Associations between organophosphate esters and bone mineral density in adults in the United States: 2011-2018 NHANES.

BACKGROUND: Organophosphate esters (OPEs) are used extensively as flame retardants and plasticizers. Laboratory studies have shown that OPEs exhibit osteotoxicity by inhibiting osteoblast differentiation; however, little is known about how OPEs exposure is associated with bone health in humans. OBJECTIVES: We conducted a cross-sectional study to investigate the association between OPEs exposure and bone mineral density (BMD) in adults in the United States using data from the 2011-2018 National Health and Nutrition Examination Survey (NHANES). METHODS: Multivariate linear regression models were used to assess the association between concentrations of individual OPE metabolites and BMDs. We also used the Bayesian kernel machine regression (BKMR) and quantile g-computation (qgcomp) models to estimate joint associations between OPE mixture exposure and BMDs. All the analyses were stratified according to gender. RESULTS: A total of 3546 participants (median age, 40 years [IQR, 30-50 years]; 50.11% male) were included in this study. Five urinary OPE metabolites with a detection rate of > 50% were analyzed. After adjusting for the potential confounders, OPE metabolite concentrations were associated with decreased total-body BMD and lumbar spine BMD in males, although some associations only reached significance for bis(1-chloro-2-propyl) phosphate (BCPP), dibutyl phosphate (DBUP), and bis(2-chloroethyl) phosphate (BCEP) (ß = -0.013, 95% CI: -0.026, -0.001 for BCPP and total-body BMD; ß = -0.022, 95% CI: -0.043, -0.0001 for DBUP and lumbar spine BMD; ß=-0.018, 95% CI: -0.034, -0.002 for BCEP and lumbar spine BMD). OPE mixture exposure was also inversely associated with BMD in males, as demonstrated in the BMKR and qgcomp models. CONCLUSIONS: This study provides preliminary evidence that urinary OPE metabolite concentrations are inversely associated with BMD. The results also suggested that males were more vulnerable than females. However, further studies are required to confirm these findings.

Revealing the mechanism of quartz sand seeding in accelerating phosphorus recovery from anaerobic fermentation supernatant through vivianite crystallization.

The recovery of phosphorus (P) through vivianite crystallization offers a promising approach for resource utilization in wastewater treatment plants. However, this process encounters challenges in terms of small product size and low purity. The study aimed to assess the feasibility of using quartz sand as a seed material to enhance P recovery and vivianite crystal characteristics from anaerobic fermentation supernatant. Various factors, including seed dosage, seed size, Fe/P ratio, and pH, were systematically tested in batch experiments to assess their influence. Results demonstrated that the effect of seed enhancement on vivianite crystallization was more pronounced under higher seed dosages, smaller seed sizes, and lower pH or Fe/P ratio. The addition of seeds increased P recovery by 4.43% in the actual anaerobic fermentation supernatant and also augmented the average particle size of the recovered product from 19.57 to 39.28 µm. Moreover, introducing quartz sand as a seed material effectively reduced co-precipitation, leading to a notable 12.5% increase in the purity of the recovered vivianite compared to the non-seeded process. The formation of an ion adsorption layer on the surface of quartz sand facilitated crystal attachment and growth, significantly accelerating the vivianite crystallization rate and enhancing P recovery. The economic analysis focused on chemical costs further affirmed the economic viability of using quartz sand as a seed material for P recovery through vivianite crystallization, which provides valuable insights for future research and engineering applications.

Phosphorus recovery from synthetic anaerobic fermentation supernatant via vivianite crystallization: Coupling effects of various physicochemical process parameters.

