Fate Of Pollutants Research Articles

Accelerated Indirect Photodegradation of Organic Pollutants at the Soil-Water Interface.

Indirect photolysis driven by photochemically produced reactive intermediates (PPRIs) is pivotal for the transformations and fates of pollutants in nature. While well-studied in bulk water, indirect photolysis processes at environmental interfaces remain largely unexplored. This study reveals a significant acceleration of indirect photodegradation of organic pollutants at the soil-water interface of wetlands. Organic pollutants experienced ubiquitously enhanced indirect photodegradation at the soil-water interfaces, with rates 1.41 ± 0.01 to 4.27 ± 0.03-fold higher than those in bulk water. This enhancement was observed across various natural and artificial wetlands, including coastal wetlands and rice paddies. In situ mapping indicated that soil-water interfaces act as hotspots, concentrating both organic pollutants and PPRIs by 9.30- and 4.27-folds, respectively. This synchronized colocation is the primary cause of the accelerated pollutant photolysis. Additionally, the contribution of each PPRI species to pollutant photolysis and a coupled transformation pathway at the soil-water interface significantly differed from those in bulk water. For instance, the contribution of singlet oxygen to metoxuron photolysis increased from 10.1% in bulk water to 44.4% at the soil-water interface. Our study highlights the rapid indirect photolysis of organic pollutants at the soil-water interfaces, offering new insights into the natural purification processes in wetlands as "Earth's kidneys."

Biosurfactant-mediated transport of tetracycline antibiotics in saturated porous media: Combined effects of the chemical properties of contaminants and solution chemistry conditions

The mobility of tetracycline antibiotics (TCs) in saturated aquifers is possibly affected by the presence of biosurfactants, which are widespread in the aquatic/soil environments. This study investigated the mobility characteristics of various tetracyclines—specifically tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC)—within quartz sand columns in the presence of rhamnolipid, a common biosurfactant. Exogenous rhamnolipid significantly inhibited the transport of the three TCs over the pH range of 5.0–9.0 (e.g., the mass of retained TC, OTC, and CTC increased from 32.6 %, 26.9 %, and 39.2 % (in the absence rhamnolipid) to 39.4 %, 38.9 %, and 51.7 % (in the presence of rhamnolipid), respectively). This observation could be attributed to the bridging effects of this biosurfactant. Specifically, the hydrophilic head of rhamnolipid molecules is likely associated with the surfaces of sand grains through surface complexation and/or hydrogen bonding interactions. Accordingly, the hydrophobic moieties of the deposited rhamnolipid molecules (i.e., the aliphatic chains) interact with the hydrophobic groups of TCs molecules via hydrophobic interactions. Interestingly, the extent of the inhibitory effect on CTC mobility was greater than that on OTC and TC, which was related to the different hydrophobic characteristics of the three antibiotics. Furthermore, the inhibitory effect of rhamnolipid on the transport of TCs diminished as the pH of the background solution increased. This observation was attributed to the weakened bridging effects, resulting from the reduced deposition of the biosurfactant on the sand surfaces. Additionally, the cation-bridging mechanism involved in the retention of TCs in the addition of rhamnolipid when the background electrolyte was Ca2+ (i.e., Ca2+ ions served as bridging agents between the deposited rhamnolipid molecules and TCs). The insightful findings enhance our understanding of the critical roles of biosurfactants in influencing the environmental dynamics and ultimate fate of conventional antibiotic pollutants within groundwater systems.

Photochemical Transformation of Ibuprofen and Chlorophene Induced by Dissolved Organic Matter.

Both ibuprofen (IBP) and chlorophene (CP) are frequently detected contaminants in surface aqueous environment. Dissolved organic matter (DOM) is an important component in water with high photo-reactivity, playing an important role in the transformation processes of various organic pollutants. This study systematically studied the influence of DOM on the photochemical transformation of IBP and CP by using humic acid as model DOM. In addition, the effect of inorganic salts on this process is also considered due to the high salt content in the ocean. Further quenching experiments and reactive oxygen species (ROSs) detection were also conducted to explore the reactive species acting on the IBP and CP transformation. Based on the products analysis and theoretical calculation, we proposed the IBP and CP transformation mechanism. Overall, this study provides some new insights into the transformation of organic pollutants in natural surface water, which is significant for assessing the fate of pollutants.

