High-Resolution Mass Spectrometry Combined with Reactive Oxygen Species Reveals Differences in Photoreactivity of Dissolved Organic Matter from Microplastic Sources in Aqueous Environments.

Microplastics (MPs)-derived dissolved organic matter (MPs-DOM) is becoming a non-negligible source of DOM pools in aquatic systems, but there is limited understanding about the photoreactivity of different MPs-DOM. Herein, MPs-DOM from polystyrene (PS), polyethylene terephthalate (PET), poly(butylene adipate-co-terephthalate) (PBAT), PE, and polypropylene (PP), representing aromatic, biodegradable, and aliphatic plastics, were prepared to examine their photoreactivity. Spectral and high-resolution mass spectrometry analyses revealed that PS/PET/PBAT-DOM contained more unsaturated aromatic components, whereas PE/PP-DOM was richer in saturated aliphatic components. Photodegradation experiments observed that unsaturated aromatic molecules were prone to be degraded compared to saturated aliphatic molecules, leading to a higher degradation of PS/PET/PBAT-DOM than PE/PP-DOM. PS/PET/PBAT-DOM was mainly degraded by hydroxyl (•OH) via attacking unsaturated aromatic structures, whereas PE/PP-DOM by singlet oxygen (1O2) through oxidizing aliphatic side chains. The [•OH]ss was 1.21-1.60 × 10-4 M in PS/PET/PBAT-DOM and 0.97-1.14 × 10-4 M in PE/PP-DOM, while the [1O2]ss was 0.90-1.35 × 10-12 and 0.33-0.44 × 10-12 M, respectively. This contributes to the stronger photoreactivity of PS/PET/PBAT-DOM with a higher unsaturated aromatic degree than PE/PP-DOM. The photodegradation of MPs-DOM reflected a decreasing tendency from aromatic-unsaturated molecules to aliphatic-saturated molecules. Special attention should be paid to the photoreactivity and environmental impacts associated with MPs-DOM containing highly unsaturated aromatic compounds.

Biofilm-Colonized versus Virgin Black Microplastics to Accelerate the Photodegradation of Tetracycline in Aquatic Environments: Analysis of Underneath Mechanisms.

Tire wear particles (TWPs) exposed to the aquatic environment are rapidly colonized by microorganisms and provide unique substrates for biofilm formation, which potentially serve as vectors for tetracycline (TC) to influence their behaviors and potential risks. To date, the photodegradation capacity of TWPs on contaminants due to biofilm formation has not been quantified. To accomplish this, we examined the ability of virgin TWPs (V-TWPs) and biofilm-developed TWPs (Bio-TWPs) to photodegrade TC when exposed to simulated sunlight irradiation. V-TWPs and Bio-TWPs accelerated the photodegradation of TC, with rates (kobs) of 0.0232 ± 0.0014 and 0.0152 ± 0.0010 h-1, respectively (kobs increased by 2.5-3.7 times compared to that for only TC solution). An important factor of increased TC photodegradation behavior was identified and linked to the changed reactive oxygen species (ROS) of different TWPs. The V-TWPs were exposed to light for 48 h, resulting in more ROS for attacking TC, with hydroxyl radicals (•OH) and superoxide anions (O2•-) playing a dominant role in TC photodegradation measured using scavenger/probe chemicals. This was primarily due to the greater photosensitization effects and higher electron-transfer capacity of V-TWPs in comparison to Bio-TWPs. In addition, this study first sheds light on the unique effect and intrinsic mechanism of the crucial role of Bio-TWPs in TC photodegradation, enhancing our holistic understanding of the environmental behavior of TWPs and the associated contaminants.

Enzymatic preparation of hydrophobic biomass with one-pot synthesis and the oil removal performance.

Oil pollution is causing deleterious damage to aquatic ecosystems and human health. The utilization of agricultural waste such as corn stalk (CS) to produce biosorbents has been considered an ecofriendly and efficient approach for removing oil. However, most previous studies focused on the modification of the whole CS, which is inefficient due to the heterogeneity of CS. In this study, corn stalk pith (CP), which has excellent amphipathic characteristics, was selected to prepare a high-efficiency oil sorbent by grafting dodecyl gallate (DG, a long-chain alkyl) onto CP surface lignin via laccase mediation. The modified biomass (DGCP) shows high hydrophobicity (water contact angle = 140.2°) and superoleophilicity (oil contact angle = 0°) and exhibits a high oil sorption capacity (46.43 g/g). In addition, DGCP has good stability and reusability for adsorbing oil from the aqueous phase. Kinetic and isotherm models and two-dimensional correlation spectroscopy integrated with FTIR analyses revealed that the main sorption mechanism involves the H-bond effect, hydrophobic effect and van der Waals force. This work provides an ecofriendly method to prepare oil sorbents and new insights into the mechanisms underlying the removal of spilled oil from wastewater.