Recovery of phosphorus (P) via vivianite crystallization is an effective strategy to recycle resources from the anaerobic fermentation supernatant. However, the presence of different components in the anaerobic fermentation supernatant (e.g., polysaccharides and proteins) might alter conditions for optimal growth of vivianite crystals, resulting in distinct vivianite characteristics. In the present study, the effect of different components on vivianite crystallization was explored. Then, the reaction parameters (pH, Fe/P, and stirring speed) for P recovery from synthetic anaerobic fermentation supernatant as vivianite were optimized using response surface methodology, and the relationship between crystal properties and supersaturation was elucidated using a thermodynamic equilibrium model. The optimized values for pH, Fe/P, and stirring speed were found to be 7.8, 1.74, and 500 rpm respectively, resulting in 90.54 % P recovery efficiency. Moreover, the variation of reaction parameters did not change the crystalline structure of the recovered vivianite but influenced its morphology, size, and purity. Thermodynamic analysis suggested the saturation index (SI) of vivianite increased with increasing pH and Fe/P ratio, leading to a facilitative effect on vivianite crystallization. However, when the SI was >11, homogenous nucleation occurred so that the nucleation rate was much higher than the crystal growth rate, causing a smaller crystal size. The findings presented herein will be highly valued for the future large-scale application of the vivianite crystallization process for wastewater treatment.

Recovery of phosphorus from wastewater containing humic substances through vivianite crystallization: Interaction and mechanism analysis.

Vivianite crystallization has been regarded as a suitable option for recovering phosphorus (P) from P-containing wastewater. However, the presence of humic substances (HS) would inevitably affect the formation of vivianite crystals. Therefore, the influences of HS on vivianite crystallization and the changes in the harvested vivianite crystals were investigated in this study. The results suggested the inhibition effect of 70 mg/L HS on vivianite crystallization reached 12.24%, while it could be attenuated by increasing the pH and Fe/P ratio of the solution. Meanwhile, the addition of HS altered the size, purity, and morphology of recovered vivianite crystals due to the blockage of the growth sites on the crystal surface. Additionally, the formation of phosphate ester group, hydrogen bonding, and COOH-Fe2+ complexes are the potential mechanisms of HS interaction with vivianite crystals. The results obtained herein will help to elucidate the underlying mechanism of HS on vivianite crystallization from P-containing wastewater.

A "Pre-Division Metal Clusters" Strategy to Mediate Efficient Dual-Active Sites ORR Catalyst for Ultralong Rechargeable Zn-Air Battery.

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal-air batteries, catalysts with dual-active centers have stood out. Here, a "pre-division metal clusters" strategy is firstly conceived to fabricate a N,S-dual doped honeycomb-like carbon matrix inlaid with CoN4 sites and wrapped Co2 P nanoclusters as dual-active centers (Co2 P/CoN4 @NSC-500). A crystalline {CoII 2 } coordination cluster divided by periphery second organic layers is well-designed to realize delocalized dispersion before calcination. The optimal Co2 P/CoN4 @NSC-500 executes excellent 4e- ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2 P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn-air battery (ZAB) assembled by Co2 P/CoN4 @NSC-500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm-2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.

Automated machine learning-based prediction of microplastics induced impacts on methane production in anaerobic digestion.

Microplastics as emerging pollutants have been heavily accumulated in the waste activated sludge (WAS) during biological wastewater treatment, which showed significantly diverse impacts on the subsequent anaerobic sludge digestion for methane production. However, a robust modeling approach for predicting and unveiling the complex effects of accumulated microplastics within WAS on methane production is still missing. In this study, four automated machine learning (AutoML) approach was applied to model the effects of microplastics on anaerobic digestion processes, and integrated explainable analysis was explored to reveal the relationships between key variables (e.g., concentration, type, and size of microplastics) and methane production. The results showed that the gradient boosting machine had better prediction performance (mean squared error (MSE) = 17.0) than common neural networks models (MSE = 58.0), demonstrating that the AutoML algorithms succeeded in predicting the methane production and could select the best machine learning model without human intervention. Explainable analysis results indicated that the variable of microplastic types was more important than the variable of microplastic diameter and concentration. The existence of polystyrene was associated with higher methane production, whereas increasing microplastic diameter and concentration both inhibited methane production. This work also provided a novel modeling approach for comprehensively understanding the complex effects of microplastics on methane production, which revealed the dependence relationships between methane production and key variables and may be served as a reference for optimizing operational adjustments in anaerobic digestion processes.

RhIII-Catalyzed C-H N-Heteroarylation and Esterification Cascade of Carboxylic Acid with Organoboron Reagents and 1,2-Dichloroethane in One-Pot Synthesis.

