Dissolved organic matter (DOM) plays a significant role in the photochemical behavior of nano- and micro-plastic particles (NPs/MPs). We investigated the influence of DOM on the mechanism on the photoaging of NPs/MPs with different molecular structures under UV₃₆₅ irradiation in water. DOM components used in this study are mainly humic acid and fulvic acid. The results showed that DOM promoted the weathering of aliphatic NPs/MPs (polypropylene (PP)), but inhibited or had only a minor effect on the photoaging of aromatic NPs/MPs (polystyrene (PS) NPs/MPs, carboxyl-modified PS NPs, amino-modified PS NPs, and polycarbonate MPs). NPs with a large surface area may adsorb sufficient DOM on the particle surfaces through π-π interactions, which competes with NPs for photon absorption sites, thus, can delay the photoaging of PS NPs. Aromatic MPs may release phenolic compounds that quench •OH, thereby weakening the photoaging process. For aliphatic MPs, the detection of peracid, aldehyde, and ketone groups on the polymer surface indicated that DOM promoted weathering of PP MPs, which was primarily because the generation of •OH due to DOM photolysis may attack the polymer by C–C bond cleavage and hydrogen extraction reactions. This study provides insight into the UV irradiation weathering process of NPs/MPs of various compositions and structures, which are globally distributed in water.

Iron (III) co-precipitation with dissolved organic matter (DOM) is pervasive in many natural environments. However, the effects of DOM on the formation of Fe(III) hydroxysulfate (FHS) and its environmental implications are poorly understood. In this study, fulvic acid (FA) was used as a model DOM compound, and experiments were devised to investigate the effects of FA on the formation of FHS. In addition, the Pb(II) adsorption capabilities of FHSs biosynthesized under various FA dosages, including kinetics and sorption isotherm experiments, were conducted. These experiments showed that co-precipitation of FA promoted the formation of Fe-FA composites, FA-doped schwertmannite, and small particles of jarosite. Co-precipitates are more enriched in carboxyl (–COOH) functional groups due to their preferential binding with FHS. The adsorption kinetics, isotherms and mechanisms of Pb onto the biosynthesized FHSs were then comprehensively characterized and modeled. Though the specific surface area decreased with increasing FA loading, the introduction of FA into FHSs increased Pb(II) adsorption, with the highest concentration of FA addition improving the removal capacity of Pb(II) to 91.54%. Kinetics studies and intra-particle diffusion models indicated that the adsorption of Pb(II) onto the FHSs was correlated with the number of active sites, and two adsorption steps: surface adsorption and the diffusion of Pb(II) in channels inside the biosynthesized FHSs, are suggested. The adsorption mechanism was attributed to cation exchange between Pb(II) and –OH and –COOH functional groups, and the co-precipitated FA provided additional sites for Pb(II) adsorption by FHS.

Selenium (Se) is regarded as a trace element for humans, but it is toxic in excess. In natural environments, the mobility of Se is dominantly controlled by the Se oxyanions with high solubility such as selenite (Se(IV)). Se(IV) is often associated with the omnipresent ferrihydrite and coexisting organic matter. However, there is little information on the dynamic interactions among Se(IV), fulvic acid, and ferrihydrite. This study investigated the influence of fulvic acid on ferrihydrite-Se(IV) coprecipitates (Fh-Se) transformation for 8 days and the subsequent behavior of Se(IV) at varied pH (5.0, 7.5, and 10.0). Results showed that fulvic acid had different effects on Fh-Se transformation at varied pH values. Fh-Se transformation was promoted by fulvic acid at initial pH 5.0 whereas it was inhibited at initial pH 10.0. Interestingly, at initial pH 7.5, Fh-Se transformation was promoted at a low C/Fe ratio while it was suppressed at a high C/Fe ratio. Besides, fulvic acid induced the generation of more extractable Se(IV) at initial pH 5.0 and more coprecipitated Se(IV) at initial pH 7.5 and blocked the release of Se(IV) at initial pH 10.0. Fulvic acid possibly interacted with Se(IV) via carboxyl complexation and weakened the inhibition of Se(IV) on Fh-Se transformation. Thus, fulvic acid increased the transformation rate of Fh-Se. These findings help to uncover the environmental behavior of Se(IV) and organic matter during ferrihydrite transformation.