Interactions between microplastics and organic contaminants: the microbial mechanisms for priming effects of organic compounds on microplastic biodegradation

The co-presence of plastics and other organic contaminants is pervasive in various ecosystems, particularly in areas with intensive anthropogenic activities. Their interactions inevitably impact the composition and functions of the plastisphere microbiome, which in turn determines the trajectory of these contaminants. Antibiotics are a group of organic contaminants that warrant particular attention due to their wide presence in environments and significant potential to disseminate antibiotic resistance genes (ARGs) within the plastisphere. Therefore, this study investigated the impacts of sulfadiazine (SDZ), a prevalent environmental antibiotic, on the composition and function of the plastisphere microbial community inhabiting micro-polyethylene (mPE), one of the most common microplastic contaminants. Our findings indicated that the presence of SDZ increased the overall plastisphere microbial abundance and enriched populations that are capable of degrading both SDZ and mPE. The abundance of Aquabacterium, a dominant plastisphere population that is capable of degrading both SDZ and mPE, increased over the course of SDZ exposure, while another abundant mPE-degrading population, Ketobacter, remained stable. Accordingly, the removal of SDZ was enhanced in the presence of mPE. Moreover, the results further revealed that not only SDZ but also other labile organic contaminants (e.g., aniline and hexane) could accelerate mPE biodegradation through a priming effect. This investigation underscores the complex dynamics among microplastics, organic contaminants, and the plastisphere microbiome, offering insights into the environmental fate of plastic and antibiotic pollutants.

Precipitation patterns strongly affect vertical migration and methylation of mercury in legacy contaminated sites

Legacy-contaminated sites act as significant sources of mercury (Hg) to their surrounding surface and underground environments. Intensified extreme precipitation is posing great threats to the environment and human health by changing the fate of pollutants, yet little is known about its effect on the vertical migration and methylation of Hg in contaminated sites. Here, we applied a range of simulated extreme precipitation patterns (frequency and intensity) to column leaching assays with soils collected near a contaminated site. We observed that precipitation with high frequency but low intensity resulted in more vertical migration of Hg through the soil profile than that with low frequency but high intensity. The majority (> 90%) of leached Hg was prone to migrate vertically within the top 10 cm of the soil profile. Furthermore, rainfall stimulated microbial Hg methylation, as demonstrated by enhanced production of methylmercury (MeHg) in both simulated and field-contaminated soils. We identified specific microbial taxa including Geobacteraceae, Desulfuromonadaceae, Syntrophaceae, Oscillospiraceae, and Methanomicrobiaceae as key predictors of MeHg production, which differed from those typically observed in overlying water of croplands. Particularly, the relative abundance of these dominant Hg methylators significantly increased during rainfall-induced leaching compared to that of the control, suggesting the crucial yet previously overlooked impacts of increased precipitation events on the process of microbial Hg methylation in industry-contaminated sites. Given the rising incidences of extreme precipitation events worldwide due to climate change, this study highlights the significance of assessing Hg mobility and microbial transformation in legacy contaminated sites.

The Influence of Pyrolysis Temperature and Feedstocks on the Characteristics of Biochar-Derived Dissolved Organic Matter: A Systematic Assessment

Biochar is a carbon-rich product obtained by pyrolyzing biomass under oxygen-limited conditions and has a wide range of potential for environmental applications. In particular, dissolved organic matter (DOM) released from biochar has an important impact on the fate of pollutants. The study aimed to systematically assess how varying pyrolysis temperatures and biomass feedstocks influence the characteristics of biochar-derived DOM. DOM samples were comprehensively characterized utilizing UV-vis spectroscopy and excitation–emission matrix (EEM) fluorescence spectroscopy, coupled with parallel factor (PARAFAC) analysis. The study discovered that pyrolysis temperature significantly affects DOM characteristics more than feedstock type. An increase in pyrolysis temperature correlated with a notable decrease in dissolved organic carbon content, aromaticity, and fluorescence intensity, alongside a marked increase in pH and hydrophilicity. PARAFAC analysis identified three distinct DOM components: two humic-like substances (C1 and C2) and one protein-like substance (C3). The proportion of protein-like substances increased with higher pyrolysis temperatures, while the humic-like substances’ proportion declined. The compositional shifts in DOM with pyrolysis temperature may significantly influence its environmental behavior and functionality. Further research is necessary to explore the long-term environmental impact and potential applications of biochar-derived DOM.

