycin resistance genes in cells would be released and then degraded in FeS2/PI system. PI preferred to be adsorbed on Fe site of FeS2 (with lower adsorption energy, more occupancy of bonding state and stronger bonding strength). The subsequent transfer of electron cloud from Fe site to PI would cleave IO bond to generate reactive species. Moreover, FeS2/PI system could also combine with sand filtration system to efficiently capture and disinfect ARB. Therefore, FeS2/PI system is a promising approach to inactivate ARB in different scenarios.

Indoor pollution of manmade semivolatile organic compounds (SVOCs) such as phthalates are a growing threat to human health. Herein we summarize the dust-phase phthalate concentrations in Chinese residences reported from 2011 to 2021 and simulate corresponding airborne concentrations based on equilibrium models. The simulation considers seasonal and regional variations in indoor temperature and PM2.5 concentration, in contrast to the common practice of using constant values. Results show that variations in these two environmental factors lead to up to ten- and six-fold variations in the monthly median gas- and particle-phase concentrations of phthalates, respectively, in residences in individual climate zones. For higher-vapor-pressure species di-n-butyl phthalate and di-isobutyl phthalate, the resultant seasonal and regional variations in aggregate non-diet intake can reach six- and three-fold, respectively. These results have important implications on exposure assessment of SVOCs and epidemiological evaluation of their health effects.

In a reverberant environment, interferences such as reflections and background noise can degrade the perception of the sound source signal. Although the DNN-based methods have made a tremendous breakthrough in addressing this issue, the performance of these models is highly dependent on the completeness of the training dataset, which will limit its generalization under unknown environments. In this article, we propose a physical model-based self-supervised learning (PMSSL) method to realize the DNN model optimization under unknown scenarios. This method incorporates a room reverberation physical model into the sound source enhancement model optimization process, realizing the self-learning of the DNN model under physical constraints. In this process, the time-frequency characteristics of the input signal and the spatial feature of the reverberation environment are utilized for parameter optimization, improving the adaptability of the DNN model under unknown scenarios. Experimental results based on simulated and measured data prove that the proposed method can obtain much more accurate source signal enhancement results compared with the pre-trained models, verifying its effectiveness and adaptability in new environments.

Summary The geographic distribution of plant diversity matches the gradient of habitat heterogeneity from lowlands to mountain regions. However, little is known about how much this relationship is conserved across scales. Using the World Checklist of Vascular Plants and high-resolution biodiversity maps developed by species distribution models, we investigated the associations between species richness and habitat heterogeneity at the scales of Eurasia and the Hengduan Mountains (HDM) in China. Habitat heterogeneity explains seed plant species richness across Eurasia, but the plant species richness of 41/97 HDM families is even higher than expected from fitted statistical relationships. A habitat heterogeneity index combining growing degree days, site water balance, and bedrock type performs better than heterogeneity based on single variables in explaining species richness. In the HDM, the association between heterogeneity and species richness is stronger at larger scales. Our findings suggest that high environmental heterogeneity provides suitable conditions for the diversification of lineages in the HDM. Nevertheless, habitat heterogeneity alone cannot fully explain the distribution of species richness in the HDM, especially in the western HDM, and complementary mechanisms, such as the complex geological history of the region, may have contributed to shaping this exceptional biodiversity hotspot.

The widespread secondary microplastics (MPs) in urban freshwater, originating from plastic wastes, have created a new habitat called plastisphere for microorganisms. The factors influencing the structure and ecological risks of the microbial community within the plastisphere are not yet fully understood. We conducted an in-site incubation experiment in an urban river, using MPs from garbage bags (GB), shopping bags (SB), and plastic bottles (PB). Bacterial communities in water and plastisphere incubated for 2 and 4 weeks were analyzed by 16S high-throughput sequencing. The results showed the bacterial composition of the plastisphere, especially the PB, exhibited enrichment of plastic-degrading and photoautotrophic taxa. Diversity declined in GB and PB but increased in SB plastisphere. Abundance analysis revealed distinct bacterial species that were enriched or depleted in each type of plastisphere. As the succession progressed, the differences in community structure was more pronounced, and the decline in the complexity of bacterial community within each plastisphere suggested increasing specialization. All the plastisphere exhibited elevated pathogenicity at the second or forth week, compared to bacterial communities related to natural particles. These findings highlighted the continually evolving plastisphere in urban rivers was influenced by the plastic substrates, and attention should be paid to fragile plastic wastes due to the rapidly increasing pathogenicity of the bacterial community attached to them.