Hyperspectral Imaging Technique to Characterize Digestate and Visualize Physical Impurities in Anaerobically Digested Biowaste.

Methods used to monitor anaerobic digestion (AD) indicators are commonly based on wet chemical analyses, which consume time and materials. In addition, physical disturbances, such as floating granules (FGs), must be monitored manually. In this study, we present an eco-friendly, high-throughput methodology that uses near-infrared hyperspectral imaging (NIR-HSI) to build a machine-learning model for characterizing the chemical composition of the digestate and a target detection algorithm for identifying FGs. A total of 732 digestate samples were used to develop and validate a model for calculating total nitrogen (TN), total organic carbon (TOC), total ammonia nitrogen (TAN), and chemical oxygen demand (COD), which are the chemical indicators of responses to disturbances in the AD process. Among these parameters, good model performance was obtained using the dried digestates data set, where the coefficient of determination (R2test) and the root-mean-square error (RMSEtest) were 0.82 and 1090 mg/L for TOC, and 0.86 and 690 mg/L for TN, respectively. Furthermore, the unique spectral features of the FGs in reactors with a lipid-rich substrate meant that they could also be identified by the HSI system. Based on these findings, developing NIR-HSI solutions to monitor the digestate properties in AD plants has great potential for industrial application.

Regular Tetrahedron Model for the Assessment of High-Resolution Mass Spectrometry Data of Four-Way Fractionated Dissolved Organic Matter.

A regular tetrahedron model was established to pierce the fractionation of dissolved organic matter (DOM) among quaternary components by using high-resolution mass spectrometry. The model can stereoscopically visualize molecular formulas of DOM to show the preference to each component according to the position in a regular tetrahedron. A classification method was subsequently developed to divide molecular formulas into 15 categories related to fractionation ratios, the relative change of which was demonstrated to be convergent with the uncertainty of mass peak area. The practicality of the regular tetrahedron model was verified by seven kinds of sludge from waste leachate treatment and sewage wastewater treatment plants by using stratification of extracellular polymeric substances coupled with Orbitrap MS as an example, presenting the DOM chemodiversity in stratified sludge flocs. Sensitivity analysis proved that classification results were relatively stable with the perturbation of four model parameters. Multinomial logistic regression analysis could further help identify the effect of molecular properties on the fractionation of DOM based on the classification results of the regular tetrahedron model. This model offers a methodology for the assessment of specificity of sequential extraction on DOM from solid or semisolid components and simplifies the complex mathematical expression of fractionation coefficients for quaternary components.

Functional Redundant Microbiome Enhanced Anaerobic Digestion Efficiency under Ammonium Inhibition Conditions.

Revealing the role of functional redundancy is of great importance considering its key role in maintaining the stability of microbial ecosystems in response to various disturbances. However, experimental evidence on this point is still lacking due to the difficulty in "manipulating" and depicting the degree of redundancy. In this study, manipulative experiments of functional redundancy were conducted by adopting the mixed inoculation strategy to evaluate its role in engineered anaerobic digestion systems under ammonium inhibition conditions. The results indicated that the functional redundancy gradient was successfully constructed and confirmed by evidence from pathway levels. All mixed inoculation groups exhibited higher methane production regardless of the ammonium level, indicating that functional redundancy is crucial in maintaining the system's efficiency. Further analysis of the metagenome-assembled genomes within different functional guilds revealed that the extent of redundancy decreased along the direction of the anaerobic digestion flow, and the role of functional redundancy appeared to be related to the stress level. The study also found that microbial diversity of key functional populations might play a more important role than their abundance on the system's performance under stress. The findings provide direct evidence and highlight the critical role of functional redundancy in enhancing the efficiency and stability of anaerobic digestion.

Optimizing the Quality of Machine Learning for Identifying the Share of Biogenic and Fossil Carbon in Solid Waste.

