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.

Molecular-weight dependent promotion and competition effects of natural organic matter on dissolved black carbon removal by coagulation.

Dissolved black carbon (DBC) is the ubiquitous component of dissolved organic matter pools with the high reactivity for disinfection byproducts formation. However, it is unknown that the influence of molecular weight (MW) of natural organic matter (NOM) on the DBC removal from potable water sources. Therefore, it was studied that the DBC removal by coagulation in the presence of the NOM with various molecular weights. The DBC removal was promoted due to the presence of NOM and the promotion degree decreased with decreasing MW of NOM. Furthermore, the removal ratio of humic-like component increased as the MW of NOM decreased, suggesting that the competition between DBC and NOM increased with decreasing MW. The functional groups after coagulation were the same with that before coagulation as the MW of NOM varied, suggesting that the molecular structure was not the key factor of influencing the DBC removal. This study will give the deep insight into the prediction of the DBC removal ratio by coagulation based on the MW of NOM in water sources.

One metal-ion-regulated AgTNPs etching sensor array for visual discrimination of multiple organic acids.

The detection and discrimination of organic acids (OAs) is of great importance in the early diagnosis of specific diseases. In this study, we established an effective visual sensor array for the identification of OA. This is the first time, to our best knowledge, that metal ions were used to regulate the etching of silver triangular nanoprisms (AgTNPs) in an OA discrimination sensor array. The sensor array was based on the oxidation etching of AgTNPs by three metal ions (Mn2+, Pb2+, and Cr3+) and accelerated etching of AgTNPs by OA. The introduction of metal ions alone led to a slight wavelength shift of the AgTNPs colloid solution, signifying the incomplete etching of the AgTNPs. Nevertheless, when metal ions and OA were introduced simultaneously to the solution, a significant blueshift of the localized surface plasmon resonance peak was detected, and a color change of the AgTNPs was observed, which were the consequences of morphological transitions of the AgTNPs. The addition of different OA accelerated AgTNPs etching in varying degrees, generating diverse colorimetric response patterns (i.e., RGB variations) as "fingerprints" associated with each specific organic acid. Pattern recognition algorithms and neural network simulation were employed to further data analysis, indicating the outstanding discrimination capability of the provided array for eight OA at the 33 µM level. Moreover, excellent results of selective experiments as well as real samples tests demonstrate that our proposed method possesses great potential for practical applications.

Quantitative structure retention relationship (QSRR) modelling for Analytes' retention prediction in LC-HRMS by applying different Machine Learning algorithms and evaluating their performance.

In metabolomics, retention prediction methods have been developed based on the structural and physicochemical characteristics of analytes. Such methods employ regression models, harnessing machine learning algorithms mapping experimentally derived retention time (tR) analytes with various structural and physicochemical descriptors, known as Quantitative Structure Retention Relationships (QSRR) models. In the present study, QSRR models have been developed by applying four Machine Learning regression algorithms, i.e. Bayesian Ridge Regression (BRidgeR), Extreme Gradient Boosting Regression (XGBR) and Support Vector Regression (SVR) using both linear and non-linear kernels, all tested and compared for their retention prediction ability on experimentally derived and on publicly available chromatographic data, using Molecular Descriptors to describe the physical, chemical or structural properties of molecules. Various configurations of the available datasets, in terms of the highly-correlated features levels (defined as the maximum absolute value of the Pearson's correlation coefficient calculated between any pair of features) they contained, were analyzed in parallel. This is the first study, to the best of our knowledge, of the effect of collinearity on the performance of QSRR predictive models. In the vast majority of cases studied there was no statistically significant difference in the performance of the generated QSRR predictive models among the specified dataset configurations, indicative of the ability of the selected regression algorithms to effectively handle collinearity. In terms of the individual performance of the selected regression algorithms, no pattern was found where one algorithm (or class of algorithms) stood out significantly relative to the others among the study datasets.

Enhanced refractory organics removal by sponge iron-coupled microbe technology: performance and underlying mechanism analysis.

