Membrane distillation of wastewater: comparison of model and real organics.

Fouling behaviour in membrane distillation (MD) processes plays a crucial role in determining their widespread acceptability. Most studies have primarily focused on model organic foulants, such as humic acid (HA) and sodium alginate (SA). This study investigates the fouling of a polytetrafluoroethylene membrane in a direct contact MD (DCMD) using model organics (i.e., HA and SA) and real wastewater. The results indicated that the flux decline (5-60%) was only observed during the initial phase of the operation with model organic foulants. In contrast, real wastewater caused a gradual decline in flux throughout the experiment in both the concentrate (40%) and continuous (90%) modes. The study also found significant differences in the fouling layer morphology, composition, and hydrophobicity between the model organic foulants and real wastewater. Fourier transform infrared spectroscopy findings demonstrated that the fouling layer formed by real wastewater varied significantly from model organics, which primarily comprised of protein-like and polysaccharide-like functional groups. Finally, liquid chromatography-organic carbon detection revealed that the fouling layer of the MD membrane with real wastewater was composed of 40.7% hydrophobic and 59.3% hydrophilic organics. This study suggests that model organics may not accurately reflect real wastewater fouling.

Advancement of membrane separation technology for organic pollutant removal.

In the face of growing global freshwater scarcity, the imperative to recycle and reuse water becomes increasingly apparent across industrial, agricultural, and domestic sectors. Eliminating a range of organic pollutants in wastewater, from pesticides to industrial byproducts, presents a formidable challenge. Among the potential solutions, membrane technologies emerge as promising contenders for treating diverse organic contaminants from industrial, agricultural, and household origins. This paper explores cutting-edge membrane-based approaches, including reverse osmosis, nanofiltration, ultrafiltration, microfiltration, gas separation membranes, and pervaporation. Each technology's efficacy in removing distinct organic pollutants while producing purified water is scrutinized. This review delves into membrane fouling, discussing its influencing factors and preventative strategies. It sheds light on the merits, limitations, and prospects of these various membrane techniques, contributing to the advancement of wastewater treatment. It advocates for future research in membrane technology with a focus on fouling control and the development of energy-efficient devices. Interdisciplinary collaboration among researchers, engineers, policymakers, and industry players is vital for shaping water purification innovation. Ongoing research and collaboration position us to fulfill the promise of accessible, clean water for all.

Electronic Structure Optimization and Proton-Transfer Enhancement on Titanium Oxide-Supported Copper Nanoparticles for Enhanced Nitrogen Recycling from Nitrate-Contaminated Water.

Electrocatalytic reduction of nitrate to NH3 (NO3RR) on Cu offers sustainable NH3 production and nitrogen recycling from nitrate-contaminated water. However, Cu affords limited NO3RR activity owing to its unfavorable electronic state and the slow proton transfer on its surface, especially in neutral/alkaline media. Furthermore, although a synchronous "NO3RR and NH3 collection" system has been developed for nitrogen recycling from nitrate-laden water, no system is designed for natural water that generally contains low-concentration nitrate. Herein, we demonstrate that depositing Cu nanoparticles on a TiO2 support enables the formation of electron-deficient Cuδ+ species (0 < δ ≤ 2), which are more active than Cu0 in NO3RR. Furthermore, TiO2-Cu coupling induces local electric-field enhancement that intensifies water adsorption/dissociation at the interface, accelerating proton transfer for NO3RR on Cu. With the dual enhancements, TiO2-Cu delivers an NH3-N selectivity of 90.5%, mass activity of 41.4 mg-N h gCu-1, specific activity of 377.8 mg-N h-1 m-2, and minimal Cu leaching (<25.4 µg L-1) when treating 22.5 mg L-1 of NO3--N at -0.40 V, outperforming most of the reported Cu-based catalysts. A sequential NO3RR and NH3 collection system based on TiO2-Cu was then proposed, which could recycle nitrogen from nitrate-contaminated water under a wide concentration window of 22.5-112.5 mg L-1 at a rate of 209-630 mgN m-2 h-1. We also demonstrated this system could collect 83.9% of nitrogen from NO3--N (19.3 mg L-1) in natural lake water.