A Critical Review of the Crucial Role of the Yellow River's Sediment in the Interfacial Migration and Fate of Pollutants and Prospects for the Application of Environmental Sediment Restoration.

Considering the increasing sediment content and increasing sediment flux of the Yellow River over the years, it is of significance to investigate the potential interfacial force mechanism between pollutants and Yellow River sediment. This article has reviewed the current research on the Yellow River sediments' mineral structures while investigating the potential interaction force between sediment and pollutants in the water environment. This article has conducted a comprehensive analysis of the influence of sediment on the migration of pollutants in the water environment. What is more, the authors have provided an outlook on the future applications of sediment in ecological environmental systems. Yellow River sediment mainly included minerals and some clay phases, while its irregular surface provided sites for the interface adsorption of pollutants. The interface force between the sediment and pollutants is mainly attributed to promoting bacterial growth on the surface of sediments, physisorption, and chemisorption forces. The sediments carry and transport pollutants during the long-distance water flow migration process. The sediment should be effectively utilized and better integrated into ecological or environmental restoration systems. This article provides a reference for studying the behavior of Yellow River sediment and the direction of future efficient utilization.

Influences of wildfire on the soil dissolved organic matter characteristics and its electron-donating capacity

Global increases in the intensity and frequency of wildfires are driving major changes in soil organic matter (SOM) characteristics, including soil dissolved organic matter (DOM). As the most crucial component of SOM, soil DOM plays a pivotal role in the carbon cycle and regulates the environmental fate of contaminants through its versatile reactivities, including electron-donating capacity (EDC). However, it is still being determined how wildfire influences key characteristics of soil DOM and subsequent effects on EDC in forest soils. Thus, we conducted our study to fill this gap with the forest soils of Jinyun Mountain Nature Reserve of China, which experienced an unprecedented wildfire event in 2022. The results from optical characterization, high-performance size-exclusion chromatography (HPSEC), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) showed decreasing molecular weight but elevating nitrogen-containing molecular formulas of soil DOM in the burned soils. This could be attributed to the Maillard reaction and microbial re-colonies. Additionally, wildfires increased the condensed aromatics and lignin components in soil DOM. In the burned soils, we observed increasing EDC of soil DOM, which accounts for an increase in lignin-derived phenolic components. Overall, the findings of this study demonstrate that eco-disturbances, such as wildfires, induce alterations in the properties of DOM, leading to variations in its reactivity and potentially influencing the fate of environmental pollutants beyond carbon dynamics alone. Thus, incorporating the dynamic properties of soil DOM, particularly in the context of climate change, can enhance the assessment of risks associated with contaminants in soil and water, providing valuable insights.

A review of ion scattering spectroscopy studies at liquid interfaces with noble gas ion projectiles

Ion scattering spectroscopy (ISS) is an analytical tool that provides direct structural, topographical, and atomic compositional information at interfaces when ions are used as projectiles. Since its development in 1967, ISS is commonly used to obtain quantitative information about solid interfaces. Over the last couple of decades, ISS has emerged as an important technique to probe liquid interfaces and their studies employing ISS has become not uncommon, more so with Neutral impact collision ion scattering spectroscopy (NICISS). Therefore, here the principle of ISS with a particular focus on NICISS and its data evaluation are summarised while reviewing some important studies at vapor-liquid interfaces that provide direct information for molecular orientation of liquids (including ionic liquids), composition and distribution of atoms (or solutes) and charges as a function of depth to gain vast variety of thermodynamical information. Employing ISS such information can be achieved with high depth resolution of ∼1–2 Å (depending on the nature of the experiment). These examples highlight the significance of ISS and show potential for its application for studies related to specific ion effects, atmospheric reaction in aerosol and sea water droplets, and even determining the fate of environmental pollutants like heavy metal ions and per-fluoroalkyl substances (PFAS). Furthermore, some limitations of ISS are also discussed relating to investigation of high-vapor pressure liquids and probing buried interfaces like liquid-liquid interfaces while presenting progresses made in probing solid-liquid interfaces.