Dissolved Organic Matter Promotes the Aging Process of Polystyrene Microplastics under Dark and Ultraviolet Light Conditions: The Crucial Role of Reactive Oxygen Species.

Microplastics (MPs) interact frequently with dissolved organic matter (DOM) commonly found in the environment, but information on the aging behavior of MPs under the participation of DOM is still lacking. Thus, the polystyrene microplastic (PSMP) aging process with DOM participation was systematically studied by electron paramagnetic resonance spectroscopy, high-performance liquid chromatography, Fourier transform infrared (FTIR) spectroscopy, and two-dimensional correlation spectroscopy analyses under dark and ultraviolet (UV) light conditions. DOM was found to promote electron transfer to generate reactive oxygen species (ROS) under dark conditions and the aging of PSMPs, while the process of DOM generating ROS under UV light was more susceptible to photoelectrons and accelerated the aging process of PSMPs. However, among the four DOM types, fulvic acid (FA) has a more significant promoting effect on the aging process of PSMPs than humic acid, which can be attributed to the stronger conversion ability of FA to semiquinone radicals. Density functional theory calculations are used to describe the difference in the aging process of different structures of plastics with the participation of DOM. This study provides a necessary theoretical basis for the study of the migration of MPs in groundwater and deep surface water.

Bioaccessibility of Microplastic-Associated Antibiotics in Freshwater Organisms: Highlighting the Impacts of Biofilm Colonization via an In Vitro Protocol.

Microplastics in the environment can be colonized by microbes capable of forming biofilms, which may act as reactive coatings to affect the bioaccessibility of pollutants in organisms. This study investigated the dynamic evolution of biofilm colonization on microplastics and its impacts and mechanisms on the bioaccessibility of microplastic-associated sulfamethazine (SMT) via microcosm incubation in surface water and sediment. After 60 days of incubation, the microbial communities formed in microplastics were distinct and more diverse than those untethered in surroundings, and photoaging treatment decreased the affinity of biofilms on microplastics due to decreased hydrophobicity. Biofilm formation further enhanced the desorption and bioaccessibility of microplastic-sorbed SMT in organisms. In vitro experiments indicated that the critical effects were mainly related to the stronger interaction of gastrointestinal components (i.e., pepsin, bovine serum albumin (BSA), and NaT) with biofilm components (e.g., extracellular polymer substances) than with the pure surface of microplastics, which competed for binding sites in microplastics for SMT more significantly. Photoaging decreased the enhancing effects of biofilms due to their lower accumulation in aged microplastics. This study is the first attempt to reveal the role of biofilms in the bioaccessibility of microplastics with associated antibiotics and provide insights into the combined risk of microplastics in the environment.

Oxygen Limitation Accelerates Regeneration of Active Sites on a MnO2 Surface: Promoting Transformation of Organic Matter and Carbon Preservation.

Birnessite (δ-MnO2) is a layered manganese oxide widely present in the environment and actively participates in the transformation of natural organic matter (NOM) in biogeochemical processes. However, the effect of oxygen on the dynamic interface processes of NOM and δ-MnO2 remains unclear. This study systematically investigated the interactions between δ-MnO2 and fulvic acid (FA) under both aerobic and anaerobic conditions. FA was transformed by δ-MnO2 via direct electron transfer and the generated reactive oxygen species (ROS). During the 32-day reaction, 79.8% of total organic carbon (TOC) in solution was removed under anaerobic conditions, unexpectedly higher than that under aerobic conditions (69.8%), suggesting that oxygen limitation was more conducive to the oxidative transformation of FA by δ-MnO2. The oxygen vacancies (OV) on the surface of δ-MnO2 were more exposed under anaerobic conditions, thus promoting the adsorption and transformation of FA as well as regeneration of the active sites. Additionally, the reaction of FA with δ-MnO2 weakened the strongly bonded lattice oxygen (Olatt), and the released Olatt was an important source of ROS. Interestingly, a part of organic carbon (OC) was preserved by forming MnCO3, which might be a novel mechanism for carbon preservation. These findings contribute to an improved understanding of the dynamic interface processes between MnO2 and NOM and provide new insights into the effects of oxygen limitation on the cycling and preservation of OC.