Enhanced ozonation of polystyrene nanoplastics in water with CeOx@MnOx catalyst.

The nanoplastics released into the environment pose a critical threat to creatures, and thus it is necessary to remove them. However, their natural decomposition usually takes years or even decades, which raises an imminent demand for an efficient removal technology. Herein we report a core-shell CeOx@MnOx catalyst for enhancing ozonation of polystyrene nanoplastics in water. Ozonation achieves 31.67% molecular weight removal of polystyrene nanoplastics in the first 10 min reaction, which is increased to 51.67% in catalytic ozonation by MnOx and further improved to 73.33% in catalytic ozonation via CeOx@MnOx. The remarkable thing is the CeOx@MnOx could achieve almost 96.70% molecular weight removal after 50 min reaction. The specific catalytic mechanism is ozone decomposes into reactive oxygen radicals (•OH, •O2- and 1O2) after capturing electrons from MnOx, improving the polystyrene nanoplastics removal. Meanwhile, the Mn averaged valence state increases, making it harder to donate electrons to ozone. This can be alleviated by encapsulating the CeOx core in the MnOx, enabling electrons replenishment from the CeOx core to the MnOx shell, which is verified by the experiment and density functional theory calculations. The repeated experiment demonstrates the CeOx@MnOx possesses excellent stability, maintaining 95.25-96.70% removal efficiency of polystyrene nanoplastics. This research provides a possibility for the efficient removal of nanoplastics in water.

Physiological suitability of sulfate-reducing granules for the development of bioconcrete.

Regular monitoring and timely repair of concrete cracks are required to minimize further deterioration. Self-healing of cracks has been proposed as an alternative to the crack maintenance procedures. One of the proposed techniques is to use axenic cultures to exploit microbial-induced calcite precipitation (MICP). However, such healing agents are not cost-effective for in situ use. As the market for bio-based self-healing concrete necessitates a low-cost bio-agent, nonaxenic sulfate reducing bacterial (SRB) granules were investigated in this study through cultivation in an upflow anaerobic sludge blanket reactor. The compact granules can protect the bacteria from adverse conditions without encapsulation. This study investigated the microbial activities of SRB granules at different temperatures, pH, and chemical oxygen demand concentrations which the microbes would experience during the concrete casting and curing process. The attenuation and recovery of microbial activities were measured before and after the exposure. Moreover, the MICP yield was also tested for a possible use in self-healing bioconcrete. The results consistently showed that SRB granules were able to survive starvation, high temperature (50-60°C), and high pH (12), together with scanning electron microscope/energy dispersive spectrometry/X-ray diffraction analysis evidence. Microbial staining analysis demonstrated the formation of spores in the granules during their exposure to harsh conditions. SRB granule was thus demonstrated to be a viable self-healing nonaxenic agent for low-cost bioconcrete.

Enhancing harvest of biodiesel-promising microalgae using Daphnia domesticated by amino acids.

Mass production of microalgal biodiesel is hindered by microalgae harvesting efficiency and costs. In this study, Daphnia domesticated by amino acids were used to harvest microalgae via ingesting. The main factors (density of Daphnia, salinity, pH, light-environment, temperature and algal concentration) that were conducive to Daphnia feeding were optimized. Under the optimal condition, Microalgae-feeding Daphnia were domesticated by adding D-glutamic acid and L-cysteine as stimulating factors. After that, the ingestion rate of domesticated Daphnia increased by 24.93%. The presence of Daphnia as a predator can induce microalgae to mass into clusters. Combining Daphnia feeding and the inductive defense flocculation of microalgae, the harvesting rate of mixed algae (Chlorella pyrenoidosa and Scenedesmus obliquus) reached over 95% after 9 h. Overall, this work suggested that Daphnia feeding process is a green and economical approach for microalgae harvesting.

SARS-CoV-2 and other pathogens in municipal wastewater, landfill leachate, and solid waste: A review about virus surveillance, infectivity, and inactivation.