A RhIII-catalyzed C(sp2)-H N-heteroarylation and esterification cascade of aryl carboxylic acids with N-heteroaromatic boronates and 1,2-dichloroethane in a one-pot synthesis has been disclosed. The strong coordinating ability of ortho- and meta-substituted pyridine boronates and pyrazoles as well as unsubstituted pyrimidine allows them to serve as the coupling partners. This protocol allows late-stage modification of the key precursor of roflumilast and compounds of pharmaceutical interest, which highlights the potential application of this synthetic method.

Interpenetrated N-rich MOF derived vesicular N-doped carbon for high performance lithium ion battery.

High-performance lithium ion batteries (LIBs) juggling high reversible capacity, excellent rate capability and ultralong cycle stability are urgently needed for all electronic devices. Here we report employing a vesicle-like porous N-doped carbon material (abbr. N/C-900) as a highly active anode for LIBs to balance high capacity, high rate and long life. The N/C-900 material was fabricated by pyrolysis of a designed crystal MOF LCU-104, which exhibits a graceful two-fold interpenetrating structural feature of N-rich nanocages {Zn6(dttz)4} linked through an N-donor ligand bpp (H3dttz = 4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole, bpp = 1,3-bis(4-pyridyl)propane). The features of LCU-104 combine high N content (35.1%), interpenetration, and explosive characteristics, which endow the derived N/C material with optimized N-doping for tuning its chemical and electronic structure, a suitably thicker wall to enhance its stability, and a vesicle-like structure to improve its porosity. As an anode material for LIBs, N/C-900 delivers a highly reversible capacity of ca. 734 mA h g-1 at a large current density of 1 A g-1 until the 2000th cycle, revealing its ultralong cycle stability and excellent rate capability. The unique structure and preferential interaction between abundant pyridinic N active sites and Li atoms are responsible for the improved excellent lithium storage capacity and durability performances of the anode according to analysis of the results of computational modeling.

Sludge reduction and microbial community evolution of activated sludge induced by metabolic uncoupler o-chlorophenol in long-term anaerobic-oxic process.

Excess sludge management is a restrictive factor for the development of municipal wastewater treatment plants. The addition of metabolic uncouplers has been proven to be effective in sludge reduction. However, the long-term effect of metabolic uncoupler o-chlorophenol (oCP) on the biological wastewater treatment system operated in anaerobic-oxic mode is still unclear. To this end, two parallel reactors operated in anaerobic-oxic mode with and without 10 mg/L of oCP addition were investigated for 91 days. The results showed that 56.1 ± 2.3% of sludge reduction was achieved in the oCP-added system, and the nitrogen and phosphorus removal ability were negatively affected. Dosing oCP stimulated the formation of microbial products and increased the DNA concentration, but resulted in a decrease in the electronic transport activity of activated sludge. Microbial community analysis further demonstrated that a significant reduction of bacterial richness and diversity occurred after oCP dosing. However, after stopping oCP addition, the pollutant removal ability of activated sludge was gradually increased, but the sludge yield, as well as species richness and diversity, did not recover to the previous level. This study will provide insightful guidance on the long-term application of metabolic uncouplers in the activated sludge system.

Hierarchical Fe-Mn binary metal oxide core-shell nano-polyhedron as a bifunctional electrocatalyst for efficient water splitting.

Electrochemical water splitting is convinced as one of the most promising solutions to combat the energy crisis. The exploitation of efficient hydrogen and oxygen evolution reaction (HER/OER) bifunctional electrocatalysts is undoubtedly a vital spark yet challenging for imperative green sustainable energy. Herein, through introducing a simple pH regulated redox reaction into a tractable hydrothermal procedure, a hierarchical Fe3O4@MnOx binary metal oxide core-shell nano-polyhedron was designed by evolving MnOx wrapped Fe3O4. The MnOx effectively prevents the agglomeration and surface oxidation of Fe3O4 nano-particles and increases the electrochemically active sites. Benefiting from the generous active sites and synergistic effects of Fe3O4 and MnOx, the Fe3O4@MnOx-NF nanocomposite implements efficient HER/OER bifunctional electrocatalytic performance and overall water splitting. As a result, hierarchical Fe3O4@MnOx only requires a low HER/OER overpotential of 242/188 mV to deliver 10 mA cm-2, a small Tafel slope of 116.4/77.6 mV dec-1, combining a long-term cyclability of 5 h. Impressively, by applying Fe3O4@MnOx as an independent cathode and anode, the overall water splitting cell supplies a competitive voltage of 1.64 V to achieve 10 mA cm-2 and super long cyclability of 80 h. These results reveal that this material is a promising candidate for practical water electrolysis application.

