High Molecular Weight Fraction Research Articles

In-depth analysis of natural organic matter fractions in drinking water treatment performance: Fate and role of humic substances in trihalomethanes formation potential

In this study we investigate the compositional changes in dissolved organic matter (DOM) fractions across diverse water sources and treatment processes in three Drinking Water Treatment Plants (DWTPs). High-Performance Size Exclusion Chromatography coupled with Diode Array Detection and Organic Carbon Detection (HPSEC-DAD-OCD) was employed to characterize DOM fractions, offering insights into treatment optimization. We examine bulk water parameters, DOM distributions, and the efficiency of treatment trains in reducing DOM fractions. Results reveal distinct DOM composition profiles in river-sourced versus reservoir-sourced waters, with implications for treatment processes. Coagulation, Granular Activated Carbon (GAC) adsorption, Electrodialysis Reversal (EDR), and Ion Exchange (IEX) were evaluated for their efficacy in removing DOM fractions. The analysis highlights the effectiveness of coagulation in reducing high molecular weight (MW) fractions, while GAC filtration targets lower MW fractions. EDR shows significant removal of anions and aromatics, while IEX demonstrates high removal efficiencies for removing humic substances (HS) fractions. Spectroscopic analysis further elucidates changes HS sub-fractions and their role in disinfection by-products (DBP) formation. To quantitatively assess the relationship between HS sub-fractions and trihalomethane formation potentials (THMFP), Pearson correlation analysis were conducted, unveiling robust associations between HS sub-fractions and THM-FP that can be predicted by surrogate parameters such as A254.

Effect of low molecular weight phenols on the in-mouth sensory perception of high molecular weight phenols by analyzing reconstituted wines

This research aimed to assess the contribution of monomeric phenols to the perception of bitterness and astringency by means of wine reconstitution experiments. Six wines with distinct total polyphenol indexes were selected and fractioned by preparative liquid chromatography into two fractions. Thirty-one reconstituted wines were prepared by combining distinct low molecular weight fractions (L) with different high molecular weight fractions (H). In-mouth attributes of reconstituted and reference wines were described by a trained sensory panel. Fractions were chemically characterized by UPLC-MS. No significant differences among sensory results were found between reference and reconstituted wines. Bitterness and astringency perception were strongly influenced by total proanthocyanidins content. Flavan-3-ol monomers and dimers were only responsible for astringency in wines with a low content of proanthocyanidins, as was the case in rosé wine. Quercetin-3-O-glucuronide and several anthocyanins presented correlations with bitterness in the reconstituted wines; notwithstanding, several interactions with this attribute were observed.

Periodic membrane fractionation of freshwater organic matter reveals various reactivity patterns during chlorine/chloramine disinfection

Although drinking water disinfection has significantly reduced mortality from waterborne diseases, the formation of potentially harmful disinfection by-products (DBPs) remains a concern today. These DBPs emerge from the reaction of dissolved organic matter (DOM) with chlor(am)ine during disinfection. Identifying these DBP precursors from heterogeneous and complex DOM mixtures is challenging and to address this, a novel membrane fractionation protocol was developed to isolate and identify the organic DBP precursors from fresh water sources. A tight ultrafiltration and nanofiltration membrane were carefully selected to partition DOM into three molecular weight (MW) fractions: high (>20 kDa), medium (0.3–20 kDa) and low (<0.3 kDa) as defined by high performance-size exclusion chromatography- total organic carbon analysis. A mathematical tool was developed to optimize the fractionation protocol. Therefore, ultrafiltration was executed before nanofiltration and the concentration factor was maximized without inducing fouling to obtain the purest fractions. The mathematical tool was also set in place to predict the necessary diafiltration factor for each individual fractionation experiment based on the initial organic matter composition of the surface water allowing the fractionation protocol to be effective at all times. The protocol was applied to surface water samples collected six times across three seasons yielding a fraction enriched in high MW compounds (up to 50 %), a fraction having more than 80 % of medium MW compounds and a fraction only containing low MW compounds. Although the medium MW fraction showed the highest reactivity for the majority of the investigated DBPs, the low MW fraction showed high reactivity for iodinated trihalomethanes during chlorination and for haloacetonitriles during chloramination. The high MW fraction had the lowest reactivity towards DBPs, which can have important implications for a drinking water treatment since this fraction is generally the most effectively removed by e.g. coagulation, while the more important fractions for DBP formation such as the medium and low MW compounds remain in the water until the disinfection step.