Insights into carbon sources (biogenic and fossil carbon) and contents in solid waste are vital for estimating the carbon emissions from incineration plants. However, the traditional methods are time-, labor-, and cost-intensive. Herein, high-quality data sets were established after analyzing the carbon contents and infrared spectra of substantial samples using elemental analysis and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), respectively. Then, five classification and eight regression machine learning (ML) models were evaluated to recognize the proportion of biogenic and fossil carbon in solid waste. Using the optimized data preprocessing approach, the random forest (RF) classifier with hyperparameter tuning ranked first in classifying the carbon group with a test accuracy of 0.969, and the carbon contents were successfully predicted by the RF regressor with R2 = 0.926 considering performance-interpretability-computation time competition. The above proposed algorithms were further validated with real environmental samples, which exhibited robust performance with an accuracy of 0.898 for carbon group classification and an R2 value of 0.851 for carbon content prediction. The reliable results indicate that ATR-FTIR coupled with ML algorithms is feasible for rapidly identifying both carbon groups and content, facilitating the calculation and assessment of carbon emissions from solid waste incineration.

Nontarget Insights into the Fate of Cl-/Br-Containing DOM in Leachate during Membrane Treatment.

Halogenated organic compounds in wastewater are persistent and bioaccumulative contaminants of great concern, but few are known at the molecular level. Herein, we focus on nontarget screening of halogenated dissolved organic matter (DOM) in highly concentrated organic matrices of waste leachates and their concentrates. Solid-phase extraction (SPE) was optimized before capturing halogenated signatures via HaloSeeker 2.0 software on mining full-scan high-resolution mass spectrometry (HRMS) fingerprints. This study identified 438 Cl-/Br-containing DOM formulas in 21 leachates and membrane concentrates. Among them, 334 formulas were achieved via SPE with mixed-sorbent cartridges (mixed-SPE), surpassing the 164 formulas achieved through Bond Elut PPL cartridges (PPL-SPE). Herein, only four samples identified via PPL-SPE exhibited a resolution of >50% for extracted Cl-/Br-containing DOM by either SPE. The halogenated DOM constituted 6.87% of the total DOM mass features. Nevertheless, more abundant adsorbable organic halogens deciphered waste leachates and highly concentrated waste streams as reservoirs for halogenated contaminants. Remarkably, 75.7-98.1% of Cl-/Br-containing DOM in primary membrane concentrates remained stable through the secondary membrane treatment, indicating the persistence of these unknown contaminants even post-treatment.

Identification of Cell Status via Simultaneous Multitarget Imaging Using Programmable Scanning Electrochemical Microscopy.

A programmable multitarget-response electrochemical imaging technique was presented using scanning electrochemical microscopy (SECM) combined with a self-designed waveform. The potential waveform applied to the tip decreased the charging current caused by the potential switch, enhancing the signal-to-noise ratio. This programmable SECM (P-SECM) method was used to scan a metal strip for verifying its feasibility in feedback mode. Since it could achieve simultaneous multitarget imaging during one single imaging process, PC12 cells status was imaged and identified through three different molecules (FcMeOH, Ru(NH3)63+, and oxygen). The FcMeOH image eliminated the error from cell height, and the Ru(NH3)63+ image verified the change of membrane permeability. Moreover, the oxygen image demonstrated the bioactivity of the cell via its intensity of respiration. Combining information from these three molecules, the cell status could be determined accurately and also the error caused by time consumption with multiple scans in traditional SECM was eliminated.

Hypermethylation of ITGBL1 is associated with poor prognosis in acute myeloid leukemia.

