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.

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.

Metal contamination in the Pearl River Estuary (PRE) is persistent-, yet a comprehensive understanding of distribution and behavior of metals in surface water of this large, multi-source estuary is still lacking. In the present study, water samples from 24 sites spanning the whole estuary during the dry and wet season were collected and fractioned. Trace metal concentrations in samples were then determined following a preconcentration technique using Nobias Chelate-PA1 resin. Distribution of trace metals exhibited variability along and across estuary, as a result of estuarine mixing, external metal loadings, addition and removal. Behavior of metals was contrasting between the dry and wet seasons, exhibiting metal-specific intercorrelations and dynamics. Colloidal metals (Mn, Ni and Cd) were primarily present in upper estuary and areas affected by external contaminant loading. Colloidal Cu was the only metal that was ubiquitous in the estuary in both seasons. It showed a high affinity for small-size organic colloids (likely fulvic acid) during the dry season. Overall, the present study demonstrated the multi-source character of the PRE and that the behavior of trace metals was controlled by the coupling of hydrologic and geochemical processes, with anthropogenic perturbations.

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.

Fulvic acid (FA) significantly influences the bioavailability and fate of heavy metals in environments, while its acid-base characters and metal binding processes are still unclear. Here, spectroscopic techniques combined with multiple models (e.g., NICA-Donnan model) and two-dimensional correlation spectroscopy (2D COS) were applied to explore the proton and copper binding properties of FA sub-fractions (FA3-FA13). The charge densities, average contents of carboxylic and phenolic groups, average dissociation constants pKa1 and pKa2 of sub-fractions ranged 0–16 meq∙g∙C−1, 5.03–9.58 meq∙g∙C−1, 2.52–4.67 meq∙g∙C−1, 4.15–4.33 and 8.52–9.72, respectively. FA sub-fractions had a relatively narrow distribution of carboxyl group and a broad distribution of phenolic group. FA sub-fractions also exhibited roughly two phenolic hydroxyl groups per every 1–3 phenyl rings. Differential absorbance spectra (DAS) derived Gaussian bands were associated to the inter-chromophore interactions, the changes of molecular conformations and functional groups with copper addition. Differential spectra slopes (DSlope275-295&325-375) were more significant with higher copper concentration and copper amounts bonded to carboxylic groups. UV–Vis and fluorescence spectra with 2D heterospectral COS revealed the copper binding heterogeneities and sequential orders of chromophores and fluorophores, quantitatively confirming by the order of conditional stability constants (log KCu: 4.64–5.56). Salicylic-/polyhydroxyphenolic, hydroxyl and amino groups were strongly associated to the basic units for fluorophores. Sequential changes followed the order of humic-like→fulvic-like materials for FA3/FA5, humic-like→fulvic-like→tryptophan-like materials for FA7, and humic-like→tryptophan-like→fulvic-like→tyrosine-like materials for FA9/FA13. Spectroscopic techniques combined with various models (especially for 2D COS) are beneficial to elucidate the binding heterogeneity and sensitivity for metal-organic matters at the functional group level.

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.

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.

With increasing demand for recycled wastewater for irrigation purposes, there is a need to evaluate the potential for manufactured nanomaterials in waste water to impact crop production and agroecosystems. Copper oxide nanoparticles (CuO NPs) have previously been shown to negatively impact the growth of duckweed (Landoltia punctata) a model aquatic plant consumed by water fowl and widely found in agricultural runoff ditches in temperate climates. However, prior studies involving CuO NP toxicity to duckweed have focused on systems without the presence of dissolved organic matter (DOM). In the current study, duckweed growth inhibition was shown to be a function of aqueous Cu²⁺ concentration. Growth inhibition was greatest from aqueous CuCl₂ and, for particles, increased with decreasing CuO particle size. The dissolution of CuO NPs in ½ Hoagland's solution was measured to increase with decreasing particle size and in the presence of Suwannee river humic and fulvic acids (HA; FA). However, the current results suggest that HA, and to a lesser extent, FA, decrease the toxicity of both CuO NPs and free ionized Cu to duckweed, likely by inhibiting Cu availability through Cu-DOM complex formation. Such results are consistent with changes to Cu speciation as predicted by speciation modeling software and suggest that DOM changes Cu speciation and therefore toxicity in natural systems.

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.

This study investigated the effect of fulvic acid (FA) on the colloidal stability and reactivity of nano zero-valent iron (nZVI) at pH 5, 7 and 9. The sedimentation behavior of nZVI differed at different pH. A biphasic model was used to describe the two time-dependent settling processes (i.e., a rapid settling followed by a slower settling) and the settling rates were calculated. Generally, the settling of nZVI was more significant at the point of zero charge (pHpzc), which could be varied in the presence of FA due to the adsorption of FA on the nZVI surface. More FA was adsorbed on the nZVI surface at pH 5–7 than pH 9, resulting in the varying sedimentation behavior of nZVI via influencing the electrostatic repulsion among particles. Moreover, it was found that there was a tradeoff between the stabilization and the reactivity of nZVI as affected by the presence of FA. When FA concentration was at a low level, the adsorption of FA on the nZVI surface could enhance the particle stabilization, and thus facilitating the Cr(VI) reduction by providing more available surface sites. However, when the FA concentrations were too high to occupy the active surface sites of nZVI, the Cr(VI) reduction could be decreased even though the FA enhanced the dispersion of nZVI particles. At pH 9, the FA improved the Cr(VI) reduction by nZVI. Given the adsorption of FA on the nZVI surface was insignificant and its effect on the settling behavior of nZVI particles was minimal, it was proposed that the FA formed soluble complexes with the produced Fe(III)/Cr(III) ions, and thus reducing the degree of passivation on the nZVI surface and facilitating the Cr(VI) reduction.