Single-crystal-to-single-crystal transformations among three Mn-MOFs containing different water molecules induced by reaction time: crystal structures and proton conductivities.

Three Mn-MOFs {[Mn3(µ4-L)2(H2O)7]·4H2O}n (1), {[Mn3(µ5-L)2(H2O)6]·4H2O}n (2) and {[Mn3(µ7-L)2(H2O)2]}n (3) (H3L = 5-(6-carboxypyridin-3-yl)isophthalic acid) were obtained under different reaction times and temperatures. Interestingly, induced by reaction time, compound 1 can lose one water molecule and SC-SC transform into compound 2. Similarly, compound 2 can also SC-SC transform into 3. Studies on two SC-SC transformation processes were carried out and the transformation mechanisms were deduced, which were verified by TG analyses. Different numbers of water molecules in the three compounds resulted in different coordination environments of the metal cation, coordination modes of the L3- ligand, continuities of hydrogen bonds, dimensions of framework and porosities. The AC impendence spectra studies revealed that compounds 1-3 can enhance the proton conductivities of the Nafion composite membrane to about 47.77%, 36.88% and 21.28%, respectively. It is speculated that the highest proton conductivity of compound 1 may be due to its continuous hydrogen bond chain and highest water uptake, which were mainly decided by the number of water molecules.

Nanocage-Based N-Rich Metal-Organic Framework for Luminescence Sensing toward Fe3+ and Cu2+ Ions.

Luminescent metal-organic frameworks (LMOFs) as sensors showing highly efficient detection toward toxic heavy-metal ions are in high demand for human health and environmental protection. A novel nanocage-based N-rich LMOF (LCU-103) has been constructed and characterized. It is a 2-fold interpenetrating structure built from N-rich {Zn6(dttz)4} nanocages extended by N-donor ligand Hdpa [H3dttz = 4,5-di(1H-tetrazol-5-yl)-2H-1,2,3-triazole; Hdpa = 4,4'-dipyridylamine]. Notably, LCU-103 contains abundant N functional sites anchoring on both the windows of nanocages and the inner channels of the framework that can interact with metal ions and then recognize them. As a result, it can serve as a luminescent sensing material for detecting trace amounts of Fe3+ and Cu2+ ions with low limits of detection (LODs) of 1.45 and 1.66 µM, respectively, through a luminescent quenching mechanism. Meanwhile, LCU-103 as a LMOF sensor exhibits several advantages such as high sensitivity, appropriate selectivity (for Fe3+ in H2O), recycling stability, and fast response times in N,N-dimethylformamide. Moreover, LCU-103 also displays good luminescent quenching activity toward Fe3+ in H2O and a simulated 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid biological system with low LODs of 1.51 and 1.52 µM, respectively. LCU-103 test papers were further prepared to offer easy and real-time detection of Fe3+ and Cu2+ ions. Importantly, when density functional theory calculations and multiple experimental evidence, including X-ray photoelectron spectroscopy, UV-vis absorption, luminescence decay lifetimes, and quantum efficiencies, are combined, a preferred N-donor site and possible weak interaction sensing mechanism is also proposed to elucidate the quenching effect.

A Co-MOF-derived Co9S8@NS-C electrocatalyst for efficient hydrogen evolution reaction.