The current study was aimed to investigate integrin beta-like 1 (ITGBL1) methylation pattern and its clinical relevance in patients with acute myeloid leukemia (AML). Real-time methylation-specific polymerase chain reaction (PCR; RQ-MSP) and bisulfite sequencing PCR (BSP) were performed to detect the methylation of ITGBL1 promoter. Real-time quantitative PCR (RT-qPCR) was performed to analyze ITGBL1 transcript level. The results showed that ITGBL1 methylation level in 131 patients with AML was significantly higher than 29 controls (p < 0.001). The ITGBL1-hypermethylated group tended to have a higher bone marrow (BM) blasts ( p = 0.076). Meanwhile, ITGBL1-hypermethylated patients tended to have a lower complete remission (CR) rate ( p = 0.102). ITGBL1-hypermethylated patients had significantly shorter overall survival (OS) and leukemia-free survival (LFS) than ITGBL1 hypomethylated patients in whole AML cohort ( p = 0.009 and 0.043, respectively) and patients with nonacute promyelocytic leukemia (APL ; p = 0.023 and 0.039, respectively). Multivariate analysis confirmed that the ITGBL1 methylation served as an independent prognostic factor in both patients with whole-cohort AML ( p = 0.030) and patients with non-APL ( p = 0.020). Furthermore, the ITGBL1 methylation level was significantly decreased in follow-up AML patients who achieved complete remission after induction therapy ( P = 0.001). ITGBL1 methylation negatively correlated with ITGBL1 expression in patients with AML ( R = -0.328, p = 0.008). Moreover, demethylation of ITGBL1 could increase the ITGBL1 expression in the K562 leukemic cell line ( p < 0.05). In conclusion, the ITGBL1 hypermethylation is a potential biomarker for predicting prognosis and monitoring disease status in patients with AML.

Methylation-associated DOK1 and DOK2 down-regulation: Potential biomarkers for predicting adverse prognosis in acute myeloid leukemia.

DOK-1 and DOK-2 (DOK1/2) are closely related members of downstream of tyrosine kinase (DOK) family genes, which are found to be frequently rearranged in several hematopoietic cancers. However, the clinical implications of DOK1/2 in acute myeloid leukemia (AML) remain largely unknown. To investigate the clinical significance, real-time quantitative PCR (RQ-PCR) was carried out to detect DOK1/2 expressions in 125 de novo AML patients and 28 healthy controls. Real-time quantitative methylation-specific PCR (RQ-MSP) and bisulfite sequencing PCR (BSP) were applied to detect DOK1/2 methylation level and density. DOK1/2 expressions were significantly down-regulated in AML patients. The promoters of DOK1/2 were highly hypermethylated and negatively correlated with DOK1/2 expressions in AML patients. In addition, we also confirmed that DOK1/2 expressions could be restored by DOK1/2 demethylation using 5-aza-2'-deoxycytidine in leukemia cell line THP-1. Survival analyses showed that low-expressed DOK1/2 were associated with markedly shorter overall survival and leukemia free survival in both whole-cohort AML and non-M3 AML patients. Multivariate analyses further revealed that DOK1/2 were act as independent prognostic factors in AML patients. These findings indicate that decreased DOK1/2 expressions associated with their promoter hypermethylations predict adverse prognosis in AML.

Intragenic hypomethylation of DNMT3A in patients with myelodysplastic syndrome.

BACKGROUND: DNMT3A is a DNA methyltransferase that acts in de novo methylation. Aberrant expression of DNMT3A has been reported in several human diseases, including myelodysplastic syndrome (MDS). However, the pattern of DNMT3A methylation remains unknown in MDS. METHODS: The present study was aimed to investigate the methylation status of DNMT3A intragenic differentially methylated region 2 (DMR2) using real-time quantitative methylation-specific PCR and analyze its clinical significance in MDS. RESULTS: Aberrant hypomethylation of DNMT3A was found in 57% (51/90) MDS cases. There were no significant differences in age, sex, white blood cell counts, platelet counts, hemoglobin counts and World Health Organization, International Prognostic Scoring System and karyotype classifications between DNMT3A hypomethylated and DNMT3A hypermethylated groups. However, the patients with DNMT3A hypomethylation had shorter overall survival time than those without DNMT3A hypomethylation (11 months vs. 36 months, p=0.033). Multivariate analysis confirmed the independent adverse impact of DNMT3A hypomethylation in MDS. CONCLUSIONS: Our data suggest that DNMT3A DMR2 hypomethylation may be a negative prognostic hallmark in MDS.

A homochiral porous organic cage with large cavity and pore windows for the efficient gas chromatography separation of enantiomers and positional isomers.