Structural characterization and immune-enhancing properties of an acidic heteroglycan from Protaetia brevitarsis seulensis larvae

Edible insects are a promising source of bioactive compounds with diverse health benefits. This study investigated the immunomodulatory properties of polysaccharides isolated from Protaetia brevitarsis seulensis larvae (PBSL). Polysaccharides were fractionated using a molecular weight cutoff membrane, and among these fractions, the higher molecular weight fraction (H-PBSL, 666.84 kDa) demonstrated significant immunomodulatory activity. Methylation and NMR structural analyses revealed H-PBSL to be an acidic heteroglycan with a complex structure, consisting of a backbone of repeating (1→4)-linked α-glucan units highly branched at O-6 positions with T-α-Glcp, T-α-GlcpA, and T-β-Galp. The immunomodulatory effects of H-PBSL were evaluated using RAW264.7 macrophage cells. H-PBSL treatment enhanced phagocytic activity and increased the expression of immune modulators and macrophage activation surface molecules. In addition, H-PBSL activated the NF-κB signaling pathway, evidenced by increased phosphorylation of IκB and NF-κB, and translocation of NF-κB from cytosol to nucleus. Moreover, inhibition of Toll-like receptor 4 (TLR4) reduced H-PBSL-induced nitric oxide synthesis, indicating TLR4′s pivotal role in H-PBSL-mediated macrophage activation. These findings highlight the potential of H-PBSL as a novel immunomodulatory agent derived from an edible insect, with possible applications in functional foods and nutraceuticals.

Spatial patterns and environmental functions of dissolved organic matter in grassland soils of China

Soil dissolved organic matter (DOM) is crucial to atmospheric, terrestrial and aquatic environments as well as human life. Here, by characterizing DOM from 89 grassland soils throughout China, we reveal the spatial association between DOM geochemistry in the dry season vs annual ecosystem exchange and cancer cases. The humic-like and high molecular weight (3.4–25 kDa) fractions with lower biodegradability, decline from the northern to the southern regions of China, and are correlated with lower soil respiration and net ecosystem productivity at the continental scale. The <1.2 kDa and proteinaceous fractions could serve as a geographical indicator of nasopharyngeal cancer incidence and mortality, while the 3.4–25 kDa and humified fractions are potentially associated with pancreatic cancer cases (P < 0.05). Our findings highlight that exploiting the environmental functions of soil DOM and mitigating the negative impacts are necessary, and require actions tailored to local soil DOM conditions.

Transethosomal gel for enhancing transdermal delivery of natural therapeutics.

Transethosomes, a fusion of transferosomes and ethosomes, combine the advantageous attributes of both vesicular systems to enhance deformability and skin permeation. While skin delivery is effective for drug transport, overcoming the skin barrier remains a significant challenge, particularly for plant-based products with poor permeability. Transethosomes offer a promising solution, but their low viscosity and retention on skin surfaces led to the development of transethosomal gels. These gels can entrap unstable and high molecular weight herbal extracts, fractions and bioactive compounds, facilitating enhanced drug delivery to the inner layers of the skin. This review focuses on the superior performance of transethosomes compared with conventional lipid-based nanovesicular systems, offering an advanced approach for transdermal delivery of plant-based drugs with improved permeability and stability.