This review discusses the techniques available for detecting and inactivating of pathogens in municipal wastewater, landfill leachate, and solid waste. In view of the current COVID-19 pandemic, SARS-CoV-2 is being given special attention, with a thorough examination of all possible transmission pathways linked to the selected waste matrices. Despite the lack of works focused on landfill leachate, a systematic review method, based on cluster analysis, allows to analyze the available papers devoted to sewage sludge and wastewater, allowing to focalize the work on technologies able to detect and treat pathogens. In this work, great attention is also devoted to infectivity and transmission mechanisms of SARS-CoV-2. Moreover, the literature analysis shows that sewage sludge and landfill leachate seem to have a remote chance to act as a virus transmission route (pollution-to-human transmission) due to improper collection and treatment of municipal wastewater and solid waste. However due to the incertitude about virus infectivity, these possibilities cannot be excluded and need further investigation. As a conclusion, this paper shows that additional research is required not only on the coronavirus-specific disinfection, but also the regular surveillance or monitoring of viral loads in sewage sludge, wastewater, and landfill leachate. The disinfection strategies need to be optimized in terms of dosage and potential adverse impacts like antimicrobial resistance, among many other factors. Finally, the presence of SARS-CoV-2 and other pathogenic microorganisms in sewage sludge, wastewater, and landfill leachate can hamper the possibility to ensure safe water and public health in economically marginalized countries and hinder the realization of the United Nations' sustainable development goals (SDGs).

Lead time of early warning by wastewater surveillance for COVID-19: Geographical variations and impacting factors.

The global data on the temporal tracking of the COVID-19 through wastewater surveillance needs to be comparatively evaluated to generate a proper and precise understanding of the robustness, advantages, and sensitivity of the wastewater-based epidemiological (WBE) approach. We reviewed the current state of knowledge based on several scientific articles pertaining to temporal variations in COVID-19 cases captured via viral RNA predictions in wastewater. This paper primarily focuses on analyzing the WBE-based temporal variation reported globally to check if the reported early warning lead-time generated through environmental surveillance is pragmatic or latent. We have compiled the geographical variations reported as lead time in various WBE reports to strike a precise correlation between COVID-19 cases and genome copies detected through wastewater surveillance, with respect to the sampling dates, separately for WASH and non-WASH countries. We highlighted sampling methods, climatic and weather conditions that significantly affected the concentration of viral SARS-CoV-2 RNA detected in wastewater, and thus the lead time reported from the various climatic zones with diverse WASH situations were different. Our major findings are: i) WBE reports around the world are not comparable, especially in terms of gene copies detected, lag-time gained between monitored RNA peak and outbreak/peak of reported case, as well as per capita RNA concentrations; ii) Varying sanitation facility and climatic conditions that impact virus degradation rate are two major interfering features limiting the comparability of WBE results, and iii) WBE is better applicable to WASH countries having well-connected sewerage system.

Successful application of wastewater-based epidemiology in prediction and monitoring of the second wave of COVID-19 with fragmented sewerage systems-a case study of Jaipur (India).

The present study tracked the city-wide dynamics of severe acute respiratory syndrome-corona virus 2 ribonucleic acids (SARS-CoV-2 RNA) in the wastewater from nine different wastewater treatment plants (WWTPs) in Jaipur during the second wave of COVID-19 out-break in India. A total of 164 samples were collected weekly between February 19th and June 8th, 2021. SARS-CoV-2 was detected in 47.2% (52/110) influent samples and 37% (20/54) effluent samples. The increasing percentage of positive influent samples correlated with the city's increasing active clinical cases during the second wave of COVID-19 in Jaipur. Furthermore, wastewater-based epidemiology (WBE) evidence clearly showed early detection of about 20 days (9/9 samples reported positive on April 20th, 2021) before the maximum cases and maximum deaths reported in the city on May 8th, 2021. The present study further observed the presence of SARS-CoV-2 RNA in treated effluents at the time window of maximum active cases in the city even after tertiary disinfection treatments of ultraviolet (UV) and chlorine (Cl2) disinfection. The average genome concentration in the effluents and removal efficacy of six commonly used treatments, activated sludge process + chlorine disinfection (ASP + Cl2), moving bed biofilm reactor (MBBR) with ultraviolet radiations disinfection (MBBR + UV), MBBR + chlorine (Cl2), sequencing batch reactor (SBR), and SBR + Cl2, were compared with removal efficacy of SBR + Cl2 (81.2%) > MBBR + UV (68.8%) > SBR (57.1%) > ASP (50%) > MBBR + Cl2 (36.4%). The study observed the trends and prevalence of four genes (E, RdRp, N, and ORF1ab gene) based on two different kits and found that prevalence of N > ORF1ab > RdRp > E gene suggested that the effective genome concentration should be calculated based on the presence/absence of multiple genes. Hence, it is imperative to say that using a combination of different detection genes (E, N, RdRp, & ORF1ab genes) increases the sensitivity in WBE.