Insight into the Photodegradation of Microplastics Boosted by Iron (Hydr)oxides.

Iron (hydr)oxides as a kind of natural mineral actively participate in the transformation of organic pollutants, but there is a large knowledge gap in their impacts on photochemical processes of microplastics (MPs). This study is the first to examine the degradation of two ordinary plastic materials, polyethylene (PE) and polypropylene (PP), mediated by iron (hydr)oxides (goethite and hematite) under simulated solar light irradiation. Both iron (hydr)oxides significantly promoted the degradation of MPs (particularly PP) with a greater effect by goethite than hematite, related to hydroxyl radical (•OH) produced by iron (hydr)oxides. Under light irradiation, the surface Fe(II) phase catalyzed the production of H2O2 and promoted the release of Fe2+, leading to the subsequent light-driven Fenton reaction which produced a large amount of •OH. As the iron (hydr)oxides were modified with NaF at various concentrations, the activity of the surface Fe(II) as well as the release of Fe2+ were greatly reduced, and thus the •OH formation and MP degradation were depressed remarkably. It is worth noting that the surface hydroxyl groups (especially ≡FeOH) affected the reaction kinetics of •OH by regulating the activity of Fe species. These findings unveil the distinct impacts and intrinsic mechanisms of iron (hydr)oxides in influencing the photodegradation of MPs.

The First Observation of the Formation of Persistent Aminoxyl Radicals and Reactive Nitrogen Species on Photoirradiated Nitrogen-Containing Microplastics.

Nitrogen-containing microplastics (N-MPs) are widely present in the atmosphere, but their potential health risks have been overlooked. In this study, the formation of persistent aminoxyl radicals (PAORs) and reactive nitrogen species (RNSs) on the N-MPs under light irradiation was investigated. After photoaging, an anisotropic triplet with the g-factor of ∼2.0044, corresponding to PAORs, was detected on the nonaromatic polyamide (PA) rather than amino resin (AmR) by electron paramagnetic resonance and confirmed by density functional theory calculations. The generated amine oxide portions on the photoaged PA were identified using X-ray photoelectron spectroscopy and Raman spectroscopy, which were considered to be the main structural basis/precursors of a PAOR. Surprisingly, RNSs were also observed on the irradiated PA. The generated ·NO due to the aphotolysis of nitrone groups simultaneously reacted with peroxide radicals and O2·- to yield ·NO2 and peroxynitrite, respectively, which were responsible for peroxyacyl nitrates (PAN) and CO3·- formation. Besides, a significantly higher oxidative potential and reductive potential were observed for the aged PA than AmR, which is assigned to the abundant RNSs, organic hydroperoxides and PANs, and a strong ability to transfer electrons from PAOR, respectively. This work provides important information for the potential risks of airborne N-MPs and may serve as a guide for future toxicological assessments.

Photocatalytic degradation of (micro)plastics using TiO2-based and other catalysts: Properties, influencing factor, and mechanism.

(Micro)plastics pollution has raised global concern because of its potential threat to the biota. The review on recent developments of photocatalytic degradation of (micro)plastics is still insufficient. In this study, we have discussed various bare and composites photocatalysts involved in the photocatalytic degradation of (micro)plastics. The photocatalytic mechanisms and factors affecting the degradation were also discussed. To improve the performance of photocatalysts, their surface is modified with metal or non-metal dopants. These doped photocatalysts are then compounded with a variety of environmentally friendly and nontoxic polymers to prepare multifunctional composites. The generation of reactive oxygen species (ROS) plays an important role in the photocatalytic degradation of (micro)plastics, and superoxide ions (O2-) and hydroxyl radicals (OH) participate in the photocatalytic degradation, leading to the breaking of the polymer chain and the production of some intermediates. Although satisfactory progress has been achieved in the photodegradation of (micro)plastics, most photocatalytic degradation technologies investigated to date cannot realize the complete mineralization of (micro)plastics. Furthermore, based on the current challenges of the existing photocatalytic degradation technologies, perspectives for future research directions have been proposed. This review presents a systematic summary of the progress made in the photocatalytic degradation of (micro)plastics and offers a comprehensive reference for future research on improving the (micro)plastics photocatalytic degradation efficiency.

Pollution characteristics and health risk assessment of potentially toxic elements in soils around China's gold mines: a meta-analysis.