Simple building blocks from forestry residues via convergent catalytic pathways

Funneling complex lignocellulose into simple and valuable building blocks has garnered significant interest in the field of biorefinery as a competitor to the petrochemical industry. Reductive Catalytic Fractionation (RCF) of lignocellulose, an innovative biorefinery technology, provides a promising strategy for complete valorization of lignocellulose into various valuable chemicals. In this study, integrated processes utilizing RCF strategies were developed to achieve complete conversion of lignocellulose into various simple and valuable platform chemicals. The core of this system is the flexible use of commercial Ni catalysts including Raney Ni and Ni/SiO2-Al2O3 which brings great benefits for future upscale and industrial applications. Surprisingly, both monomers derived from lignin and high molecular weight fractions could be converted to 4-ethylcyclohexanol while carbohydrate pulp was converted to furfural and 5-methoxymethylfurfural (MMF) in one-pot. MMF could be further upgraded to 2,5-Furandicarboxylicacid (FDCA) via catalytic oxidation by Ru/C catalysts. This work could inspire the development of more sustainable and economically viable biorefinery processes.

Study of humic-like substances of dissolved organic matter using size exclusion chromatography and chemometrics

The study of dissolved organic matter (DOM) presents a significant challenge for environmental analyses and the monitoring of wastewater treatment plants (WWTPs). This is particularly true for the tracking of recalcitrant to biodegradation dissolved organic matter (rDOM) compounds, which is generated during the thermal pretreatment of sludge. This study aims to develop analytical and chemometric methods to differentiate melanoidins from humic acids (HAs), two components of rDOM that require monitoring at various stages of wastewater treatment processes due to their distinct biological effects. The developed method implements the separation of macromolecules through ultra-high-performance liquid chromatography size-exclusion chromatography (U-HPLC SEC) followed by online UV and fluorescence detection. UV detection was performed at 210, 254, and 280 nm, and fluorescence detection at six excitation/emission pairs: 230/355 nm, 270/355 nm, 240/440 nm, 270/500 nm, 330/425 nm, and 390/500 nm. Chromatograms obtained for each sample from these nine detection modes were integrated and separated into four molecular fractions: >40 kDa, 20–40 kDa, 10–20 kDa, and <10 kDa. To enhance analytical resolution and normalize the data, ratios were calculated from the areas of chromatographic peaks obtained for each detection mode. The results demonstrate the utility of these ratios in discriminating samples composed of HAs, melanoidins, and their mixtures, through principal component analysis (PCA). Low molecular weight fractions were found to be specific to melanoidins, while high molecular weight fractions were characteristic of HAs. For the detection modes specific to melanoidins, UV absorbance at 210, 254, and 280 nm were predominantly present in the numerators, with tryptophan-like fluorescence emissions in the denominators. Conversely, fluorescence emissions largely represented both numerators and denominators for HAs. This online method also enables the discrimination of pseudo-melanoidins, compounds revealing a nitrogen deficiency in their chemical structures.

Impact of biochemical properties on the gelation of EPS extracted from aerobic granules

Extracellular Polymeric Substances (EPS) extracted from aerobic granular sludge are a promising source of gel-forming biopolymers. Gaining insights on the charge distribution of these polymers was performed through a fractionation using anionic chromatography. A gelling factor (GF) based on the apparent gel volume and the reactivity of polymers to calcium was attributed to each eluted fraction. The GF values of the eluted anionic EPS correlated with their negative charge. A GF of 0.04 ± 0.03 is measured for molecules eluted at NaCl 0.25 M and a GF of 0.32 ± 0.02 for the molecules eluted at NaCl 0.75 M. However, upon reaching a very high negative charge (elution at NaCl 1 M), the gelation capacity decreases. The size distribution of gelling molecules was analyzed by Size Exclusion Chromatography. High Molecular Weight (MW) molecules are predominantly involved in gelation (between 65 % and 100 % of the high molecular weight fraction from each sample) while low MW molecules participation is relatively limited (lower than 40 % of the low molecular weight fraction from each sample). Moreover, infra-red spectroscopy analysis of the molecules before and after calcium addition showed that mostly proteins and polysaccharides contribute to the hydrogel formation. Colorimetric methods showed that around 60 % of the uronic acids present in the samples could form hydrogels whereas proteins’ participation varied between 0 % and 100 % depending on the fraction.Thus, modulating EPS extraction and purification methods to ensure the preservation of their molecular weight and the selection of appropriate negative charge could be a strategy for EPS valorization.

Molecular Weight Distribution of Humic Acids Isolated from Calcic Cryosol in Central Yakutia, Russia.