Effects of pH, Temperature, Suspended Solids, and Biological Activity on Transformation of Illicit Drug and Pharmaceutical Biomarkers in Sewers.

In-sewer stability of biomarkers is a critical factor for wastewater-based epidemiology, as it could affect the accuracy of the estimated prevalence of substances in the community. The spatiotemporal variations of environmental and biological conditions in sewers can influence the transformation of biomarkers. To date, the relationship between environmental variables and biomarker stability in sewers is poorly understood. Therefore, this study evaluated the transformation of common illicit drug and pharmaceutical biomarkers in laboratory sewer reactors with different levels of pH, temperature, and suspended solids. The correlations between degradation rates of 14 biomarkers, 3 controlled environmental variables (pH, temperature, and suspended solids concentration), and 3 biological activity indicators (sulfide production rate, methane production rate, and the removal rate of soluble chemical oxygen demand (SCOD)) were assessed using correlation matrix, stepwise regression method, and principal component analysis. The consistent results affirmed the dominant effects of biological activities and pH on biomarker transformation in sewers, particularly for labile compounds, whereas the impact of temperature or suspended solids was less significant. This study enhances the understanding of factors affecting the fate of micropollutants in sewer systems and facilitates the interpretation of WBE results for assessing drug use and public health in communities.

Uncertainties in estimating SARS-CoV-2 prevalence by wastewater-based epidemiology.

Wastewater-based epidemiology (WBE) is a promising approach for estimating population-wide COVID-19 prevalence through detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA in wastewater. However, various methodological challenges associated with WBE would affect the accuracy of prevalence estimation. To date, the overall uncertainty of WBE and the impact of each step on the prevalence estimation are largely unknown. This study divided the WBE approach into five steps (i.e., virus shedding; in-sewer transportation; sampling and storage; analysis of SARS-CoV-2 RNA concentration in wastewater; back-estimation) and further summarized and quantified the uncertainties associated with each step through a systematic review. Although the shedding of SARS-CoV-2 RNA varied greatly between COVID-19 positive patients, with more than 10 infected persons in the catchment area, the uncertainty caused by the excretion rate became limited for the prevalence estimation. Using a high-frequency flow-proportional sampling and estimating the prevalence through actual water usage data significantly reduced the overall uncertainties to around 20-40% (relative standard deviation, RSD). And under such a scenario, the analytical uncertainty of SARS-CoV-2 RNA in wastewater was the dominant factor. This highlights the importance of using surrogate viruses as internal or external standards during the wastewater analysis, and the need for further improvement on analytical approaches to minimize the analytical uncertainty. This study supports the application of WBE as a complementary surveillance strategy for monitoring COVID-19 prevalence and provides methodological improvements and suggestions to enhance the reliability for future studies.

Reduction of excess sludge production by membrane bioreactor coupled with anoxic side-stream reactors.