Adsorption behavior and mechanism of different types of (aged) microplastics for napropamide in soils

The role of microplastics (MPs) as pollutant carriers and their influence on the fate of organic pollutants has received considerable attention. However, the impacts of MPs on the adsorption of amide herbicides in soil, have not been investigated. In this study, non-biodegradable (polyethylene, PEM) and biodegradable (polybutylene adipate terephthalate, PBATM) MPs were aged by exposure to one month of ultraviolet irradiation. The impacts of MPs on the adsorption of napropamide (Nap) in two agricultural soils (black soil [BS] and fluvo-aquic soil [CS]) were investigated through batch experiments. The findings suggested that the adsorption of Nap onto PEM was mainly governed by physical processes, while, chemical mechanisms, should not be overlooked on PBATM. With the addition of 0.2% MPs, the maximum adsorption capacity (Qm) and adsorption distribution coefficient (KF) of soil containing PEM (soil-PEM) were higher than that of soil-PBATM, however, the Qm and KF values of soil-PBATM for Nap were higher when the addition of MPs was 2%. After UV aging, the increased specific surface area of MPs led to an increased adhesion of soil particles. These were attributed to the different surface properties and concentrations of different (aged) MPs, resulting in differences in the inhibition effect by soil particles. The adhesion of soil particles was confirmed by X-ray photoelectron spectroscopy. Additionally, regardless of the addition of MPs, the Qm values of BS for Nap were higher than those for CS. In summary, MPs can alter the adsorption of Nap in soil, influencing both its mobility within the soil ecosystem and the environmental risk.

Eutrophication Levels of Hydropower Plant Water Reservoirs Via Trophic State Index With Evaluation of the Fate of Pollutants Affected By the Land Use Model

Eutrophication Levels of Hydropower Plant Water Reservoirs Via Trophic State Index With Evaluation of the Fate of Pollutants Affected By the Land Use Model

The fate of hazardous textile pollutants in an upcycling process for post-consumer garments

The environmental impact is a strong incentive for the development of upcycling processes for textile waste. However, toxic chemicals may occur in both brand-new textiles and post-consumer garments, and the chemical transfer in such routes is important to investigate. The present study applied non-target screening and quantification with liquid chromatography/mass spectrometry to follow the fate of hazardous chemicals from post-consumer polycotton garments to a new material, cellulose nanocrystals, in a chemical upcycling utilizing strongly acidic conditions. The majority of hazardous chemicals detected within the process were found to be transferred to a residual of polyester material and not to the enriched cellulose. However, phthalates were found to be mainly attached to the cellulose nanocrystals. The detected total concentration, in this case, was below 5 μg/g, at least 200 times lower than the limit set by the European Union. This indicates the importance of monitoring and controlling the phthalate content in the starting material of the process, i.e., the post-consumer garments. The chemical release into the process waste effluent could be estimated based on water solubility data for chemicals under the applied conditions. Three compounds, the water-repellent substance perfluorooctanesulfonic acid and the dyes Crystal Violet and Victoria Pure Blue, were almost entirely transferred into the process waste effluent. Although the levels detected were very low in the present pilot process, their presence eventually indicates the need for wastewater purification at further upscaling, depending on the exposure and dose in relation to toxicological relevant thresholds.

Participation of strong charge-assisted hydrogen bonds in interactions of dissolved organic matter represented by Suwannee River Humic Acid