The transition of soils into fallow state has a significant impact on the accumulation and transformation of soil organic matter (SOM). However, the issue of SOM transformation as a result of soil transition to fallow state in cryolithozone conditions is insufficiently studied. The aim of this study is to investigate the molecular weight (MW) distribution of humic acids (HAs) isolated from soils of central Yakutia. Native, fallow and agricultural soils in the vicinity of Yakutsk city were studied. MW distributions of HA preparations were obtained on an AKTAbasic 10 UPS chromatographic system (Amersam Biosciences, Uppsala, Sweden) using a SuperdexTM 200 10/300 GL column (with cross-linked dextran gel, fractionation range for globular proteins 10-600 kDa). The data on the molecular-mass distribution of HAs of fallow and agricultural soils of Central Yakutia were obtained for the first time. According to the obtained data, it was found that the highest carbon content in the structure of HAs was observed in agricultural soils (52.56%), and is associated with soil cultivation and fertilizer application. Among the HAs of fallow soils, we note that those soils that are in the process of self-vegetation have a relatively high carbon content in the HAs (45.84%), but the highest content was observed in fallow soils used as hayfields (49.98%), indicating that the reinvolvement of agriculture in fallow soils leads to an increase in the carbon content of HAs. According to the data of the MW distribution of HAs, it was found that the highest content of a high MW fraction of HAs was recorded in native soil (18.8%); this is due to the early stages of humification and the low maturity of organic matter. The highest content of a low MW fraction of HAs was recorded in agricultural soil (73.3%); this is due to the formation of molecular complexes of a "secondary" nature, which are more stable in the environment than the primary transformation products of humification precursors. The molecular composition of the HAs of fallow soils in the process of self-overgrowing is characterized by values closer to the HAs of native soils, which indicates their transformation towards HAs of native soils. The obtained results indicate that the reinvolvement of fallow soils leads to the transformation of the molecular composition of HAs towards HAs of agricultural soils, and to an increase in the resistance of SOM to biodegradation.

Molecular weight-dependent differences in spectral properties and metal-binding behaviors of dissolved organic matter from different lakes

Dissolved organic matter (DOM) plays an important role in governing metal speciation and migration in aquatic systems. In this study, various DOM samples were collected from Lakes Erhai, Kokonor, and Chaka, and size-fractionated into high molecular weight (HMW, 1 kDa–0.7 μm) and low molecular weight (LMW, <1 kDa) fractions for measurements of dissolved organic carbon (DOC), spectral properties, and metal binding behaviors. Our results demonstrated that samples from Lake Chaka exhibited the highest DOC concentration and fluorescence indices but the lowest percentage of carbohydrates. Regardless of sampling locations, the HMW-DOM fractions contained higher abundances of aromatic DOM, carbohydrates and protein-like substances, but lower abundance of fulvic acid-like substances compared to those in the LMW fractions. Metal titration experiments coupled with the excitation-emission matrix (EEM)-parallel factor (PARAFAC) modeling revealed that the quenching of the PARAFAC-derived fluorescent components was more pronounced in the presence of Cu(II) compared to Pb(II). Humic-like components emerged as a superior model, exhibiting higher binding affinities for Cu(II) than protein-like substances, while the opposite trend was observed for Pb(II). In samples obtained from Lakes Erhai and Kokonor, the condition stability constants (Log KM) for the binding of both Cu(II) and Pb(II) with the HMW-DOM fraction were higher than those with the LMW-DOM fraction. Conversely, a contrasting trend was observed for Lake Chaka. This study highlighted the heterogeneity in spectral properties and metal-binding behaviors of natural DOMs, contributing to an improved understanding of the molecular interactions between DOM components and metal ions and their environmental fate in aquatic ecosystems.