While cleaning wastewater, biological wastewater treatment processes such as membrane bioreactors (MBR) produce a significant amount of sludge that requires costly management. In the oxic-settling-anoxic (OSA) process, sludge is retained for a temporary period in side-stream reactors with low oxygen and substrate, and then it is recirculated to the main reactor. In this way, excess sludge production is reduced. We studied the influence of the rate of sludge exchange between MBR and side-stream anoxic reactors on sludge yield reduction within MBR. Two MBRs, namely, MBROSA and MBRcontrol, each coupled with separate external anoxic side-stream reactors, were run in parallel for 350 days. Unlike MBRcontrol, MBROSA had sludge exchange with the external reactors connected to it. During the investigation over a sludge interchange rate (SIR) range of 0-22%, an SIR of 11% achieved the highest sludge reduction (58%). Greater volatile solids destruction i.e., bacterial cell lysis and extracellular polymeric substance (EPS) destruction occurred at the SIR of 11%, which helped to achieve the highest sludge reduction. The enhanced volatile solids destruction was evident by the release of nutrients in the external anoxic reactors. It was confirmed that the sludge yield reduction was achieved without compromising the wastewater treatment quality, sludge settleability and hydraulic performance of the membrane in MBR.

Transformation of Illicit Drugs and Pharmaceuticals in Sewer Sediments.

In-sewer stability of human excreted biomarkers is a critical factor of wastewater-based epidemiology in back-estimating illicit drug and pharmaceutical use in the community. Biomarker stability has been investigated in sewers with the presence of biofilms, but the understanding in sewer sediments is still lacking. This study for the first time employed a laboratory sediment reactor to measure 18 illicit drug and pharmaceutical biomarkers under gravity sewer environments with the presence of sediments. Biomarkers exhibited various stability patterns due to transformation processes occurring in the bulk wastewater and sediments. The attenuation of a biomarker by sediments is driven by complex processes involving biodegradation, diffusion, and sorption, which is directly proportional to the ratio of sediment surface area against wastewater volume. The sediment-driven transformation coefficients of biomarkers are higher than the accordingly biofilm-mediated rates because of stronger microbial activities in sediments. Additionally, the stability of most biomarkers was insensitive to the natural pH variation in sewers, except for a few compounds (e.g., methadone, ketamine, and paracetamol) susceptible to pH changes. In general, this study delineates the stability data of various biomarkers in gravity sewers with sediments, which are novel and long-missing information for wastewater-based epidemiology and improve the reliability of back-estimation in complex sewer networks.

Increased Resistance of Nitrite-Admixed Concrete to Microbially Induced Corrosion in Real Sewers.

Microbially induced concrete corrosion is a major deterioration process in sewers, causing a huge economic burden, and improved mitigating technologies are required. This study reports a novel and promising effective solution to attenuate the corrosion in sewers using calcium nitrite-admixed concrete. This strategy aims to suppress the development and activity of corrosion-inducing microorganisms with the antimicrobial free nitrous acid, which is generated in situ from calcium nitrite that is added to the concrete. Concrete coupons with calcium nitrite as an admixture were exposed in a sewer manhole, together with control coupons that had no nitrite admixture, for 18 months. The corrosion process was monitored by measuring the surface pH, corrosion product composition, concrete corrosion loss, and the microbial community on the corrosion layer. During the exposure, the corrosion loss of the admixed concrete coupons was 30% lower than that of the control coupons. The sulfide uptake rate of the admixed concrete was also 30% lower, leading to a higher surface pH (0.5-0.6 unit), in comparison to that of the control coupons. A negative correlation between the calcium nitrite admixture in concrete and the abundance of sulfide-oxidizing microorganisms was determined by DNA sequencing. The results obtained in this field study demonstrated that this novel use of calcium nitrite as an admixture in concrete is a promising strategy to mitigate the microbially induced corrosion in sewers.

Serum Levels of OPG, RANKL, and RANKL/OPG Ratio in Patients with Ankylosing Spondylitis: A Systematic Review and Meta-analysis.