The quality and quantity of dissolved organic matter (DOM) greatly controls the fate of heavy metals. The characteristics of DOM and its interaction with metals are essential for the metal ecological risk assessment of soils. In this study, the DOM spectral characteristics of representative forest soils and the complex capacities between fluorescent DOM components and cadmium (Cd) were analyzed. Functional groups, such as carboxylic acids, alcohols and phenols, were determined by FT-IR analysis. Chromophoric DOM, fluorescent DOM and dissolved organic carbon (DOC) concentrations exhibited strong correlations with each other, indicating that variations of DOC could be well explained by Chromophoric DOM or fluorescent DOM due to high correlation coefficients. The spectral slope ratio was in the range of 0.85–5.90, implying an abundance of heavy macromolecular humic acids, peptides, and polycondensates. The absorbance spectral at 254 nm (SUVA₂₅₄) strongly correlated with SUVA₂₆₀ (r = 0.992, P < 0.01), indicating that hydrophobicity closely related with aromatic structure, and aromatic groups could be broadly hydrophobic. Fluorescence indices were from 1.62 to 2.21 and biological index values ranged from 0.54 to 1.14, where the DOM was mainly sourced from mixed terrestrial and autogenous inputs in most sites. Four universal fluorescence components were identified and characterized by fluorescence EEM-PARAFAC, including two humic-like (components 1 and 2), one tyrosine-like (components 3) and one fulvic-like (components 4) component. Both components 3 and 4 showed fluorescence quenching with increasing Cd concentrations, while components 1 and 2 had no evident change in fluorescence intensity. The logK₃ and logK₄ values ranged from 4.41 to 5.29 and 4.71 to 5.54, respectively, with most logK values of component 3 for Cd binding being smaller than that of component 4, thus, indicating that the fulvic acid substances exhibited stronger and more stable interactions with Cd than protein-like components.

Soot nanoparticles (SNPs) produced from incomplete combustion have strong impacts on aquatic environments as they eventually reach surface water, where their environmental fate and transport are largely controlled by aggregation. This study investigated the aggregation kinetics of SNPs in the presence of macromolecules including fulvic acid (FA), humic acid (HA), alginate polysaccharide, and bovine serum albumin (BSA, protein) under various environmentally relevant solution conditions. Our results showed that increasing salt concentrations induced SNP aggregation by suppressing electrostatic repulsion and that CaCl2 exhibited stronger effect than NaCl in charge neutralization, which is in agreement with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The aggregation rates of SNPs were variously reduced by macromolecules, and such stabilization effect was the greatest by BSA, followed by HA, alginate, and FA. Steric repulsion resulting from macromolecules adsorbed on SNP surfaces was mainly responsible for enhancing SNP stability. Such steric repulsion appeared to be affected by macromolecular structure, as BSA having a more compact globular structure on SNP surfaces imparted long-range steric repulsive forces and retarded the SNP aggregation rate by 10–100 times. In addition, alginate was shown to enhance SNP aggregation by ∼10 times at high CaCl2 concentrations due to alginate gel formation via calcium bridging. The results may bear strong significance for the fate and transport of SNPs in both natural and controlled environmental systems.

The effects of fulvic acid (FA) and ions on mesophilic pathogenic bacteria survival under freeze-thaw (FT) stress in natural water and its resistant mechanisms are rarely understood. Therefore, survival patterns of Escherichia coli in river water added with various concentrations of FA or FA-ion under FT stress were studied in this work. Meanwhile, cell surface hydrophobicity (CSH), unit activities of superoxide dismutase (SOD) and catalase (CAT) were determined and Escherichia coli morphologies were observed to explore the bacterial resistant mechanisms against FT stress. The results demonstrated that FT cycles significantly reduced bacterial quantities as sampling time, i.e. freeze-thaw cycle time increased. And the biggest reducing rate was observed after the first FT cycle in every system. Ttd values, time needed to reach detection limit under FT stress decreased under FT stress as FA was added into water, while the changes of ttd values were quite complicated when FA and various ions existed together. Generally, the ttd values of FA-cation systems exceeded that of FA system except FA-Ca²⁺ systems, but it was opposite for FA-anion systems. CSH was heightened after FT cycles and reached peak value at last sampling time in every system. Mechanical constraint from extracellular ice crystals and high CSH induced bacterial aggregation, which protect inner cells of aggregation from extracellular ice crystals. And the unit activities of SOD were significantly higher than those of CAT. Unit activities of SOD and CAT in large part of tested systems increased with sampling time under FT stress, which reduced reactive oxygen species produced from repeated FT cycles. Thus, these could improve the resistance of Escherichia coli to freeze-thaw stress and promote their survival. This work explored the survival pattern and strategy of Escherichia coli in natural water under FT stress.