Since toxic element pollution is widespread in soils near gold mines due to increasing mining activities, the adverse effects of potentially toxic elements (PTEs) in the soils on ecological systems and human health cannot be ignored. However, assessments of PTE pollution in soils and their ecological-health risks on a national scale are still limited. Here, the concentrations of eight PTEs in soils near gold mines throughout China were obtained from published articles. Based on these data, the pollution levels and ecological-health risks of the eight PTEs in soils were comprehensively estimated. The results showed that the average contents of As, Cr, Cd, Pb, Hg, Cu, Ni, and Zn were 81.62, 79.82, 1.04, 206.03, 2.05, 40.82, 71.82, and 130.42 mg kg-1, respectively, which exceeded the corresponding background values for soils. Most of the examined soils were heavily polluted by Hg and Cd, and higher pollution levels were found in the Henan and Shaanxi Provinces than in other regions. The average potential ecological risk value of all PTEs was 2534.71, indicating the presence of very high risks. Contribution of Hg to the potential ecological risk was more than 80%. For adults, all hazard index (HI) values of noncarcinogenic risks were below the safe level of 1.00. For children, none of the HI values exceeded the safe level, with the exception of As (HI = 1.81); nevertheless, four PTEs (As, Cr, Cu, and Ni) presented unacceptable carcinogenic risks. This study provides scientific basis for controlling PTE contamination and reducing the health risks in soils near gold mines worldwide.

Effect of cadmium on the sorption of tylosin by polystyrene microplastics.

Microplastics are widespread in the environment and might transport readily by ocean currents, wind and atmospheric deposition. Simultaneously, antibiotics and heavy metals could often be detected in the environment. They are both positively charged, it is necessary to clarify the interactions of these pollutants with microplastics when they were coexist. In this study, the most commonly used polystyrene (PS) was selected as a representative microplastic. This study investigated the effect of Cd(II) on the sorption of TYL by PS in different coexistence systems. The results showed that: in the composite system, when TYL and Cd(II) coexist, the presence of Cd(II) could inhibit the sorption of TYL by PS, and the inhibitory effect increases with the increase of the concentration of Cd(II), indicating that competitive sorption dominates the sorption. When PS adsorbed Cd(II) first and then adsorbed TYL, the presence of Cd(II) was conducive to the sorption of TYL, and the sorption strengthened with the increase of Cd(II) concentration, indicating that the complexation between TYL and Cd(II) enhanced the sorption of TYL. In addition, initial pH values and ionic strength were essential in the sorption process. Therefore, this study could provide an important basis for evaluating the environmental behavior and ecological risk of microplastics in the process of compound pollution.

Sorption properties of cadmium on microplastics: The common practice experiment and A two-dimensional correlation spectroscopic study.

Microplastics (MPs) that have accumulated in the environment are emerging as contaminating pollutants due to their interactions with metal ions. MPs change the migration and transformation of metal ions in the environment and afterward impact their environmental presence. Therefore, it is necessary to evaluate the interaction characteristics and mechanisms between Cd2+and MPs for assessing the ecological impacts of MPs. The traditional sequencing batch equilibrium test demonstrated that the sorption of Cd2+ onto MPs was related to the type of MPs present, the pH value of the solution, the ionic strength of the participants and the presence of humic acid. The sorption dynamics and isotherm experiment illustrated that the interactions were controlled by surface sorption and distribution effects. The specific surface area and surface charge were the main factors in managing the sorption process. FTIR spectra and a 2D-COS analysis showed that different functional groups played an important role in the sorption of Cd2+onto MPs. The results from this work afford new insights on how MPs may play an important role in the fate and transport of heavy metals and present a new analysis method for evaluating the environmental behavior of MPs and their role in transporting other contaminants.

Formation of Environmentally Persistent Free Radicals on Microplastics under Light Irradiation.

Microplastics (MPs) are presumed to be inert during aging under ambient conditions. In this study, four types of virgin MPs, including polystyrene (PS), phenol-formaldehyde resin (PF), polyethylene (PE), and polyvinyl chloride (PVC), were aged under simulated solar light irradiation. Surprisingly, several environmentally persistent free radicals (EPFRs), which are considered to be a type of emerging contaminant, were detected on the irradiated PS and PF, rather than PE and PVC, by electron paramagnetic resonance (EPR) spectroscopy. Depending on the photoaging duration time, the characteristic g-factors of the EPFRs produced on PS and PF were 2.0044-2.0049 and 2.0043-2.0044, respectively. The generated EPFRs on PS and PF decayed rapidly at the initial stage and then slowly disappeared with the elapsed aging time. Analyses by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) suggested that MPs might experience chemical chain scission, O2/H2O addition, and EPFR formation under the light irradiation. Accompanying with the formation of EPFRs, reactive oxygen species, such as O2•- and •OH, were also observed. The findings provide a novel insight to evaluate the potential hazards of MPs to organisms and ecosystems.