Objectives: To investigate the role of osteoprotegerin (OPG), receptor activator of nuclear factor-kB ligand (RANKL), and RANKL/OPG ratio in the pathogenesis of ankylosing spondylitis (AS). Methods: Studies that compared serum levels of OPG, RANKL, and RANKL/OPG ratio between AS patients and healthy controls were gathered. Pooled standardized mean differences (SMDs) with 95% confidence intervals (CIs) were calculated by the random-effects model. Results: Twenty studies containing 1592 AS patients and 1064 healthy controls were included in this meta-analysis. Serum levels of OPG, RANKL, and RANKL/OPG ratio in AS patients were significantly higher than that in normal controls (OPG: SMD = 0.401, 95%CI = 0.026-0.777, p = 0.036; RANKL: SMD = 1.116, 95%CI = 0.510-1.723, p < 0.001; RANKL/OPG ratio: SMD = 0.691, 95%CI = 0.084-1.299, p = 0.026, respectively). Subgroup analysis suggested that Asian AS patients and patients with elevated ESR (ESR >20 mm/h) had higher serum OPG levels compared to normal controls. Asian patients, CRP >10 mg/L, ESR >20 mm/h, duration of disease ≤8 years, and BASDAI score >4 points subgroups showed increased RANKL levels compared to controls. Conclusions: Serum levels of OPG, RANKL, and RANKL/OPG ratio may be used as potential susceptible biomarkers for AS, but they could be influenced by race, inflammatory factors, and disease activity of AS patients.

Experimental Investigation and Modeling of the Transformation of Illicit Drugs in a Pilot-Scale Sewer System.

In-sewer stability of illicit drug biomarkers has been evaluated by several reactor-based studies, but less has been done in sewer pipes. Experiments conducted in sewer pipes have advantages over lab-scale reactors in providing more realistic biomarker stability due to the flow and biological dynamics. This study assessed the transportation and transformation of seven illicit drug biomarker compounds in a pilot-scale rising main and a gravity sewer pipe. Biomarkers presented diverse stability patterns in the pilot sewers, based on which a drug transformation model was calibrated. This model was subsequently validated using transformation data sets from the literature, aiming to demonstrate the predictability of the pilot-based transformation coefficients under varying sewer conditions. Furthermore, transformation coefficients for five investigated biomarkers were generated from four studies, and their prediction capabilities under the pilot-sewer conditions were jointly assessed using performance statistics. The transformation model was successful in simulating the in-sewer stability for most illicit drugs. However, further study is required to delineate the sources and pathways for those compounds with potential formations to be simulated in the transformation model. Overall, the transformation model calibrated using the pilot-sewer data is a credible tool for the application of wastewater-based epidemiology.

Removal of Pharmaceuticals and Illicit Drugs from Wastewater Due to Ferric Dosing in Sewers.

Ferric (Fe3+) salt dosing is an efficient sulfide control strategy in the sewer network, with potential for multiple benefits including phosphorus removal in the biological reactors and sulfide emission control in the anaerobic digesters of wastewater treatment plant (WWTP). This paper extends the knowledge on the benefit of iron dosing by exploring its impact on the fate of organic micropollutants (MPs) in the wastewater using sewer reactors simulating a rising main sewer pipe. The sulfide produced by the sewer biofilms reacted with Fe3+ forming black colored iron sulfide (FeS). Among the selected MPs, morphine, methadone, and atenolol had >90% initial rapid removal within 5 min of ferric dosing in the sewer reactor. The ultimate removal after 6 h of retention time in the reactor reached 93-97%. Other compounds, ketamine, codeine, carbamazepine, and acesulfame had 30-70% concentration decrease. The ultimate removal varied between 35 and 70% depending on the biodegradability of those MPs. In contrast, paracetamol had no initial removal. The rapid removal of MPs was likely due to adsorption to the FeS surface, which is further confirmed by batch tests with different FeS concentrations. The results showed a direct relationship between the removal of MPs and FeS concentration. The transformation kinetics of these compounds in the reactor without Fe3+ dosing is in good agreement with biodegradation associated with the sewer biofilms in the reactor. This study revealed a significant additional benefit of dosing ferric salts in sewers, that is, the removal of MPs before the sewage enters the WWTP.

Evaluation of data-driven models for predicting the service life of concrete sewer pipes subjected to corrosion.