Sponge iron (SFe) is a zero-valent iron (Fe0) composite with a high-purity and porous structure. In this study, SFe was coupled with microorganisms that were gradually domesticated to form a Fe0/iron-oxidizing bacteria system (Fe0-FeOB system). The enhancement effect of the Fe0-FeOB system on refractory organics was verified, the mechanism of its strengthening action was investigated, and the relationship and influencing factors between the Fe0 and microorganisms were revealed. The average removal rates of the Fe0-FeOB system were 8.98%, 5.69%, and 40.67% higher than those of the SBR system for AF, AN, and NB wastewater treatment, respectively. With the addition of SFe, the microbial community structure was gradually enhanced with a large number of FeOB were detected. Moreover, the bacteria with strong iron corrosion and Fe(II) oxidation abilities plays a critical role in improving the Fenton-like effect. Interestingly, the variation trend of ⋅OH was fairly consistent with that of Fe(II). Thus, the main drivers of the Fenton-like effect are biological corrosion and metabolism. Consequently, microbial degradation and Fenton-like effect contributed to the degradation performance of the Fe0-FeOB system. Among them, the microbial degradation accounted for 96.09%, of which the biogenic Fenton effect accounted for 8.9%, and the microbial metabolic activity accounted for 87.19%. However, the augmentation of the Fe0-FeOB system was strongly dependent on SFe for the strengthening effect of microorganisms disappeared after leaving the SFe 35 days.

Novel nanohybrids for effervescence enhanced magnetic solid-phase microextraction of wide-polarity organic pollutants in roasted meat samples.

To simultaneously and efficiently extract pollutants with differential polarities, we herein fabricated and characterized a multifunctional nanocomposite. The novel nanohybrids used NiFe2 O4 as magnetic cores, and NH2 -MIL-101(Al), ß-cyclodextrin and graphene oxide as functional components combined with magnetic cores. With the aid of graphene oxide's large π-conjugated system, NH2 -MIL-101(Al)'s strong adsorption to moderately/strongly polar chemicals, and ß-cyclodextrin's specific recognition effect, the nanohybrids realized synergistically efficient extraction of polyaromatic hydrocarbons and bisphenols with a logKow range of 3-6. Combined with acidic and alkaline sources, the nanohybrids-based effervescent tablets were prepared. Based on effervescent reaction-enhanced nanohybrids-based efficient adsorption/extraction and high performance liquid chromatography and fluorescence detection, we successfully developed an excellent microextraction method for the simultaneous determination of both polyaromatic hydrocarbons and bisphenols in roasted meat samples. Several important variables were optimized as follows: Na2 CO3 and tartaric acid as acidic and alkaline sources, 900 µLof the mixed solvent (acetone and hexane at 2:1 by v/v) as the eluent, 5 min of elution time. Under optimized conditions, the novel method gave low limits of detection (0.07-0.30 µg kg-1 ), satisfactory recoveries (86.9-103.9%), and high precision (relative standard deviations of 1.9-6.7%) in roasted lamb, beef, pork, chicken, and sausage samples.

Characterisation and optimisation of a novel laccase from Sulfitobacter indolifex for the decolourisation of organic dyes.

Laccases are multi­copper oxidases that possess the potential for industrial wastewater treatments. In this study, a putative laccase from Sulfitobacter indolifex was recombinantly produced and characterised. The enzyme was found to be stable and active at low to ambient temperature and across a range of pH conditions. The ability of the putative bacterial laccase to catalyse the decolourisation of seven common industrial dyes was also examined. Our results showed that the putative laccase could efficiently decolourise Indigo Carmine, Coomassie Brilliant Blue R-250, Congo Red, Malachite Green and Alizarin in the presence of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) as a redox mediator. Furthermore, the use of enzyme immobilisation technology to improve the operational stability and reusability of the putative laccase was also investigated. We found that immobilising the enzyme through the cross-linked enzyme aggregate method significantly improved its tolerance towards extreme pH as well as the presence of organic solvents. This work expands the arsenal of bacterial laccases available for the bioremediation of dye-containing wastewater.