Terrestrial dissolved organic matter (DOM) plays critical roles in many biotic and abiotic environmental reactions as well as in water treatment. Its structure is therefore of great interest. We examined dissolved Suwannee River Humic Acid (HA) to probe the potential participation of exceptionally strong, negative charge-assisted hydrogen bonds, (−)CAHB, in DOM cohesion and interaction with small weak acids using high performance size exclusion chromatography (HPSEC), transmission electron microscopy, zeta-pH curves, and pH drift experiments. The results support a previously proposed two-tier state of aggregation, in which tightly-knit primary particles (≤ ∼10 kDa) form larger secondary aggregates (up to micrometer in size). Evidence for (−)CAHB is gained through zeta potential changes and pH drift experiments. The primary particles interact with (−)CAHB-capable solutes (simple carboxylic acids and phosphate) but not (−)CAHB-incapable solutes. We identified disruption of intra-segmental and inter-molecular (−)CAHB leading to swelling and disaggregation, as well as formation of nouveau (−)CAHB with free groups on HA. The effects were solute-concentration dependent and greater at pH 5 than pH 6, consistent with CAHB theory. Phosphate induced the greatest shifts in the HPSEC molecular size distribution curves. The shifts were unaffected by prior stripping of innate polyvalent metals. We conclude that the (−)CAHB contributes to the cohesion of DOM, affecting its size and charge, and provides a means by which weak acid pollutants, nutrients, and natural compounds can interact with DOM. Such interactions have implications for the behavior of DOM in the environment, the fate and transport of anthropogenic pollutants, and the roles DOM play in water treatment technologies.

Skyrocketing pollution: assessing the environmental fate of July 4th fireworks in New York City.

Pyrotechnic displays often lead to significant increases in poor air quality. The widespread environmental fate-involving air, water, and spatial-temporal analyses-of fireworks-produced pollutants has seldom been investigated. This study examined the environmental fate of pollutants from the largest fireworks event in the U.S.: Macy's Fourth of July Fireworks show in New York City (NYC). Real-time PM2.5 and gravimetric PM2.5 and PM10 were collected at locations along the East River of NYC. Airborne particles were assayed for trace elements (X-ray fluorescence) and organic and elemental carbon (OC/EC). River water samples were evaluated by ICP-MS for heavy-metal water contamination. Spatial-temporal analyses were created using PM2.5 concentrations reported by both EPA and PurpleAir monitoring networks for NYC and 5 other major metropolitan areas. The fireworks event resulted in large increases in PM2.5 mass concentrations at the river-adjacent sampling locations. While background control PM2.5 was 10-15 µg/m3, peak real-time PM2.5 levels exceeded 3000 µg/m3 at one site and 1000 µg/m3 at two other locations. The integrated gravimetric PM2.5 and PM10 concentrations during the fireworks event ranged from 162 to 240 µg/m3 and 252 to 589 µg/m3, respectively. Zn, Pb, Sb, and Cu more than doubled in river water samples taken after the event, while S, K, Ba, Cu, Mg, Fe, Sr, Ti, and Zn increased in airborne PM2.5 from the fireworks. Data from hyperlocal monitoring networks for NYC and other metropolitan areas yielded similar, but generally smaller, increases in PM2.5 levels. Fireworks shows have been associated with environmental contamination. This comprehensive analysis considers the fate of pollutants from the largest annual U.S. pyrotechnic show through air, water, and hyperlocal temporal characterization.

Correlative Effects on Nanoplastic Aggregation in Model Extracellular Biofilm Substances Investigated with Fluorescence Correlation Spectroscopy.

Recent studies show that biofilm substances in contact with nanoplastics play an important role in the aggregation and sedimentation of nanoplastics. Consequences of these processes are changes in biofilm formation and stability and changes in the transport and fate of pollutants in the environment. Having a deeper understanding of the nanoplastics-biofilm interaction would help to evaluate the risks posed by uncontrolled nanoplastic pollution. These interactions are impacted by environmental changes due to climate change, such as, e.g., the acidification of surface waters. We apply fluorescence correlation spectroscopy (FCS) to investigate the pH-dependent aggregation tendency of non-functionalized polystyrene (PS) nanoparticles (NPs) due to intermolecular forces with model extracellular biofilm substances. Our biofilm model consists of bovine serum albumin (BSA), which serves as a representative for globular proteins, and the polysaccharide alginate, which is a main component in many biofilms, in solutions containing Na+ with an ionic strength being realistic for fresh-water conditions. Biomolecule concentrations ranging from 0.5 g/L up to at maximum 21 g/L are considered. We use non-functionalized PS NPs as representative for mostly negatively charged nanoplastics. BSA promotes NP aggregation through adsorption onto the NPs and BSA-mediated bridging. In BSA-alginate mixtures, the alginate hampers this interaction, most likely due to alginate-BSA complex formation. In most BSA-alginate mixtures as in alginate alone, NP aggregation is predominantly driven by weaker, pH-independent depletion forces. The stabilizing effect of alginate is only weakened at high BSA contents, when the electrostatic BSA-BSA attraction is not sufficiently screened by the alginate. This study clearly shows that it is crucial to consider correlative effects between multiple biofilm components to better understand the NP aggregation in the presence of complex biofilm substances. Single-component biofilm model systems based on comparing the total organic carbon (TOC) content of the extracellular biofilm substances, as usually considered, would have led to a misjudgment of the stability towards aggregation.