Concrete corrosion is one of the most significant failure mechanisms of sewer pipes, and can reduce the sewer service life significantly. To facilitate the management and maintenance of sewers, it is essential to obtain reliable prediction of the expected service life of sewers, especially if that is based on limited environmental conditions. Recently, a long-term study was performed to identify the controlling factors of concrete sewer corrosion using well-controlled laboratory-scale corrosion chambers to vary levels of H2S concentration, relative humidity, temperature and in-sewer location. Using the results of the long-term study, three different data-driven models, i.e. multiple linear regression (MLR), artificial neural network (ANN), and adaptive neuro fuzzy inference system (ANFIS), as well as the interaction between environmental parameters, were assessed for predicting the corrosion initiation time (ti) and corrosion rate (r). This was performed using the sewer environmental factors as the input under 12 different scenarios after allowing for an initiation corrosion period. ANN and ANFIS models showed better performance than MLR models, with or without considering the interactions between environmental factors. With the limited input data available, it was observed that ti prediction by these models is quite sensitive, however, they are more robust for predicting r as long as the H2S concentration is available. Using the H2S concentration as a single input, all three data driven models can reasonably predict the sewer service life.

Association of TLR7 gene copy number variations with ankylosing spondylitis in a Chinese population: a case control study.

OBJECTIVES: To explore the association of TLR7 gene copy number variations (CNVs) with the susceptibility of ankylosing spondylitis (AS). METHODS: The case control study was performed in 649 Chinese Han patients with AS and 628 healthy controls. The copy numbers of TLR7 gene (2 fragments) were measured by AccuCopyTM methods. Chi-square and logistic regression models were performed to investigate the association of TLR7 gene CNVs with AS. Odds ratio (ORs) and 95% confidence intervals (CIs) was calculated to estimate AS risk and the Bonferroni correction was applied owing to multiple testing. RESULTS: The logistic regression analysis showed that one copy was significantly associated with AS susceptibility after Bonferroni correction (for the TLR7_1 fragment: OR=1.458, 95%CI(1.098,1.936), p=0.009; for the TLR7_2 fragment: OR=1.451, 95%CI (1.093,1.927), p=0.010), and this association still exists after adjustment of age and sex (for the TLR7_1 fragment: adjusted OR=2.066, 95%CI (1.318,3.238), p=0.002; for the TLR7_2 fragment: adjusted OR=2.061, 95%CI (1.315,3.230), p=0.002). However, logistic regression analysis stratified by gender showed a higher OR in males (for the TLR7_1 fragment: OR(95%CI)=7.987(3.756,16.983); for the TLR7_2 fragment: OR(95%CI)=7.947(3.738,16.897)) than in females (for the TLR7_1 fragment: OR(95%CI)=0.204(0.080,0.524); for the TLR7_2 fragment: OR(95%CI)=0.204(0.080,0.524)). CONCLUSIONS: We conclude that the lower copy number (=1) of TLR7 gene confers a risk factor for AS susceptibility in males but protective factor in females.

Unraveling the Mechanisms of Visible Light Photocatalytic NO Purification on Earth-Abundant Insulator-Based Core-Shell Heterojunctions.

Earth-abundant insulators are seldom exploited as photocatalysts. In this work, we constructed a novel family of insulator-based heterojunctions and demonstrated their promising applications in photocatalytic NO purification, even under visible light irradiation. The heterojunction formed between the insulator SrCO3 and the photosensitizer BiOI, via a special SrCO3-BiOI core-shell structure, exhibits an enhanced visible light absorbance between 400-600 nm, and an unprecedentedly high photocatalytic NO removal performance. Further density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) analysis revealed that the covalent interaction between the O 2p orbital of the insulator (SrCO3, n-type) and the Bi 6p orbital of photosensitizer (BiOI, p-type) can provide an electron transfer channel between SrCO3 and BiOI, allowing the transfer of the photoexcited electrons from the photosensitizer to the conduction band of insulator (confirmed by charge difference distribution analysis and time-resolved fluorescence spectroscopy). The •O2- and •OH radicals are the main reactive species in photocatalytic NO oxidation. A reaction pathway study based on both in situ FT-IR and molecular-level simulation of NO adsorption and transformation indicates that this heterojunction can efficiently transform NO to harmless nitrate products via the NO → NO+ and NO2+ → nitrate or nitrite routes. This work provides numerous opportunities to explore earth-abundant insulators as visible-light-driven photocatalysts, and also offers a new mechanistic understanding of the role of gas-phase photocatalysis in controlling air pollution.