Non-thermal plasma oxidation of Cu(II)-EDTA and simultaneous Cu(II) elimination by chemical precipitation.

Cu2+ readily complexes with ethylenediaminetetraacetic acid (EDTA) to form a heavy metal complex (Cu-EDTA) that is typical in the effluents from mining and electroplating industries. It was difficult for the classical alkaline precipitation method to eliminate the heavy metal complex due to the strong bonding ability between Cu(II) and EDTA. Cu(II) release and removal performance after Cu-EDTA decomplexation in a non-thermal plasma oxidation system was carried out in this study. The removal process was characterized by chemical oxygen demand, total organic carbon, atomic force microscopy, and electroconductivity analysis. The toxicity effect of the treated Cu-EDTA solution was also tested by photobacterium bioassay. The experimental results showed that 80.2% of Cu was released and removed within 60 min of the non-thermal plasma treatment/alkaline precipitation. Relatively higher energy input, lower Cu-EDTA concentration, and acidic conditions were necessary to obtain greater Cu release and removal performance, and there existed an appropriate air flow rate for high-efficient Cu release and removal. O2-, OH, 1O2, and O3 were the main active substances leading to Cu2+ release. Its residual toxicity to P.phosphoreum sp.-T3 was significantly reduced after treatment.

Novel Cu(II)-EDTA Decomplexation by Discharge Plasma Oxidation and Coupled Cu Removal by Alkaline Precipitation: Underneath Mechanisms.

Strong complexation between heavy metals and organic complexing agents makes the heavy metals difficult to be removed by classical chemical precipitation. In this study, a novel decomplexation method was developed using discharge plasma oxidation, which was followed by alkaline precipitation to treat water containing heavy metal-organic complex, that is, Cu-ethylenediaminetetraacetic acid (Cu-EDTA). The decomplexation efficiency of Cu complex reached up to nearly 100% after 60 min's oxidation by discharge plasma, which was accompanied by 82.1% of total organic carbon removal and energy efficiency of 0.62 g kWh-1. Presence of free Cu2+ favored Cu-EDTA decomplexation, whereas the presence of excessive EDTA depressed this process. Cu-EDTA decomplexation was mainly driven by the produced 1O2, O2•-, O3, and •OH by discharge plasma. Cu-EDTA decomplexation process was characterized by UV-vis, ATR-FTIR, total organic carbon, and three-dimensional fluorescence diagnosis. The main intermediates including Cu-EDDA, Cu-IDA, Cu-NTA, small organic acids, NH4+, and NO3- were identified, accompanied by Cu2+ releasing. The followed precipitation process removed 78.1% of Cu2+, and Cu-associated precipitates included CuCO3, Cu2CO3(OH)2, CuO, and Cu(OH)2. A possible pathway of Cu complex decomplexation and Cu2+ removal in such a system was proposed.

Maize straw decorated with sulfide for tylosin removal from the water.

MS-ZnS and MS-ZnS:Mn complexes were synthesized via a simple method. The results showed that sulfide was successfully loaded on the maize straw. The results of fitting the experimental data showed that the sorption conforms to the pseudo-second-order kinetics, and the TYL sorption on MS fit the Henry model well, but the Freundlich model was more suited to MS-ZnS and MS-ZnS:Mn. In addition, the kf values of MS-ZnS (206.0(mg/kg)/(mg/L)n) and MS-ZnS:Mn (382.5(mg/kg)/(mg/L)n) were significantly greater than that of MS (72.2(mg/kg)/(mg/L)n), indicating that ZnS and ZnS:Mn could improve the sorption capacity of TYL on MS. The pH, ionic strength and temperature influence the sorption process, and the sorption ability of TYL on MS-ZnS and MS-ZnS:Mn showed little change when the solution pH was > 5; the amount of TYL sorption on the adsorbents gradually decreased with the increasing concentration of KNO3. Electrostatic interactions, H bonding and hydrophobic interactions are involved in the sorption of TYL on MS, MS-ZnS and MS-ZnS:Mn, and compared with MS, the main mechanism is surface complexation. This research can provide technical support for the utilization of biomass and the restoration of water polluted by antibiotics.