Porous organic cages composed of discrete cage molecules have attracted considerable recent attention as gas adsorption materials and separation media. In this study, we report a homochiral porous organic cage CC5 with a large cavity and pore windows as a novel stationary phase for high-resolution gas chromatographic separations. The capillary column was prepared by a static coating method. A large number of racemic compounds have been resolved on the coated capillary column, including derivatized amino acids, alcohols, alcohol amines, esters, ethers, ketones, and epoxides. It is interesting that the CC5-coated capillary column exhibits significant chiral recognition complementarity to a commercial ß-DEX 120 column and a previously reported homochiral porous organic cage CC3-R-coated column, which could expand the range of the analytes amenable to separation on porous organic cage-based capillary columns. Moreover, the fabricated column also shows excellent selectivity for the separation of positional isomers, including the challenging ethylbenzene and xylene isomers. Experimental results demonstrate an excellent separation performance and stability of the CC5-coated column, making it promising for gas chromatography applications.

Phytotoxicity and groundwater impacts of leaching from thermal treatment residues in roadways.

The use of coal fly ash (CFA), municipal solid waste incinerator bottom ash (MSWIBA) and flue gas desulfurization residue (FGDR) in road construction has become very common owing to its economical advantages. However, these residues may contain toxic constituents that pose an environmental risk if they leach out and flow through the soil, surface water and groundwater. Therefore, it is necessary to assess the ecotoxicity and groundwater impact of these residues before decisions can be made regarding their utilization for road construction. In this study, the physico-chemical characteristics, leaching and phytotoxicity of these residues were investigated. Specifically, multivariate analyses were used to evaluate the contributions of the leaching constituents of the CFA, MSWIBA and FGDR leachates to the germination index of wheat seeds. B, Ba, Cr, Cu, Fe and Pb were found to be more toxic to the wheat seeds than the other heavy metals. Furthermore, the leached concentrations of the constituents from the CFA, MSWIBA and FGDR were below the regulatory threshold limits of the Chinese identification standard for hazardous wastes. Analyses conducted using a numerical groundwater model (WiscLEACH) indicated that the predicted field concentrations of metals from the CFA, MSWIBA and FGDR increased with time up to about 30years at the point of compliance, then decreased with time and distance. Overall, this study demonstrated that the risks resulting from MSWIBA, CFA and FGDR leaching could be assessed before its utilization for road construction, providing crucial information for the adoption of these alternative materials.

A comparison of chemical MSW compositional data between China and Denmark.

Chemical waste compositions are important for municipal solid waste management, as they determine the pollution potentials from different waste strategies. A representative dataset for chemical characteristics of individual waste fractions is frequently required to assess chemical waste composition, but it is usually reported in developed countries and not in developing countries. In this study, a dataset for Chinese waste was established through careful data screening and assessment, named as CN dataset. Meanwhile, a dataset for Danish waste (DK dataset) was also summarized based on previous studies. In order to quantitatively evaluate the reliabilities of CN and DK datasets, the chemical waste compositions in four Chinese cities were estimated by utilizing both of them, respectively. It is indicated that the usage of CN datasets led to significantly lower discrepancies from the actual values based on laboratory analysis in most cases. Within the datasets, the moisture contents of food waste, paper, textiles, and plastics, the carbon content of food waste, as well as the oxygen content of plastics would induce significant divergences, which should be paid special attention when gathering the information. In addition, the fractional waste compositions in China showed similar features with other developing countries but differ significantly with developed countries. Thus the above-mentioned conclusions could also be true in other developing countries.

Inhibitory effect of high calcium concentration on municipal solid waste leachate treatment by the activated sludge process.

This research focused on the inhibitory effects of Ca on the aerobic biological treatment of landfill leachate containing extremely high Ca concentrations. When the Ca concentration in leachate to be treated was more than 4500 mg l-1, the total organic carbon removal rate was significantly reduced and the processing time to achieve the same removal efficiency was 1.4 times that in the control treatment without added Ca. In contrast, the total nitrogen and ammonia nitrogen (NH4+-N) removal efficiencies were positively related to the Ca concentration, increasing from 65.2% to 81.2% and from 69.2% to 83.7%, respectively, when the dosage of added Ca increased from zero to 8000 mg l-1. During aerobic treatment, the reductions of solution Ca concentration were in the range of 1003-2274 mg l-1 and were matched with increases in the Ca content in the residual sludge. The inhibition threshold of Ca in the leachate treated by the activated sludge process appeared to be 4500 mg l-1, which could be realized by controlling the influent Ca concentration and using an appropriate sludge return ratio in the activated sludge process.