Glutaraldehyde-cross-linked chitosan-alginate composite for organic dyes removal from aqueous solutions.

We present an approach for synthesis of a micro-porous composite of two well-known biopolymers, namely chitosan and alginate, using glutaraldehyde as the cross-linking agent. Alginate and chitosan were pre-treated before being mixed, and the two biopolymers' proportions were also monitored. Chitosan was modified using aniline with the help of formaldehyde crosslinker and then the twizer was further crosslinked with alginate using glutaraldehyde. The synthesized composite, glutaraldehyde cross-linked chitosan-alginate composite [(Cs-F-An)-G-Al] was characterized using spectral techniques and employed as a potential adsorbent for three dyes namely Brilliant green, Methyl orange and Patent Blue V. The pHPZC of the material was 7.5 and the maximum monolayer adsorption capacity (Qmax) was found to be 235.82, 198.09 and 117.34 mg g-1 for BG (at pH 8.0), MO (at pH 6.0) and PBV (at pH 3.0) respectively. It was found that the adsorption process follows a Freundlich adsorption isotherm and pseudo second order kinetics. A thermodynamic study revealed that the process of adsorption was enthalpy-driven and spontaneous in nature. Interestingly, the values of the adsorption capacity obtained in column adsorption method are in close agreement with those obtained in batch adsorption experiments, which shows the potential of the synthesized composite for uptake of dyes.

Supercritical Carbon Dioxide Extraction of Four Medicinal Mediterranean Plants: Investigation of Chemical Composition and Antioxidant Activity.

With everyday advances in the field of pharmaceuticals, medicinal plants have high priority regarding the introduction of novel synthetic compounds by the usage of environmentally friendly extraction technologies. Herein, a supercritical CO2 extraction method was implemented in the analysis of four plants (chamomile, St. John's wort, yarrow, and curry plant) after which the non-targeted analysis of the chemical composition, phenolic content, and antioxidant activity was evaluated. The extraction yield was the highest for the chamomile (5%), while moderate yields were obtained for the other three plants. The chemical composition analyzed by gas chromatography-high-resolution mass spectrometry (GC-HRMS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS) demonstrated extraction of diverse compounds including terpenes and terpenoids, fatty acids, flavonoids and coumarins, functionalized phytosterols, and polyphenols. Voltammetry of microfilm immobilized on a glassy carbon electrode using square-wave voltammetry (SWV) was applied in the analysis of extracts. It was found that antioxidant activity obtained by SWV correlates well to 1,1-diphenyl-2-picrylhidrazine (DPPH) radical assay (R2 = 0.818) and ferric reducing antioxidant power (FRAP) assay (R2 = 0.640), but not to the total phenolic content (R2 = 0.092). Effective results were obtained in terms of activity showing the potential usage of supercritical CO2 extraction to acquire bioactive compounds of interest.

Ionic chitosan/silica nanocomposite as efficient adsorbent for organic dyes.

A new adsorbent from chitosan and anionic silica was prepared by ionic interaction followed by sol-gel process. The obtained nanocomposite was characterized by different techniques: FTIR, XRD, SEM/EDX, TGA, and TEM. The results showed that silica precursor interacts with chitosan and deposits as regular spherical nanoparticles. The methylene blue (MB) adsorption by chitosan/silica nanocomposite achieved the adsorption equilibrium within 60 min. The adsorption method is fitted to the pseudo-second-order kinetic model and the Langmuir adsorption model with a maximum adsorption capacity of 847.5 mg/g at slight alkaline solution. Chitosan/silica composite displayed high regeneration capability and recovery of MB up to five cycles without the loss of the adsorption efficiency. The current study showed that as-prepared chitosan/silica nanocomposite is an appropriate material for the adsorption of organic pollutants from wastewater.

Gas chromatography/mass spectrometry analysis of organic acid profiles in human serum: A protocol of direct ultrasound-assisted derivatization.