Drivers of change behind the spatial distribution and fate of typical trace organic pollutants in fresh waste leachate across China

There have been growing concerns regarding the health and environmental impacts of trace organic pollutants (TOPs). However, fresh leachate from municipal solid waste (MSW) has been overlooked as a potential reservoir of TOPs. Therefore, we investigated 90 legacy and emerging TOPs in fresh leachate from 14 provinces and municipalities in China. Additionally, the fate and final discharge impacts of TOPs in 14 leachate treatment systems were analyzed. The results revealed that the detection rate of 90 TOPs was over 50 % in all samples. Notably, polychlorinated biphenyls, banned for 40 years, were frequently detected in fresh leachate. The concentration of pseudo-persistent TOPs (105–107 ng/L) is significantly higher than that of persistent TOPs (102–104 ng/L). Spatial distribution patterns of TOPs in fresh leachate suggest that economy, population, climate, and policies impact TOPs discharge from MSW. For example, economically developed and densely populated areas displayed higher TOPs concentrations, whereas warmer climates facilitate TOPs leaching from MSW. We confirmed that waste classification policies were a key driver of the decline in multiple TOPs in leachate. Mass balance analysis shows that the final effluent and sludge from current dominant leachate treatment systems contain refractory TOPs, especially perfluoroalkyl acids, which must be prioritized for control. This paper was the first comprehensive investigation of multiple TOPs in fresh leachate at a large geographic scale. The factors affecting the occurrence, spatial distribution, and fate of TOPs in fresh leachate were revealed. It provides a valuable reference for the establishment of policies for the management of TOPs in MSW and the associated leachate.

Molecular response to the influences of Cu(II) and Fe(III) on forming biogenic manganese oxides by Pseudomonas putida MnB1

The biogeochemical cycle of biogenic manganese oxides (BioMnOx) is closely associated with the environmental behavior and fate of various pollutants. It is significantly interfered by many metals, such as Cu and Fe. However, the bacterial molecular responses are not clear. Here, the effects of Cu(II) and Fe(III) on oxidation of manganese by Pseudomonas putida MnB1 and the bacterial molecular response mechanisms have been studied. The bacterial oxidation of manganese were promoted by both Fe(III) and Cu(II) and the final manganese oxidation rate of the Cu(II) group exceeded 16 % that of the Fe(III) group. The results of transcriptome indicated that Cu(II) promoted manganese oxidation by up-regulating the expression levels of multicopper oxidase (MCO) and peroxidase(POD), and by stimulating electron transfer, while Fe(III) promoted this process by accelerating the electron transfer and nitrogen cycling, and activating POD. The protein-protein interaction (PPI) network indicated that the MCO genes (mnxG and mcoA) were directly linked to the copper homeostasis proteins (cusA, cusB, czcC and cusF). Cytochrome c was closely related to the genes related to nitrogen cycling (glnA, glnL, and putA) and electrons transfer (cycO, cycD, nuoA, nuoK, and nuoL), which also promoted manganese oxidation. This study provides a molecular level insight into the oxidation of Mn(II) by Pseudomonas putida MnB1 with Cu(II) and/or Fe(III) ions.