Synthesis and Antitumor Evaluation of Novel 5-Hydrosulfonyl-1H-benzo[d]imidazol-2(3H)-one Derivatives.

A series of novel 5-hydrosulfonyl-1H-benzo[d]imidazol-2(3H)-one derivatives bearing natural product substructures has been successfully synthesized and their antitumor activity studied. These newly synthesized derivatives were characterized by ¹H-NMR, (13)C-NMR and high resolution mass spectral data, then screened as antitumor agents against the A549, HCC1937, and MDA-MB-468 human tumor cell lines using MTT cell proliferation assays. The results show that some of these compounds can effectively inhibit the growth of these cancerous cells, with compound 5b being the best one (IC50 = 2.6 µM). Flow cytometry data revealed that compound 5b induced apoptosis of HCC1937 cells with increased solution concentration. The structure and activity relationships (SAR) of these compounds is summarized.

Homochiral Porous Organic Cage with High Selectivity for the Separation of Racemates in Gas Chromatography.

Porous organic molecular cages as a new type of porous materials have attracted a tremendous attention for their potential applications in recent years. Here we report the use of a homochiral porous organic cage (POC) (CC3-R) diluted with a polysiloxane (OV-1701) as a stationary phase for high-resolution gas chromatography (GC) with excellent enantioselectivity. A large number of optical isomers have been resolved without derivatization, including chiral alcohols, diols, amines, alcohol amines, esters, ketones, ethers, halohydrocarbons, organic acids, amino acid methyl esters, and sulfoxides. Compared with commercial ß-DEX 120 and Chirasil-L-Val columns, the CC3-R coated capillary column offered more preeminent enantioselectivity. In addition, CC3-R also exhibits good selectivity for the separation of isomers, linear alkanes, alcohols, and aromatic hydrocarbons. The excellent resolution ability, repeatability, and thermal stability make CC3-R a promising candidate as a novel stationary phase for GC. The study described herein first proves useful commercially. This work also indicates that porous organic molecular materials will become more attractive in separation science.

Novel inorganic mesoporous material with chiral nematic structure derived from nanocrystalline cellulose for high-resolution gas chromatographic separations.

Chiral nematic mesoporous silica (CNMS) has attracted widespread attention due to some unique features, such as its nematic structure, chirality, large pore size, high temperature resistance, low cost, and ease of preparation. We first reported the use of CNMS as a stationary phase for capillary gas chromatography (GC). The CNMS-coated capillary column not only gives good selectivity for the separation of linear alkanes, aromatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and isomers but also offers excellent enantioselectivity for chiral compounds. Compared with enantioseparations on commercial ß-DEX 120 and Chirasil-l-Val columns, a CNMS-coated capillary column offers excellent enantioselectivity, chiral recognition complementarity, and the separation of analytes within short elution times. It can also be potentially applied in high-temperature GC at more than 350 °C. This work indicates that CNMS could soon become very attractive for separations.

Greenhouse gas emissions during MSW landfilling in China: influence of waste characteristics and LFG treatment measures.

