Sulfamethoxazole (SMX), which is a commonly used antibiotic, poses persistent risks to aquatic environments owing to its recalcitrance. Adsorption mediated by sludge-derived biochar is a beneficial strategy as an emergency sorbent for antibiotic pollution control. However, its application is limited by the low pore volume and small specific surface area (SSA) of the sorbent owing to the high ash content of sludge. In this study, CaCl2-modified sewage sludge-derived biochar (CaSBC) was prepared via impregnation–pyrolysis followed by acid washing. The treatment increased the pore volume and SSA to 0.3015 cm3/g and 129.50 m2/g, respectively, providing additional accessible pores for adsorption. Furthermore, the modification induced changes in the surface charge and functional groups, which improved electrostatic attraction over a wide pH range and enhanced π–π electron donor–acceptor and hydrogen bonding interactions between CaSBC and SMX. Consequently, CaSBC exhibited an adsorption capacity of 22.30 ± 0.74 mg/g, which was 2.3 and 2.9 times higher than that of unmodified biochar and commercial activated carbon (AC), respectively. Furthermore, CaSBC exhibited stable adsorption in the pH range of 2–8 and in the presence of competing ions, and its estimated production cost was lower than that of AC by 27%. This study presents a practical and cost-effective method for the reusage of sludge as a value-added resource and the concurrent enhancement of SMX removal from wastewater.
Polycyclic aromatic hydrocarbons (PAHs) and mineral dusts are the key toxic and reactive components of atmospheric particulate matter (PM2.5). Their synergistic conversion poses significant adverse environmental concerns but remains underexplored, especially for photoactive particles. Here, we conduct an in-depth study of the photochemical transformation mechanism of acenaphthylene (ACY), a common atmospheric PAH, on the surface of typical mineral dusts. Notably, TiO2 induces the formation of environmentally persistent free radical (EPFR) upon the “cation-π” interaction with ACY, thereby promoting the generation of atmospheric oxidants and significantly enhancing the photochemical conversion of ACY. In contrast, Fe2O3 and SiO2 primarily serve as inert carriers with minimal effect. EPFR-mediated hydroxyl radical (·OH) is identified to be the dominant reactive species in the photochemical transformation of ACY, driving nearly 100% conversion. Oxygenated PAHs (OPAHs), which likely aggravate the formation of secondary organic aerosols (SOA), are the main products. In addition, the enhanced ACY transformation has also been verified on the natural kaolinite, underscoring the universality of this mechanism in atmospheric chemistry. This work proposes a new pathway for the photochemical transformation of PAH on the surface of photoactive mineral particles mediated by EPFR, providing unique perspectives and deep insights into the enhanced atmospheric oxidizing capacity and the photochemical transformation from organic carbon (OC) into SOA.
Both Ozone (O3) and volatile organic compounds (VOCs) pose substantial risks to human health and ecosystems. Catalytic decomposition of O3 and catalytic ozonation of VOCs are effective degradation strategies. This review elucidates the mechanisms underlying catalytic O3 decomposition and catalytic ozonation of VOCs, while simultaneously establishing the interconnections between these two processes. This review comprehensively delineates the catalysts and control methodologies pertinent to both catalytic O3 decomposition and catalytic ozonation of VOCs, endeavoring to draw parallels between the catalysts employed in these processes. Transition metals, with their versatile valence states and rich electronic structures, exhibit remarkable efficacy in catalytic O3 decomposition and catalytic ozonation of VOCs. Modulating surface structure and concentration of oxygen vacancies emerges as the powerful regulatory strategies. Although the approach to enhancing catalytic ozonation of VOCs parallels that of catalytic O3 decomposition, the intricate environmental context of VOCs necessitates increased focuses on selective adsorption during the initial adsorption phase of the catalyst. Furthermore, a meticulous examination of catalyst stability, especially in relation to resistance against water, sulfur, and chlorine, is imperative. Reactive oxygen species act as pivotal active agents in the catalytic ozonation of VOCs, highlighting the strategic importance of screening catalysts that can generate reactive oxygen species from catalytic O3 decomposition to expedite the degradation of VOCs.