Soluble microbial products (SMPs) discharged into rivers from sewage treatment plants may increase the health risk for downstream drinking water by acting as a precursor of DBPs. Biotransformation or biodegradation could alter the characteristics of SMPs and affect the subsequent formation of DBPs. This study observed the relative contribution of chemical fractions in SMPs and explored the biodegradation of each fraction and their effect on disinfection by-products (DBPs) formation in surface water. The hydrophilic acid (HPIA) and hydrophobic acid (HPOA) constituted the major portion of the SMPs, which were dominated by fulvic acid and humic acids. The transphilic acid (TPIA) and hydrophobic bases (HPOB) were relatively minor but it contained a relative substantial portion of protein-like materials in SMPs. TPIA and HPOB produced insignificant amounts of DBP corresponding to 13% and 14% in the original samples, but they were collectively responsible for 50% of the DBPs yield. Much larger amounts of hydrophobic fractions were utilized than hydrophilic fractions after biodegradation. The increase in SUVA values indicating aromatic structures, except for HPOA fraction, was observed after biodegradation. The protein-like materials in both the HPOA and HPIA fractions and polycarboxylate-type humic acid in the HPIA fraction decreased but the enrichment of HPOA (MW > 100 kDa) and TPIA (MW < 1 kDa) was observed after biodegradation. The production of = C–H in HPIA fraction and the appearance of double peak at 1100 cm⁻¹ in TPIA and HPOB fractions occurred after biodegradation. In overall level, microorganisms effectively utilized DBP precursors from HPIA, HPOA and HPOB fractions but increased the DBPs precursors from the TPIA fraction. TPIA and HPOB fractions had higher DBP yield with chlorine but the DBPs yield of HPIA and HPOA changed little after biodegradation.

Application of biochar in the field has received considerable attention in recent years, but there is still little known about the fate and transport of biochar colloids (BCs) in the subsurface. Natural organic matter (NOM), which mainly consists of humic substance (HS) and proteins, is ubiquitous in the natural environment and its dissolved fraction is active and mobile. In this study, the transport of BCs in saturated porous media has been examined in the presence of two HS (humic and fulvic acids) and two proteins. Bull serum albumin (BSA) and Cytochrome c (Cyt) were selected to present the negatively and positively charged protein, respectively. At low and high salt concentration and different pH conditions, the transport of BCs was strongly promoted by HS. HS significantly increased the mobility of BCs in porous media under both low and high salt conditions due to the enhanced electrostatic repulsion and modification of surface roughness and charge heterogeneity. While BC mobility in porous media was suppressed by both BSA and Cyt in the low salt solution, the presence of BSA largely promoted and Cyt slightly enhanced the transport of BCs in high salt solutions. BSA and Cyt adsorption onto BC surface decreased the negative charge of BC and resulted in a less repulsive interaction in low salt solutions. In high salt solutions, the adsorbed BSA layers disaggregated BCs and reduced the strength of the interaction between BC and the sand. Adsorbed Cyt on BCs caused more attractive patches between BC and sand surface, and greater retention than BSA.

The humic-like substances were the main organic components in most wastewater (e.g. domestic sewage, toilet wastewater and landfill leachate). Two types of actual humic-like substances (fulvic acid (FA) and biologically treated landfill leachate (BTLL)) were selected to describe the changes in the properties of humic-like substances (complexation ability, aromaticity and mobility) during electrochemical oxidation. Meanwhile, the acute cytotoxicity of FA and BTLL was also tested by acute toxicological test of luminescent bacteria. The results showed that the consumption of coordinating groups such as phenolic groups and hydrogen bonds reduced the complexation ability of FA and BTLL. The functional groups were degraded with the removal order of quinone group, phenolic group and aromatic group, and finally realized the molecular saturation and aromaticity decrease for humic-like substances. The mobility of FA and BTLL was decreased because of the enhancement of hydrophobicity during electrolysis process. Furthermore, the available chlorine produced during electrochemical oxidation was the main acute cytotoxicity substance, therefore, it is necessary to remove it before discharge in order to reduce ecological risks. This study provides a basis for understanding and evaluating the electrochemical degradation process of humic-like substances in detail.

Better understanding of the colloidal behaviors of nanomaterials impacted by aquatic chemistry parameters is needed for appropriate evaluation of the environmental risks posed by nanomaterials in natural waters. In the study, the colloidal stability of Fe3O4 magnetic nanoparticles (Fe-MNPs) was evaluated over a range of chemistry characteristics [e.g., pH, dissolved organic matter (DOM), salt types, cationic strength] in six synthetic water samples. The findings from the synthetic water samples were further examined with eight “real world” environmental water samples. Our results demonstrated that DOM fraction, humic acid (HA), promoted suspension of Fe-MNPs more by hydrophobic interactions in addition to ligand exchange and electrostatic effects compared with fulvic acid (FA). Capability of cations to increase aggregation of Fe-MNPs were in the order of Ca2+ > Mg2+ >> Na+ because of their different degrees of bridging complexation with DOM molecules on particle surfaces. As a key parameter for indicating Fe-MNPs colloidal stability, Zeta (ζ) potentials of Fe-MNPs in these waters samples were well correlated to (R2 = 0.880, P < 0.001) the contents, types and adsorption forms of DOM and cations. However, several other factors could also affect the hydrodynamic diameter (HDD) of Fe-MNPs in the “real world” environmental waters. It assumed that ampholytic-DOM molecules such as amino acid- and protein-like molecules caused great aggregation of Fe-MNPs. These findings would be helpful for better understanding and evaluating the colloidal behaviors of nanomaterials when they released into natural water environment, thus could shed light on developing relevant pollution control strategies.