Reducing greenhouse gas (GHG) emissions from municipal solid waste (MSW) treatment can be highly cost-effective in terms of GHG mitigation. This study investigated GHG emissions during MSW landfilling in China under four existing scenarios and in terms of seven different categories: waste collection and transportation, landfill management, leachate treatment, fugitive CH4 (FM) emissions, substitution of electricity production, carbon sequestration and N2O and CO emissions. GHG emissions from simple sanitary landfilling technology where no landfill gas (LFG) extraction took place (Scenario 1) were higher (641-998 kg CO2-eq·t(-1)ww) than those from open dump (Scenario 0, 480-734 kg CO2-eq·t(-1)ww). This was due to the strictly anaerobic conditions in Scenario 1. LFG collection and treatment reduced GHG emissions to 448-684 kg CO2-eq·t(-1)ww in Scenario 2 (with LFG flare) and 214-277 kg CO2-eq·t(-1)ww in Scenario 3 (using LFG for electricity production). Amongst the seven categories, FM was the predominant contributor to GHG emissions. Global sensitivity analysis demonstrated that the parameters associated with waste characteristics (i.e. CH4 potential and carbon sequestered faction) and LFG management (i.e. LFG collection efficiency and CH4 oxidation efficiency) were of great importance. A further learning on the MSW in China indicated that water content and dry matter content of food waste were the basic factors affecting GHG emissions. Source separation of food waste, as well as increasing the incineration ratio of mixed collected MSW, could effectively mitigate the overall GHG emissions from landfilling in a specific city. To increase the LFG collection and CH4 oxidation efficiencies could considerably reduce GHG emissions on the landfill site level. While, the improvement in the LFG utilization measures had an insignificant impact as long as the LFG is recovered for energy generation.

Improving the performance of thermophilic anaerobic digester through recirculation of low hydrogen biogas.

Biogas recirculation was conducted to improve the performance of two thermophilic anaerobic sequenced batch reactors (ASBRs), in which high concentrations of volatile fatty acids (VFAs) were accumulated. To accelerate degradation of VFAs, facilitating acetate consumption via syntrophic acetate oxidation coupled with hydrogenotrophic methanogenesis (SAO-HM) was expected to be effective. Hence, to promote the SAO-HM pathway, hydrogen was removed to create low hydrogen partial pressure (pH2) in reactor RH, yet in reactor RB, hydrogen was not treated. The performance of RB and RH on VFAs degradation and methane production processes was compared at steady stage; the VFAs and soluble microbial products (SMP) in the effluents were monitored. The results showed that low pH2 intensified the SAO reaction, thereby accelerating conversion of acetate to methane, as well as acetate production from glucose and VFAs. Glucose fermentation type was also influenced. VFAs and SMP in the effluents were reduced after the introduction of biogas mixing, which proceeded much faster in RH with low pH2. Recirculation of low hydrogen biogas with SAO-HM pathway being promoted should be more effective to alleviate high acid level stress and to improve the reactor performance.

A Novel Analog Interpolation Method for Heterodyne Laser Interferometer.

Laser interferometer technology is used in the precision positioning stage as an encoder. For better resolution, laser interferometers usually work with interpolation devices. According to the interpolation factor, these devices can convert an orthogonal sinusoidal signal into several square-wave signals via digital processing. The bandwidth of the processing will be the limitation of the moving speed of the positioning stage. Therefore, the user needs to make a trade-off between the interpolation factor and the moving speed. In this investigation, a novel analog interpolation method for a heterodyne laser interferometer has been proposed. This method is based on the principle of the lock-in amplifier (LIA). By using the proposed interpolation method, the bandwidth of the laser encoder system can be independent of the interpolation factor. This will be a significant benefit for the ultra-high resolution encoder system and the laser interferometers. The concept, design, and experiment are revealed in this manuscript. The experimental results show that the proposed interpolation method can reach nanometer resolution with a heterodyne laser interferometer, and the bandwidth of the signal is independent of the resolution.

High-Bonding-Strength Polyimide Films Achieved via Thermal Management and Surface Activation.

In this study, thermal and argon (Ar) plasma/wetting treatments were combined to enhance the bonding strength of polyimide (PI) films. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) was used to analyze the changes in the PI imidization degrees. The contact angles of the PI films were also measured. The results show that the contact angles of the fully cured PI films markedly decreased from 78.54° to 26.05° after the Ar plasma treatments. X-ray photoelectron spectroscopy (XPS) analysis was also conducted on the PI surfaces. We found that the intensities of the C-OH and C-N-H bonds increased from 0% to 13% and 29% to 57%, respectively, after Ar plasma activation. Such increases in the C-OH and C-N-H intensities could be attributed to the generation of dangling bonds and the breakage of the imide ring or polymer long chains. Shear tests were also conducted to characterize the bonding strength of the PI films, which, after being treated with the appropriate parameters of temperature, plasma power, and wetting droplets, was found to be excellent at greater than 35.3 MPa.