Co-formulated antibiotics may exert more complex effects on sludge anaerobic digestion (AD) due to their synergistic mechanisms. However, studies on the transformation and effects of antibiotic combinations in AD systems remain limited. This study investigates the impacts of the representative co-formulated antibiotics sulfamethoxazole and trimethoprim (SMX/TMP) on sludge AD. Results demonstrated that both antibiotics interfered with key metabolic pathways, resulting in marked suppression of methane generation. Bliss Independence Model (BIM) analysis demonstrated that their joint effects were concentration-dependent, with synergistic inhibition occurred at lower doses and higher levels produced antagonistic interactions, likely reflecting metabolic saturation. Further experiments revealed co-exposure triggered excessive reactive oxygen species (ROS) accumulation, decreased key enzyme activity, cell activities. While partial biotransformation of SMX/TMP was observed, transformation products did not serve as carbon sources for methane enhancement. Partitioning assessment showed that both compounds were predominantly retained within extracellular polymeric substances (EPS), with notable fractions remaining in soluble EPS, indicating restricted cellular penetration and potential antibiotic residues in effluent. Microbial community analysis showed severe inhibition of hydrolytic and acidogenic microorganisms such as Syntrophomonas and Romboutsia, but significantly enhanced the abundance of antibiotic degrading functional microorganisms such as norank_f_Anaerolineaceae, which mean a potential degradation in AD system. Moreover, conventional methanogens decreased severely but Candidatus Methanofastidiosum displayed notable resilience, indicating a methane production feasibility in antibiotics stress AD system. These findings provide a comprehensive understanding of the concentration-dependent interaction, transformation, and partitioning behavior of co-occurring SMX/TMP, offering new mechanistic insights into their ecological risks and persistence in AD systems.
Organophosphate esters (OPEs) are widely used synthetic chemicals associated with increased plasma glucose in the general populations; however, evidence regarding their associations among pregnant women remains limited. In the Shanghai-Minhang Birth Cohort Study, urinary concentrations of eight OPE metabolites were measured at 12−16 weeks of gestation. Data on fasting plasma glucose (FPG) and 1 h-plasma glucose (1 h-PG) were obtained from medical records. Women were classified as having elevated glucose levels based on abnormal FPG, 1 h-PG, or a diagnosis of gestational diabetes mellitus (GDM). Multiple linear regression and Bayesian Kernel Machine Regression (BKMR) were employed to estimate associations between individual OPE metabolites or OPE mixtures and plasma glucose levels. Modified Poisson regression assessed the associations of OPE metabolites with the risk of elevated glucose levels. Compared with the lowest exposure group, the highest exposure to bis(1,3-dichloro-2-propyl) phosphate, dibutyl phosphate, and diphenyl phosphate was significantly associated with lower FPG levels. However, 1 h-PG levels tended to increase in the moderate exposure group, with ∑Cl-OPEs showing a marginally significant association. Poisson regression results similarly indicated that pregnant women with moderate exposure had an increased risk of elevated glucose levels, though without statistical significance. The BKMR model produced similar findings, indicating that chlorinated-OPE primarily contributed to altered FPG and 1 h-PG, with bis(1,3-dichloro-2-propyl) phosphate and bis(1-chloro-2-propyl) phosphate being the major contributors, respectively. Additionally, associations between OPE exposure and decreased FPG levels were predominantly observed among pregnant women with daily fruit and vegetable intake. The present study observed different association patterns between OPE exposure and FPG or 1 h-PG levels, suggesting potential disruptive effects of OPEs on glucose homeostasis during pregnancy.
The anaerobic oxidation of methane linked to metal oxide reduction (metal-dependent AOM) plays a crucial role in regulating methane fluxes within deep-sea sedimentary environments. While metal-dependent AOM has been reported, current understanding is primarily derived from in situ investigations and enrichment experiments conducted under atmospheric pressure, leaving its applicability to the high-pressure, low-temperature deep-sea environment uncertain. In this study, we established long-term enrichment cultures of microbial communities from South China Sea cold seep sediments (1392 m) with manganese/iron oxides as electron acceptors under simulated in situ pressure-temperature conditions (12 MPa, 4 °C). Our results demonstrate significant methane consumption (approximately 30%) accompanied by the accumulation of Mn (II) and Fe (II) over 150 d. Microbial community analysis revealed that anaerobic methanotrophic archaea (ANME-1) dominated the archaeal community. Their predicted extracellularly secreted multi-heme cytochromes (MHCs) may facilitate direct electron transfer under high pressure. Metagenomic analysis further revealed a diversity of methane metabolic pathways within the community. Horizontal gene transfer may have facilitated microbial electron exchange, while ANME archaea engaged in cross-feeding with bacterial groups via metabolites such as acetate and amino acids. This study underscores the critical role of microbial community synergy and adaptive evolution in regulating methane oxidation under simulated deep-sea conditions, providing new insights into the marine carbon cycle.