Critical roles of low-molecular-weight organic acid in enhancing hydroxyl radical production by ferrous oxidation on γ-Al2O3 mineral surface

Recognizing the pervasive presence of alumina minerals and low-molecular-weight organic acids (LMWOAs) in the environment, this study addressed the gap in the interaction mechanisms within the ternary system involving these two components and Fe(II). Specifically, the impacts of LMWOAs on hydroxyl radicals (•OH) production and iron species transformation during Fe(II) oxidation on γ-Al2O3 mineral surface were examined. Results demonstrated that adding 0.5 mM oxalate (OA) or citrate (CA) to the γ-Al2O3/Fe(II) system (28.1 μM) significantly enhanced •OH production by 1.9-fold (51.9 μM) and 1.3-fold (36.2 μM), respectively, whereas succinate (SA) exhibited limited effect (30.7 μM). Raising OA concentration to 5 mM further promoted •OH yield to 125.0 μM after 24 h. Deeper analysis revealed that CA facilitated the dissolution of adsorbed Fe(II) and its subsequent oxygenation by O2 through both one- and two-electron transfer mechanisms, whereas OA enhanced the adsorption of dissolved Fe(II) and more efficient two-electron transfer for H2O2 production. Additionally, LMWOAs presence favored the formation of iron minerals with poor crystallinity like ferrihydrite and lepidocrocite rather than well-crystallized forms such as goethite. The distinct impacts of various LMWOAs on Fe(II) oxidation and •OH generation underscore their unique roles in the redox processes at mineral surface, consequently modulating the environmental fate of prototypical pollutants like phenol.

Comparison of rhodamine B adsorption and desorption on the aged non-degradable and degradable microplastics: Effects of charge-assisted hydrogen bond and underline mechanism

The accumulation of microplastics (MPs) in the environment and their role as carriers for ionic organic pollutants are increasingly attracting attention. This study evaluated the adsorption-desorption characteristics of the cationic organic pollutant on virgin and UV-aged non-degradable polystyrene (PS) as well as degradable poly(butylene succinate) (PBS) and poly(butylene adipate-co-terephthalate) (PBAT) MPs. The results showed that aging treatment made the surface of MPs rougher and more porous, causing the adsorption to shift from monolayer to multilayer adsorption. Aging increased the oxygen-containing groups on MPs, significantly enhancing the H bond (HB) donor capabilities of degradable aged PBS and PBAT, thereby improving adsorption by more than 10 times. This significant increase in adsorption is mainly due to the combined effects of strong HB (including ordinary HB (OHB) and charge-assisted HB (CAHB)), electrostatic interactions, and π-π interactions. Notably, the stronger HB enabled aged PBS and PBAT to achieve efficient and stable adsorption of rhodamine B over a wide pH range, with significant desorption hysteresis (HI > 1.80). This indicates that degradable aged MPs can act as carriers for long-distance pollutant transport. The significant total desorption of cationic pollutants from aged PBS and PBAT in simulated animal gastrointestinal fluids confirmed the greater environmental hazards of degradable aged MPs. This work is the first to demonstrate that degradable aged MPs, as unique HB donors, can primarily adsorb ionic organic pollutants through strong HB (CAHB and OHB), which helps assess the environmental fate of biodegradable microplastics and pollutants in aquatic systems.

Unveiling the Mechanism and Kinetics of Pollutant Attenuation by Free Radicals Triggered from Goethite in Water Distribution Systems.

Investigating the fate of persistent organic pollutants in water distribution systems (WDSs) is of great significance for preventing human health risks. The role of iron corrosion scales in the migration and transformation of organics in such systems remains unclear. Herein, we determined that hydroxyl (•OH), chlorine, and chlorine oxide radicals are generated by Fenton-like reactions due to the coexistence of oxygen vacancy-related Fe(II) on goethite (a major constituent of iron corrosion scales) and hypochlorous acid (HClO, the main reactive chlorine species of residual chlorine at pH ∼ 7.0). •OH contributed mostly to the decomposition of atrazine (ATZ, model compound) more than other radicals, producing a series of relatively low-toxicity small molecular intermediates. A simplified kinetic model consisting of mass transfer of ATZ and HClO, •OH generation, and ATZ oxidation by •OH on the goethite surface was developed to simulate iron corrosion scale-triggered residual chlorine oxidation of organic compounds in a WDS. The model was validated by comparing the fitting results to the experimental data. Moreover, the model was comprehensively applicable to cases in which various inorganic ions (Ca2+, Na+, HCO3-, and SO42-) and natural organic matter were present. With further optimization, the model may be employed to predict the migration and accumulation of persistent organic pollutants under real environmental conditions in the WDSs.