The exploitation of efficient hydrogen evolution reaction (HER) electrocatalysts has become increasingly urgent and imperative; however, it is also challenging for high-performance sustainable clean energy applications. Herein, novel Co9S8 nanoparticles embedded in a porous N,S-dual doped carbon composite (abbr. Co9S8@NS-C-900) were fabricated by the pyrolysis of a single crystal Co-MOF assisted with thiourea. Due to the synergistic benefit of combining Co9S8 nanoparticles with N,S-dual doped carbon, the composite showed efficient HER electrocatalytic activities and long-term durability in an alkaline solution. It shows a small overpotential of -86.4 mV at a current density of 10.0 mA cm-2, a small Tafel slope of 81.1 mV dec-1, and a large exchange current density (J 0) of 0.40 mA cm-2, which are comparable to those of Pt/C. More importantly, due to the protection of Co9S8 nanoparticles by the N,S-dual doped carbon shell, the Co9S8@NS-C-900 catalyst displays excellent long-term durability. There is almost no decay in HER activities after 1000 potential cycles or it retains 99.5% of the initial current after 48 h.

Fe-MOF-Derived Efficient ORR/OER Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

The construction of an efficient oxygen reduction reaction and oxygen evolution reaction (ORR/OER) bifunctional electrocatalyst is of great significance but still remains a giant challenge for high-performance metal-air batteries. In this study, uniform FeS/Fe3C nanoparticles embedded in a porous N,S-dual doped carbon honeycomb-like composite (abbr. FeS/Fe3C@NS-C-900) have been conveniently fabricated by pyrolysis of a single-crystal Fe-MOF, which has a low potential gap ΔE of ca. 0.72 V, a competitive power density of 90.9 mW/cm2, a specific capacity as high as 750 mAh/gZn, and excellent cycling stabilities over 865 h (1730 cycles) at 2 mA/cm2 when applied as a cathode material for rechargeable zinc-air batteries. In addition, the two series-linked Zn-air batteries successfully powered a 2.4 V LED light as a real power source. The efficient ORR/OER bifunctional electrocatalytic activity and long-term durability of the obtained composite might be attributed to the characteristic honeycomb-like porous structure with sufficient accessible active sites, the synergistic effect of FeS and Fe3C, and the N,S codoped porous carbon, which provides a promising application potential for portable electronic Zn-air battery related devices.

An integrated approach based on virtual data augmentation and deep neural networks modeling for VFA production prediction in anaerobic fermentation process.

Data-driven models are suitable for simulating biological wastewater treatment processes with complex intrinsic mechanisms. However, raw data collected in the early stage of biological experiments are normally not enough to train data-driven models. In this study, an integrated modeling approach incorporating the random standard deviation sampling (RSDS) method and deep neural networks (DNNs) models, was established to predict volatile fatty acid (VFA) production in the anaerobic fermentation process. The RSDS method based on the mean values (x¯) and standard deviations (α) calculated from multiple experimental determination was initially developed for virtual data augmentation. The DNNs models were then established to learn features from virtual data and predict VFA production. The results showed that when 20000 virtual samples including five input variables of the anaerobic fermentation process were used to train the DNNs model with 16 hidden layers and 100 hidden neurons in each layer, the best correlation coefficient of 0.998 and the minimal mean absolute percentage error of 3.28% were achieved. This integrated approach can learn nonlinear information from virtual data generated by the RSDS method, and consequently enlarge the application range of DNNs models in simulating biological wastewater treatment processes with small datasets.

Formation of microbial products by activated sludge in the presence of a metabolic uncoupler o-chlorophenol in long-term operated sequencing batch reactors.

Metabolic uncouplers are widely used for reducing excess sludge in biological wastewater treatment systems. However, the formation of microbial products, such as extracellular polymeric substances, polyhydroxyalkanoate and soluble microbial products by activated sludge in the presence of metabolic uncouplers remains unrevealed. In this study, the impacts of a metabolic uncoupler o-chlorophenol (oCP) on the reduction of activated sludge yield and formation of microbial products in laboratory-scale sequencing batch reactors (SBRs) were evaluated for a long-term operation. The results show the average reduction of sludge yield in the four reactors was 17.40%, 25.80%, 33.02% and 39.50%, respectively, when dosing 5, 10, 15, and 20 mg/L oCP. The oCP addition slightly reduced the pollutant removal efficiency and decreased the formation of soluble microbial products in the SBRs, but stimulated the productions of extracellular polymeric substances and polyhydroxyalkanoate in activated sludge. Furthermore, the significant reduction of electronic transport system activity occurred after the oCP addition. Microbial community analysis of the activated sludge indicates dosing oCP resulted in a decrease of sludge richness and diversity in the SBRs. Hopefully, this study would provide useful information for reducing sludge yield in biological wastewater treatment systems and behaviors of activated sludge in the presence of uncouplers.