Investigation of the Distribution and Binding Affinity of Copper to Size-Fractioned Dissolved Organic Matter (DOM) in a Constructed Wetland

This study investigated the distribution and binding affinity of dissolved copper (Cu) and organic carbon (OC) in size-fractioned dissolved organic matter (DOM) in a constructed wetland (CW). Two sites were studied: one at the inflow (P-1) and one within the wetland (P-2). The DOMs (&lt;0.45 μm) were separated into six size fractions using a cross-flow ultrafiltration system. In the wetland (P-2), the concentrations of dissolved organic carbon (DOC) increased while the concentrations of Cu decreased. The high molecular weight fraction (1 kDa–0.45 μm, HMW) contained most of the OC mass (57.4–71.2% averages). On the other hand, Cu was almost equally distributed in HMW and low molecular weight fractions (&lt;1 kDa, LMW) with mean HMW percentages of 50.3–51.3%. The mean Cu binding affinity to DOM ratios (CuBADOM) was 74.9 ± 24.0 μmol/g-C at site P-1 and 17.3 ± 2.6 μmol/g-C at site P-2. The CuBADOM ratios were decreased in wetlands of bulk and size-fractioned DOM (p &lt; 0.001 to p = 0.073). The SUVA254 values for bulk DOM solution were 2.54 ± 0.15 and 1.68 ± 0.18 L/mg-C/m, and humidification index (HIX) values were 1.74 ± 0.16 and 2.09 ± 0.19 for sites P-1 and P-2, respectively. Optical indicators suggested that the wetland process decreased aromaticity but increased the humification degree of DOM. Furthermore, the CuBADOM ratios positively correlated with SUVA254 and HIX within the constructed wetland DOM but not in the influent DOM. Understanding the Cu distribution and binding affinity to size-fractioned DOM makes it possible to develop strategies to mitigate the potential effects of copper pollution in wetlands.

Local injection therapy with hyaluronic acid preparations: in focus of rheumatologists and orthopedic traumatologists

Hyaluronic acid (HA) is an effective and safe medication for local injection therapy (LIT) widely used in the treatment of osteoarthritis (OA) of large joints. The therapeutic effect of HA is determined both by the replacement of the lubricating function of natural hyaluronate (viscosupplementation), which leads to an improvement in the biomechanical parameters of the joint, and by the biological effects that unfold when interacting with cellular receptors (CD44, RHAMM, etc.), resulting in an anti-inflammatory, anti-nociceptive and anabolic effect of HA. HA therapy has a reliable evidence base. According to a number of clinical studies and meta-analyses, LIT with HA – reduces pain intensity by 28–54 % and improves the function of the affected joint by 9–32 % compared to baseline over a 12-24 week observation period. Repeated administration of HA can delay the need for orthopedic surgery. HA extremely rarely causes serious adverse events and can also be prescribed to patients with concomitant diseases. The use of HA for the treatment of OA is included in Russian and several foreign clinical guidelines (in particular OARSI and ESCEO). A new direction in LIT for OA is therapy with combined (hybrid) HA preparations containing high molecular weight (HMW) and low molecular weight (LMW) fractions. A new HA preparation has appeared in our country, which is a stabilized, highly purified hydrogel containing 80 % HMW HA (molecular weight – 30,000 kDa) with transverse "crosslinking" BDDE (innovative ECHATM technology) and 20 % "uncluttered" linear HA (molecular weight – 1500 kDa). This product is characterized by favorable rheological parameters, which guarantee a long-term improvement in the biomechanics of the affected joint and a rapid onset of biological effects, reduction in pain and inflammation and activation of the synthesis of natural hyaluronate.

Investigation of scaling inhibition and biofouling potential of different molecular weight fractions of a PAA antiscalant

This study investigates the scale inhibition performance of a commercial polyacrylic acid-based (PAA) antiscalant used for drinking water production and its molecular weight fractions (≤ 500 Da, ≥ 500 Da). The investigated antiscalant is used to prevent sulfate and carbonate scaling in treatment of drinking water sources by reverse osmosis or nanofiltration (RO/NF). Based on two complementary tests involving determination of induction time in a batch test and rate of flux decline in a lab-scale RO/NF plant, concordant results were obtained, proving that the overall performance of commercial PAA was controlled almost entirely by the higher molecular weight fraction. The low molecular weight fraction, which is potentially more permeable through the NF/RO membrane, showed poor inhibition against both sulfate and carbonate scalants. Furthermore, measurements on the assimilable organic carbon (AOC) by flow cytometry reveals that the low molecular weight PAA fraction has low biological stability, as its potential transport into the permeate of a NF270 nanofiltration membrane was inferred by elevated AOC values in the NF-permeate. These results are crucial information for water utilities, plant engineering, regulatory bodies and public authorities with respect to the possible operation of RO/NF especially in drinking water production.

