Ice is an important physical and chemical sink for various pollutants in cold regions. The photodegradation of emerging fluoroquinolone (FQ) antibiotic contaminants with dissolved organic matter (DOM) in ice remains poorly understood. Here, the photodegradation of ciprofloxacin (CIP) and fulvic acid (FA) in different proportions as representative FQ and DOM in ice were investigated. Results suggested that the photodegradation rate constant of CIP in ice was 1.9 times higher than that in water. When CFA/CCIP ≤ 60, promotion was caused by FA sensitization. FA increased the formation rate of cleavage in the piperazine ring and defluorination products. When 60 < CFA/CCIP < 650, the effect of FA on CIP changed from promoting to inhibiting. When 650 ≤ CFA/CCIP ≤ 2600, inhibition was caused by both quenching effects of 143.9%–51.3% and light screening effects of 0%–48.7%. FA inhibited cleavage in the piperazine ring for CIP by the scavenging reaction intermediate of aniline radical cation in ice. When CFA/CCIP > 2600, the light screening effect was greater than the quenching effect. This work provides new insights into how DOM affects the FQ photodegradation with different concentration proportions, which is beneficial for understanding the environmental behaviors of fluorinated pharmaceuticals in cold regions.

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 long-term contamination of soil by microplastics may pose risks that are often still not well understood, and the ecological effects of microplastics are mainly dependent on their environmental behavior in environments. This study used saturated quartz sand as a solid porous medium to study the migration and influencing factors of 40–48 μm polyethylene (PE) particles in saturated porous media. The breakthrough curves at different injection concentrations (0.3, 0.4, 0.5 mg/L), flow rates (1.0, 1.5, 2.0, 2.5 ml/L), porous medium particle sizes (1–2, 2–4 mm), ionic strengths (0, 0.01, 0.05 mol/L) and concentrations of fulvic acid (FA) (0, 5, 10 mg/L) were compared and analyzed. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was used to more accurately explain relevant transport behaviors. The results showed that the input concentration, flow rate, and particle size can affect the migration of PE particles individually or in combination. As ionic strength increased, the repulsion between microplastics and quartz sand gradually disappeared according to DLVO theory, and their attraction gradually strengthened. As a result, fewer microplastics could penetrate the sand column and reach the water body. With the continuous addition of FA, the repulsive energy between microplastics and quartz sand rose from DLVO theory, and the migration ability of microplastics initially increased before becoming stable because of the effect of straining. In all cases, the migration ability of PE was low (C/C₀ < 0.35), and most PE particles remained in the porous media during the whole experimental periods. This study provides new insights of understanding the migration of microplastics in environment.

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.

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.

Bromoxynil is a widely used nitrile herbicide applied to maize and other cereals in many countries. To date, still little is known about bromoxynil turnover and the structural identity of bromoxynil non-extractable residues (NER) which are reported to occur in high amounts. Therefore, we investigated the microbial turnover of ¹³C-labeled bromoxynil for 32 days. A focus was laid on the estimation of biogenic NER based on the turnover of ¹³C into amino acids (AA). At the end, 25% of ¹³C₆-bromoxynil equivalents were mineralized, 2% assigned to extractable residues and 72.5% to NER. Based on 12% in the ¹³C-total AA and an assumed share of AA of 50% in microbial biomass we arrived at 24% of total ¹³C-biogenic NER. About 33% of the total ¹³C-NER could thus be explained by ¹³C-biogenic NER; 67% was unknown and by definition xenobiotic NER with potential for toxicity. The ¹³C label from ¹³C₆-bromoxynil was mainly detected in the humic acids (28.5%), but significant amounts were also found in non-humics (17.6%), fulvic acids (13.2%) and humins (12.7%). The ¹³C-total amino acids hydrolyzed from humic acids, humins and fulvic acids amounted to 5.2%, 6.1% and 1.2% of ¹³C₆-bromoxynil equivalents, respectively, corresponding to total ¹³C-biogenic NER amounts of 10.4%, 12.2% and 2.4%. The humins contained mostly ¹³C-biogenic NER, whereas the humic and fulvic acids may be dominated by the xenobiotic NER. Due to the high proportion of unknown ¹³C-NER and particularly in the humic and fulvic acids, future studies should focus on the detailed characterization of these fractions.