Key Processes of Silicon-On-Glass MEMS Fabrication Technology for Gyroscope Application.

MEMS fabrication that is based on the silicon-on-glass (SOG) process requires many steps, including patterning, anodic bonding, deep reactive ion etching (DRIE), and chemical mechanical polishing (CMP). The effects of the process parameters of CMP and DRIE are investigated in this study. The process parameters of CMP, such as abrasive size, load pressure, and pH value of SF1 solution are examined to optimize the total thickness variation in the structure and the surface quality. The ratio of etching and passivation cycle time and the process pressure are also adjusted to achieve satisfactory performance during DRIE. The process is optimized to avoid neither the notching nor lag effects on the fabricated silicon structures. For demonstrating the capability of the modified CMP and DRIE processes, a z-axis micro gyroscope is fabricated that is based on the SOG process. Initial test results show that the average surface roughness of silicon is below 1.13 nm and the thickness of the silicon is measured to be 50 µm. All of the structures are well defined without the footing effect by the use of the modified DRIE process. The initial performance test results of the resonant frequency for the drive and sense modes are 4.048 and 4.076 kHz, respectively. The demands for this kind of SOG MEMS device can be fulfilled using the optimized process.

Rates and equilibria of perfluorooctanoate (PFOA) sorption on soils from different regions of China.

Understanding sorption of PFOA on soil particles is crucial to evaluate its environmental risk. Here, sorption of PFOA onto ten agricultural soils was examined. The influence of soil physico-chemical properties on PFOA sorption was investigated. The sorption rate of PFOA followed a pseudo-second-order kinetics. Isotherm data of PFOA sorption was fitted with both Freundlich and linear models and the latter fitted better. The sorption-desorption of PFOA onto ten soil samples depended on soil organic carbon content and composition of soil minerals. The sorption and desorption isotherms of PFOA on ten soils were linear, except for the sorption of PFOA onto a few soils, which was described by the Freundlich equation with the parameter N >1. The main sorption mechanism of PFOA was hydrophobic interaction between the perfluorinated carbon chain and the organic matter of soil, as evidenced by the correlation between the solid-liquid distribution coefficient and the fraction of soil organic carbon. The sorption of PFOA in soils was highly irreversible.

Safety evaluation of chemically modified beta-lactoglobulin administered intravaginally.

Currently, there is no specific antiviral therapy for treatment of HPV infection. Jiang and colleagues previously reported that anhydride-modified proteins have inhibitory activities against multiple viruses including HPV. Here, we evaluated the safety of 3-hydroxyphthalic anhydride-modified bovine beta-lactoglobulin, designated JB01, vaginally applied in women infected by high-risk HPV. After the vaginal application of JB01 in 38 women for 3 months, no serious adverse events were reported, and normalization of the vaginal micro-environment has been observed. It can be concluded that JB01-BD is safe for vaginal use in HPV-infected women, suggesting its potential application for the treatment of HPV infection.

Sorption of tylosin and sulfamethazine on solid humic acid.

Tylosin (TYL) and sulfamethazine (SMT) are ionizable and polar antimicrobial compounds, which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SMT onto humic acid (HA) may affect their environmental fate. In this study, the sorption of TYL and SMT on HA at different conditions (pH, ionic strength) was investigated. All sorption isotherms fitted well to the Henry and Freundlich models and they were highly nonlinear with values of n between 0.5 and 0.8, which suggested that the HA had high heterogeneity. The sorption of TYL and SMT on HA decreased with increasing pH (2.0-7.5), implying that the primary sorption mechanism could be due to cation exchange interactions between TYL(+)/SMT(+) species and the functional groups of HA. Increasing ionic strength resulted in a considerable reduction in the Kd values of TYL and SMT, hinting that interactions between H bonds and π-π EDA might be an important factor in the sorption of TYL and SMT on HA. Results of Fourier transform infrared (FT-IR) and (13)C-nuclear magnetic resonance (NMR) analysis further demonstrated that carboxyl groups and O-alkyl structures in the HA could interact with TYL and SMT via ionic interactions and H bonds, respectively. Overall, this work gives new insights into the mechanisms of sorption of TYL and SMT on HA and hence aids us in assessing the environmental risk of TYL and SMT under diverse conditions.