Water-soluble compounds from Lignosus rhinocerus TM02® (xLr™) modulate ACE2 activity and inhibit its interaction with SARS-CoV-2 Spike-Protein

Water-soluble compounds from Lignosus rhinocerus TM02® (xLr™) modulate ACE2 activity and inhibit its interaction with SARS-CoV-2 Spike-Protein

Thorough Validation of Optimized Size Exclusion Chromatography-Total Organic Carbon Analysis for Natural Organic Matter in Fresh Waters.

Size exclusion chromatography with total organic carbon detection (HPSEC-TOC) is a widely employed technique for characterizing aquatic natural organic matter (NOM) into high, medium, and low molecular weight fractions. This study validates the suitability of HPSEC-TOC for a simplified yet efficient routine analysis of freshwater and its application within drinking water treatment plants. The investigation highlights key procedural considerations for optimal results and shows the importance of sample preservation by refrigeration with a maximum storage duration of two weeks. Prior to analysis, the removal of inorganic carbon is essential, which is achieved without altering the NOM composition through sample acidification to pH 6 and subsequent N2-purging. The chromatographic separation employs a preparative TSK HW-50S column to achieve a limit of detection of 19.0 µgC dm-3 with an injection volume of 1350 mm-3. The method demonstrates linearity up to 10,000 µgC dm-3. Precision, trueness and recovery assessments are conducted using certified reference materials, model compounds, and real water samples. The relative measurement uncertainty in routine analysis ranges from 3.22% to 5.17%, while the measurement uncertainty on the bias is 8.73%. Overall, the HPSEC-TOC represents a reliable tool for NOM fractions analysis in both treated and untreated ground and surface water.

Evaluation and Modeling of Polylactide Photodegradation under Ultraviolet Irradiation: Bio-Based Polyester Photolysis Mechanism.

In our study, we investigated the accelerated aging process of PLA under 253.7 nm UV-C irradiation with the use of the GPC, NMR, FTIR, and DSC methods and formal kinetic analysis. The results of GPC and DSC indicated a significant degree of destructive changes in the PLA macromolecules, while spectroscopic methods NMR and FTIR showed maintenance of the PLA main structural elements even after a long time of UV exposure. In addition to that, the GPC method displayed the formation of a high molecular weight fraction starting from 24 h of irradiation, and an increase in its content after 144 h of irradiation. It has been shown for the first time that a distinctive feature of prolonged UV exposure is the occurrence of intra- and intermolecular radical recombination reactions, leading to the formation of a high molecular weight fraction of PLA decomposition products. This causes the observed slowdown of the photolysis process. It was concluded that photolysis of PLA is a complex physicochemical process, the mechanism of which depends on morphological changes in the solid phase of the polymer under UV radiation.

Zwitterionic ring expansion polymerization of tert‐butyl glycidyl ether with B(C6F5)3 towards the generation of cyclic chains

AbstractThe synthesis of cyclic polymers via zwitterionic ring expansion polymerization is limited to a few number of monomer and catalyst pairs. Herein we report the synthesis of cyclic poly(tert‐butyl glycidyl ether) through the polymerization of tert‐butyl glycidyl ether (tBGE) with B(C6F5)3 in different reaction conditions that include different solvents, monomer to initiator ratio, monomer concentration and temperature. We found that bimodal molecular weight distribution is formed in almost all reaction conditions caused by cyclization of short chains. Subsequent chain elongation leads to the formation of cycles of higher molecular weight, particularly in cyclohexane and under bulk conditions. The formation of non‐cyclic byproducts is common in all the systems investigated. Low molecular weight cyclic chains (Mn = 0.7 kDa, Ð = 1.1) of high topological purity were successfully isolated by preparative gel permeation chromatography. By using a click scavenging protocol, the non‐cyclic byproducts were eliminated from the high molecular weight fraction (Mn = 3 kDa, Ð = 1.3) generating pure cyclic chains. Mechanistic investigation using density functional theory calculations was performed on the formation of zwitterionic intermediates and the transfer reaction to the monomer, which notably affects chain growth by the attack of the glycidyl oxygen of the monomer on the growing chain.