RATIONALE: Low-molecular-weight organic acids that generally contain one to three carboxyl groups are involved in many important biological processes; therefore, it is important to develop a quantitative method for analyzing organic acids in serum in order to allow an evaluation of metabolic changes. In this study, we evaluated a protocol for detecting 26 organic acids in serum based on ultrasound-assisted derivatization by gas chromatography/mass spectrometry (GC/MS). METHODS: Serum samples were prepared using ultrasound-assisted silane derivatization before GC/MS analysis to quantify concentrations of organic acids. Additionally, we investigated the variables affecting derivatization yields, including the extraction solvent, derivatization reagents, and derivatization conditions (reaction temperature, duration, and sonication parameters). The protocol was ultimately applied to detect organic acid profiles related to obesity. RESULTS: We used acetone as the extraction solvent and determined suitable derivatization conditions, as follows: BSTFA + 1% TMCS, 50°C, 10 min, and 100% ultrasound power. The protocol showed satisfactory linearity (r = 0.9958-0.9996), a low limit of detection (0.04-0.42 µmol/L), good reproducibility (coefficient of variation (CV) %: 0.32-13.76%), acceptable accuracy (recovery: 82.97-114.96%), and good stability within 5 days (CV%: 1.35-12.01% at room temperature, 1.24-14.09% at 4°C, and 1.01-11.67% at -20°C). Moreover, the protocol was successfully applied to obtain the organic acid profiles from obese and healthy control subjects. CONCLUSIONS: We identified and validated a protocol for ultrasound-assisted derivatization prior to GC/MS analysis for detecting 26 kinds of organic acids in serum. The results suggest the efficacy of this protocol for clinical applications to determine metabolic changes related to fluctuations in organic acid profiles.

Characterization and significance of extracellular polymeric substances, reactive oxygen species, and extracellular electron transfer in methanogenic biocathode.

The microbial electrolysis cell assisted anaerobic digestion holds great promises over conventional anaerobic digestion. This article reports an experimental investigation of extracellular polymeric substances (EPS), reactive oxygen species (ROS), and the expression of genes associated with extracellular electron transfer (EET) in methanogenic biocathodes. The MEC-AD systems were examined using two cathode materials: carbon fibers and stainless-steel mesh. A higher abundance of hydrogenotrophic Methanobacterium sp. and homoacetogenic Acetobacterium sp. appeared to play a major role in superior methanogenesis from stainless steel biocathode than carbon fibers. Moreover, the higher secretion of EPS accompanied by the lower ROS level in stainless steel biocathode indicated that higher EPS perhaps protected cells from harsh metabolic conditions (possibly unfavorable local pH) induced by faster catalysis of hydrogen evolution reaction. In contrast, EET-associated gene expression patterns were comparable in both biocathodes. Thus, these results indicated hydrogenotrophic methanogenesis is the key mechanism, while cathodic EET has a trivial role in distinguishing performances between two cathode electrodes. These results provide new insights into the efficient methanogenic biocathode development.

Silica Monolith for the Removal of Pollutants from Gas and Aqueous Phases.

This study focused on the application of mesoporous silica monoliths for the removal of organic pollutants. The physico-chemical textural and surface properties of the monoliths were investigated. The homogeneity of the textural properties along the entire length of the monoliths was assessed, as well as the reproducibility of the synthesis method. The adsorption properties of the monoliths for gaseous toluene, as a model of Volatile Organic Compounds (VOCs), were evaluated and compared to those of a reference meso-structured silica powder (MCM-41) of commercial origin. Silica monoliths adsorbed comparable amounts of toluene with respect to MCM-41, with better performances at low pressure. Finally, considering their potential application in water phase, the adsorption properties of monoliths toward Rhodamine B, selected as a model molecule of water soluble pollutants, were studied together with their stability in water. After 24 h of contact, the silica monoliths were able to adsorb up to the 70% of 1.5 × 10-2 mM Rhodamine B in water solution.

Removing Iron and Organic Substances from Water over the Course of Its Treatment with the Application of Average and Highly Alkaline Polyaluminium Chlorides.