Microplastics (MPs) pose a significant threat to soil and groundwater quality. Yet, investigating their transport in soils has so far been limited to conventional packed column experiments where particles suspended in a stock dispersion are injected from one side of the column. This, however, does not represent the natural condition where buoyant MPs are released on the surface of the soil and storm or irrigation water induces their penetration into the soil depth. To consider such prevailing natural condition, we develop a new column experiment setup and a corresponding modeling approach to study the transport of low-density polyethylene MPs in different farmland soil types and investigate the impact of photodegradation and natural organic matter. Results revealed a substantial penetration of buoyant MPs in the soil due to the irrigation or rainfall scenarios. Mathematical modeling showed that processes such as attachment, detachment, blocking, and straining, previously observed for colloidal particles in direct injection scenarios, occur for buoyant MPs irrigation or rainfall release scenario. MPs transport increased in silt compared to the silt loam and in the presence of natural organic matter. UV-photodegraded MPs transport was greater than pristine MPs because of increased surface charge and electrostatic repulsion, reducing MPs attachment to soil.
Quantifying commercial cooking emissions is non-negligible for mitigating urban PM2.5 and O3 pollution, given their significant and spatiotemporally concentrated releases of PM2.5 and volatile organic compounds (VOCs). However, the accuracy of existing commercial cooking emission inventories remains unsatisfactory because generalized estimation parameters fail to represent the dynamic emission variations of this sector. Here, we develop a unified online-source framework (UOS) that simultaneously refines emission magnitudes and spatiotemporal allocations by integrating sample-based calibrated online oil fumes monitoring and point-of-interest data. Our framework corrected a 5.95- and 2.09-fold underestimation of VOCs and PM2.5 emissions in Guangdong Province in 2023 compared to the legacy version, in which hourly-scale emission factors significantly increased up to 159.13 g/h for VOCs and 52.47 g/h for PM2.5, respectively. Moreover, the spatial distribution was optimized to 70% of emission hotspots captured in the Pearl River Delta (PRD) region relative to the 50% population-based allocation of the legacy inventory. With improved spatiotemporal performance in simulated PM2.5 and O3, the UOS framework demonstrated a substantially greater annual contribution of commercial cooking emissions to PM2.5 (2.93 μg/m3) than to O3 (1.02 μg/m3), as well as more pronounced contributions of both PM2.5 (12.06 μg/m3) and O3 (8.39 μg/m3) in high-emission areas during pollution episodes. This work offers a scalable methodology to develop accurate commercial cooking emission inventories, thereby providing a scientific foundation for making targeted emission-reduction policies in commercial cooking.
Feammox, i.e., anaerobic ammonium oxidation coupled with ferric iron (Fe(III)) reduction, has been considered as a promising option for autotrophic nitrogen removal in wastewater with low carbon/nitrogen ratio. This study proposed a novel technology coupling Feammox and vivianite crystallization for the simultaneous removal of ammonium and phosphate in low-strength wastewater. The results showed that the Feammox process achieved high-level phosphate removal with the selective addition of amorphous ferric oxyhydroxide (amorphous FeOOH) as the iron source, compared to the other iron oxides hematite (α-Fe2O3) and magnetite (Fe3O4). The removal efficiencies of nitrogen and phosphate reached 77.6% and 77.1%, respectively, with the addition of 0.4 g/L amorphous FeOOH (equivalent to 0.3 g Fe/L). Fundamental investigations through a combination of microscopic images, X-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy, Mössbauer spectroscopy and sequential phosphate extraction method revealed potential mechanisms for phosphate removal. With the addition of amorphous FeOOH, phosphate was firstly adsorbed to mineral surface sites, and then formed vivianite crystals along with microbial Fe(III) reduction (i.e., Feammox reaction) for iron availability. As a result, the Fe(II) formed in Feammox served as a phosphate sink through vivianite precipitation. This study improves the understanding of nitrogen and phosphate transformations in the proposed innovative Feammox-based process and supports the development of next-generation wastewater treatment technologies.