Distribution, chemical, and molecular composition of high and low molecular weight humic-like substances in ambient aerosols

Abstract. Humic-like substances (HULIS) encompass a continuum of molecular weight (MW) ranges, yet our understanding of how HULIS characteristics vary with MW is still limited and not well established. In this study, a combination of ultrafiltration and solid-phase extraction protocols was employed to fractionate the high MW (HMW; &gt; 1 kDa) and low MW (LMW; &lt; 1 kDa) HULIS fractions from ambient aerosols collected during summer and winter at a rural site. Subsequently, comprehensive characterization using total organic carbon, high-performance size exclusion chromatography (HPSEC), UV-visible (UV-vis) and fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), and negative electrospray ionization high-resolution mass spectrometry (ESI–HRMS) were conducted. The results revealed that HMW HULIS were dominated by larger-sized chromophores, substantially constituting a higher fraction of total organic carbon and UV absorption at 254 nm than LMW HULIS. While both HMW and LMW HULIS shared similar fluorophore types and functional groups, the former exhibited higher levels of humification and a greater presence of polar functional groups (e.g., −COOH; &gt; C=O). HRMS analysis further unveiled that molecular formulas within HMW HULIS generally featured smaller sizes but higher degrees of unsaturation and aromaticity compared to those within LMW HULIS fractions. This observation suggests the possibility of small molecules assembling to form the HMW HULIS through intermolecular weak forces. Moreover, HMW HULIS contained a higher proportion of CHON but fewer CHO compounds than LMW HULIS. In both HMW and LMW HULIS, the unique molecular formulas were primarily characterized by lignin-like species, yet the former displayed a prevalence of N-enriched and highly aromatic species. Additionally, HMW HULIS contained more unique lipid-like compounds, while LMW HULIS exhibited a distinct presence of tannin-like compounds. These findings provide valuable insights into the distribution, optical properties, and molecular-level characteristics of HULIS in atmospheric aerosols, thereby advancing our understanding of their sources, composition, and environmental implications.

Effect of ciprofloxacin on the one-stage partial nitrification and anammox biofilm system: A multivariate analysis focusing on size-fractionated organic components

The impact of ciprofloxacin (CIP) in the partial nitrification and anammox biofilm system was investigated by multivariate analysis, focusing on size-fractionated organic components. The CIP dose of 10 μg/L did not inhibit the total nitrogen (TN) removal efficiency, even though the abundance of antibiotic resistant genes (ARGs) (i.e., qnrD, qnrB, qnrA, qnrS, and arcA) was elevated. However, a gradual higher CIP dosing up to 100 μg/L inhibited the TN removal efficiency, while the abundance of ARGs was still increased. Moreover, both the TN removal efficiency and the abundant ARGs were dwindled at 470 μg/L of CIP. As the CIP dose increased from 0 to 100 μg/L, the abundance of high molecular weight (MW) fractions (14,000 to 87,000 Da; 1000 to 14,000 Da) and humic/fulvic acid-like components in the soluble extracellular polymeric substances (HSS) decreased, with more increases of low MW (84–1000 Da; less than 84 Da) fractions and soluble microbial by-products in soluble extracellular polymeric substances (SMPS). Continuously increasing the CIP dose till 470 μg/L, an inverse trend of the changes of these organic components was noted, along with clear reductions of the microbial diversity and richness, and the abundance of key functional genes responsible for nitrogen removal. The predominance of functional gene amoA (related with ammonia oxidizing bacteria) was more significantly with more distribution of SMPS with relatively low MW and less distribution of HSS with relatively high MW, as well as polymer decomposing microorganisms such as Bryobacteraceae and the unclassified Saprospirales.