Antibiotics residuals in the environments receive wide concerns due to the high risk of generating antibiotic resistance. Natural organic matters (NOM) existed in the environments are considered to have the capacity of binding with organic contaminants, consequently influencing their speciation and transformation in the natural environments. To assess the migration of antibiotics in the environments, it is crucial to understand the binding mechanisms between NOM and antibiotics, which is still unclear due to the limit of available research methods. In this study, the interaction between fulvic acids (FA), one of the main components of NOM, and sulfamethazine (SMZ) was characterized by nuclear magnetic resonance (NMR) combined with surface plasmon resonance (SPR) and isothermal titration calorimetry (ITC) technology. The parameters related to kinetics and thermodynamics of the interaction were determined, and the possible mechanisms driving the interaction were also proposed. In addition, density functional theory (DFT) was used to predict the binding mode between FA and SMZ to reveal the interaction mechanism. Results indicate that FA can effectively bound with SMZ to form a stable complex with a binding constant at the level of 10³ L/mol. The kinetic parameters including association and dissociation constants were 29.4 L/mol/s and 6.64 × 10⁻³ 1/s, respectively. Hydrophobic interaction might play significant roles in the binding interaction with ancillary contribution of π-π conjunction arising from the aromatic rings stacking of FA and SMZ.

Microplastics have a great potential to sorb organic pollutants from the adjacent environment. In this study, the sorption of tetracycline, a polar and ionizable antibiotic, on three types of microplastics (polyethylene (PE), polypropylene (PP) and polystyrene (PS)) were investigated in batch sorption experiments. The sorption isotherms were well fitted by the Langmuir model, indicating that not only hydrophobic interactions but also other interactions (e.g. electrostatic interactions) played important roles in the sorption process. PS had the maximum sorption capacity, following the order PS > PP > PE, which can be attributed to polar interactions and π-π interactions. The sorption of tetracycline on microplastics was significantly influenced by pH, with sorption capacity increasing gradually, peaking at pH 6.0 and then decreasing, likely due to the influence of tetracycline speciation with the change of pH. Fulvic acid was selected as representative dissolved organic matter (DOM) to examine the effect on sorption. The increasing concentration of fulvic acid inhibited the sorption of tetracycline on three microplastics, decreasing them by more than 90% at the fulvic acid concentration of 20 mg/L, which implied a greater affinity of tetracycline to fulvic acid than to microplastics. Increasing salinity from 0.05 to 3.5% had negligible effects on the sorption of tetracycline on the three microplastics. Our results highlight the importance of pH and DOM on the sorption of tetracycline on microplastics, and suggest the relatively minor role of microplastics in the fate and transport of tetracycline in the aquatic environment in the presence of DOM.

Microplastic polystyrene foam has been found widely in the environment and is readily transported by wind or water. Beached and virgin foams of size 0.45–1 mm were prepared as sorbents to study oxytetracycline sorption. Enhanced adsorption were found in the beached foams compared to the virgin foams, corresponding to the higher specific surface area, micropore area and the degree of oxidation of the former. The Freundlich Kf value was 894 ± 84 ((mg kg⁻¹) (mg L⁻¹)¹/ⁿ) for oxytetracycline adsorption on the beached foams, approximately twice as high as on the virgin foams. Effects of solution pH on adsorption to the beached foams were more pronounced to the virgin foams. Maximum adsorption occurred at pH 5 at which electrostatic repulsion between the microplastic surface and the oxytetracycline zwitterion was minimal, indicating that electrostatic interaction may have regulated adsorption. Moreover, H-bonding and multivalent cationic bridging mechanisms may also have affected the adsorption of oxytetracycline to the beached foams as reflected by the ionic effects. Adsorption was promoted more in the presence of humic acid than of fulvic acid, perhaps owing to π-π conjugation between the humic acid and the microplastic surface which led to enhanced electrostatic attraction for oxytetracycline. This study suggests that weathered polystyrene foams may act as carriers of antibiotics in the environment and their potential risks to ecosystem and human health merit further investigation.