In topic-related literature pertaining to the treatment of water, there is a lack of information on the influence of iron ions in highly basic polyaluminum chlorides on the efficiency of purifying water with increased contents of organic substance. The aim of this work was to determine the changes in the content of organic substances as well as iron compounds in water intended for human consumption following unit treatment processes with particular attention paid to the coagulation process. As coagulants, polyaluminium chloride PAXXL10 with an alkalinity of 70%, as well as polyaluminium chloride PAXXL1911 with an alkalinity of 85% the composition of which also contained iron, were tested. The analysis of the obtained results showed that iron compounds and organic substances were removed to the greatest extent by the coagulation process, which also had a significant influence on the final efficiency of water treatment. The effectiveness of water treatment was determined by the type of tested polyaluminum chloride, which influenced the formation of iron-organic complexes. The reason behind the formation of colored iron-organic complexes during coagulation using PAXXL1911 coagulant was the high pH (approx. 8), at which the functional groups of organic substances, due to their dissociation, are more reactive in relation to iron, and possibly the fact of introducing additional iron ions along with the coagulant.

Automated liquid-liquid extraction of organic compounds from aqueous samples using a multifunction autosampler syringe.

Liquid-liquid extraction is one of the most widely used and simplest sample preparation techniques. However, consumption of large volumes of organic solvent and manual handling are two major drawbacks of this technique. A multifunction autosampler syringe is introduced which permits automated liquid-liquid extraction in an enclosed operating environment, with low consumption of organic solvents. The device described herein features a micromixer function in addition to common autosampler syringe features like accurate and precise aspirating and dispensing. To test the functionality of the micromixer syringe, manual extraction of caffeine from a tea infusion and semi-automated extraction of dichloroethane from water were carried out. Excellent recoveries of caffeine from a tea infusion (89% recovery with 1.3% RSD) and dichloroethane from water (107% recovery with 10% RSD) were obtained. Two automated workflows were tested using the micromixer syringe mounted in a laboratory autosampler. Standalone automated micro liquid-liquid extraction was performed for sample preparation of selected polychlorinated biphenyl (PCB) congeners prior to comprehensive two-dimensional gas chromatography - electron capture detection analysis. Extraction of PCBs using the described approach used substantially less solvent than a validated solid-phase extraction approach whilst delivering equivalent results for samples with high-level PCBs. Finally, fully automated extraction and GC-MS analysis of polynuclear aromatic hydrocarbons (PAHs) from water samples was performed. Mean recoveries of extraction for PCB and PAH analysis were > 70% using 4 min automated liquid-liquid extractions.

Organic contamination in online laser-based plant stem and leaf water isotope measurements for pre-extracted samples.

Water stable isotopes have been widely used as natural tracers to investigate soil-plant-atmosphere interactions. Recent developments in induction module cavity ring-down spectroscopy (IM-CRDS) have made it possible to rapidly complete isotope analyses, and to combust co-extracted organic compounds at the same time. However, the agreement between IM-CRDS and isotope ratio mass spectrometry (IRMS) analyses has generally been poor and was primarily attributable to spectral interference of IM-CRDS. Here we evaluated the impacts of organic contamination on the isotope ratios using IM-CRDS with two different methods. No spectral interference was observed for solid samples measured directly by IM-CRDS, whereas clear organic contamination occurred in isotope analyses for pre-extracted plant stem and leaf samples. Our results demonstrate that IM-CRDS can fully combust co-extracted organic compounds by in-line oxidation in the direct measurement of solid samples, although this may not guarantee that the IM-CRDS can obtain better isotopic data than IRMS. It may be risky to evaluate the performance of IM-CRDS by measuring pre-extracted water samples because cryogenic vacuum distillation is likely to introduce extra organic compounds, which may not be fully removed during subsequent IM-CRDS measurement. In addition, spectral variables are useful for post-processing corrections.

Subcritical water extraction of organic acids from chicken manure.