Two microporous CoII-MOFs with dual active sites for highly selective adsorption of CO2/CH4 and CO2/N2.

Simultaneously involving abundant [NH2(CH3)2]+ cations and uncoordinated carboxylate oxygen atoms as dual active sites, two microporous CoII-MOFs (LCU-105 and LCU-106, LCU = Liaocheng University) both exhibit highly selective adsorption of CO2/CH4 and CO2/N2. GCMC theoretical simulations provide good verification of the experimental results.

Production of polyhydroxyalkanoates and enrichment of associated microbes in bioreactors fed with rice winery wastewater at various organic loading rates.

This study aimed to explore the production of polyhydroxyalkanoates (PHA) and selection of PHA-accumulating microorganisms in bioreactors fed with rice winery wastewater at various organic loading rates (OLRs). The substrate utilization, sludge properties, PHA synthesis and microbial community structure of three sequencing batch reactors were monitored. The results show the highest PHA yield (0.23 g/g) was achieved in one of the three reactors with an OLR of 2.4 g COD/L/d, in which Zoogloea was the most dominant PHA-accumulating microorganism. To quantify the PHA production and track the population changing profiles of the PHA-accumulating microorganisms in the long-term reactor operation, the Activated Sludge Model No. 3 was modified with two different heterotrophic microorganisms responding differently with the same substrate. The modeling results indicate that a moderate OLR (>2.4 gCOD/L/d) was beneficial for PHA production. The results are useful for understanding the PHA production from industrial wastewaters and selection of PHA-accumulating microorganisms.

Characterization of interactions between a metabolic uncoupler O-chlorophenol and extracellular polymeric substances of activated sludge.

Metabolic uncouplers are widely used for the in-situ reduction of excess sludge from activated sludge systems. However, the interaction mechanism between the metabolic uncouplers and extracellular polymeric substances (EPS) of activated sludge is unknown yet. In this study, the interactions between a typical metabolic uncoupler, o-chlorophenol (oCP), and the EPS extracted from activated sludge were explored using a suite of spectral methods. The binding constants calculated for the four peaks of three-dimensional excitation-emission matrix fluorescence were in a range of 1.24-1.76 × 103 L/mol, implying that the tyrosine protein-like substances governed the oCP-EPS interactions. Furthermore, the results of Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and 1H nuclear magnetic resonance indicated that the carboxyl, carbonyl, amine, and hydroxyl groups of EPS were the main functional groups involved in the formation of the oCP-EPS complex. The results of this study are useful for understanding the interactions between metabolic uncouplers and the EPS of activated sludge as well as their fates in biological wastewater treatment systems.

A dinuclear cobalt cluster as electrocatalyst for oxygen reduction reaction.

Dinuclear metal clusters as metalloenzymes execute efficient catalytic activities in biological systems. Enlightened by this, a dinuclear {CoII 2} cluster was selected to survey its ORR (Oxygen Reduction Reaction) catalytic activities. The crystalline {CoII 2} possesses defined structure and potential catalytic active centers of {CoN4O2} sites, which was identified by X-ray single crystal diffraction, Raman and XPS. The appropriate supramolecular porosity combining abundant pyridinic-N and triazole-N sites of {CoII 2} catalyst synergistically benefit the ORR performance. As a result, this non-noble metal catalyst presents a nice ORR electrocatalytic activity and abides by a nearly 4-electron reduction pathway. Thus, this unpyrolyzed crystalline catalyst clearly provide precise active sites and the whole defined structural information, which can help researcher to design and fabricate efficient ORR catalysts to improve their activities. Considering the visible crystal structure, a single cobalt center-mediated catalytic mechanism was also proposed to elucidate the ORR process.