BACKGROUND: Chicken manure waste has a wide range of organic substances and mineral elements. This enriched source has stimulated great scientific interest in finding cleaner and more environmentally benign nutrient recovery options. This study aimed to determine an effective and eco-friendly method (i.e. subcritical water extraction) for processing fresh poultry manure. RESULTS: The high content of total organic carbon, including humic acids carbon and fulvic acids carbon, in extract was found to release under subcritical conditions. The organic compounds obtained by extraction with subcritical water correspond to humic acid in composition because of the presence in the sample of all the functional groups: polymer bonded by molecular hydrogen bond (3400 cm-1 ), the presence of CH2 and CH3 groups (2870 cm-1 ), the presence of carboxyl groups (1720 cm-1 ) and quinones (1640-1680 cm-1 ). The solid phase left over was characterized by a high content of organic carbon, phosphorus, potassium, and microelements. The maximum extraction of humic acid and fulvic acid carbon was found between 210 and 250 °C at a pressure of 50-60 atm, and the content was a maximum of 3647.2 × 10-6 g kg-1 at an extraction temperature of 250 °C. CONCLUSION: Given the high content of humic acid found in the extracted medium, the proposed subcritical extraction opens up new opportunities for nutrients recovery in the poultry industry. © 2020 Society of Chemical Industry.

Non-chromatographic Speciation of As by HG Technique-Analysis of Samples with Different Matrices.

The applicability of the hydride generation (HG) sample introduction technique combined with different spectrochemical detection methods for non-chromatographic speciation of toxic As species, i.e., As(III), As(V), dimethylarsinate (DMA) and monomethylarsonate (MMA), in waters and other environmental, food and biological matrices is presented as a promising tool to speciate As by obviating chromatographic separation. Different non-chromatographic procedures along with speciation protocols reported in the literature over the past 20 year are summarized. Basic rules ensuring species selective generation of the corresponding hydrides are presented in detail. Common strategies and alternative approaches are highlighted. Aspects of proper sample preparation before analysis and the selection of adequate strategies for speciation purposes are emphasized.

Miniaturized LC in Molecular Omics.

Miniaturized LC has evolved at an exponential rate over the last 50 years. In the past decade, it has received considerable attention in the field of bioanalytical separation science and technology due to the need to measure different classes of biomolecules present in a variety of matrixes on a global scale to gain a deeper understanding of complex biological processes. This field has become a dominant area underpinning the molecular omics research (e.g., proteomics, metabolomics, lipidomics, and foodomics), allowing key insights into the function and mechanism of small to very large biomolecules on a molecular level. This Feature highlights the recent advances in molecular omics focusing on miniaturized LC technology combined with mass spectrometry-based platforms, with a particular emphasis on the strategies adopted and applications using new and sensitive nanoscale analytical methodologies.

Method development and validation for the quantification of organic acids in microbial samples using anionic exchange solid-phase extraction and gas chromatography-mass spectrometry.

Organic acids play a key role in central metabolic functions of organisms, are crucial for understanding regulatory processes and are ubiquitous inside the cell. Therefore, quantification of these compounds provides a valuable approach for studying dynamics of metabolic processes, in particular when the organism faces changing environmental conditions. However, the extraction and analysis of organic acids can be challenging and validated methods available in this field are limited. In this study, we developed a method for the extraction and quantification of organic acids from microbial samples based on solid-phase extraction on a strong anionic exchange cartridge and gas chromatographic-mass spectrometric analysis. Full method validation was conducted to determine quality parameters of the new method. Recoveries for 12 of the 15 aromatic and aliphatic acids were between 100 and 111% and detection limits between 3 and 272 ng/mL. The ranges for the regression coefficients and process standard deviations for these compound classes were 0.9874-0.9994 and 0.04-0.69 µg/mL, respectively. Limitations were encountered when targeting aliphatic acids with hydroxy, oxo or enol ester functions. Finally, we demonstrated the applicability of the method on cell extracts of the bacterium Escherichia coli and the dinoflagellate Prorocentrum minimum. Graphical abstract.