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.

Incessant release of a large spectrum of agro-industrial pollutants into environmental matrices remains a serious concern due to their potential health risks to humans and aquatic animals. Existing remediation techniques are unable to remove these pollutants, necessitating the development of novel treatment approaches. Due to its unique structure, physicochemical properties, and broad application potential, graphene has attracted a lot of attention as a new type of two-dimensional nanostructure. Given its chemical stability, large surface area, electron mobility, superior thermal conductivity, and two-dimensional structure, tremendous research has been conducted on graphene and its derived composites for environmental remediation and pollution mitigation. Various methods for graphene functionalization have facilitated the development of different graphene derivatives such as graphene oxide (GO), functional reduced graphene oxide (frGO), and reduced graphene oxide (rGO) with novel attributes for multiple applications. This review provides a comprehensive read on the recent progress of multifunctional graphene-based nanocomposites and nanohybrids as a promising way of removing emerging contaminants from aqueous environments. First, a succinct overview of the fundamental structure, fabrication techniques, and features of graphene-based composites is presented. Following that, graphene and GO functionalization, i.e., covalent bonding, non-covalent, and elemental doping, are discussed. Finally, the environmental potentials of a plethora of graphene-based hybrid nanocomposites for the abatement of organic and inorganic contaminants are thoroughly covered.

Salt marsh estuaries serve as sources and sinks for nutrients and elements to and from estuarine water, which enhances and alleviates watershed fluxes to the coastal ocean. We assessed sources and sinks of mercury in the intertidal Plum Island Sound estuary in Massachusetts, the largest salt marsh estuary of New England, using 25-km spatial water sampling transects. Across all seasons, dissolved (FHg) and total (THg) mercury concentrations in estuarine water were highest and strongly enhanced in upper marshes (1.31 ± 0.20 ng L⁻¹ and 6.56 ± 3.70 ng L⁻¹, respectively), compared to riverine Hg concentrations (0.86 ± 0.17 ng L⁻¹ and 0.88 ± 0.34 ng L⁻¹, respectively). Mercury concentrations declined from upper to lower marshes and were lowest in ocean water (0.38 ± 0.10 ng L⁻¹ and 0.56 ± 0.25 ng L⁻¹, respectively). Conservative mixing models using river and ocean water as endmembers indicated that internal estuarine Hg sources strongly enhanced estuarine water Hg concentrations. For FHg, internal estuarine Hg contributions were estimated at 26 g yr⁻¹ which enhanced Hg loads from riverine sources to the ocean by 44%. For THg, internal sources amounted to 251 g yr⁻¹ and exceeded riverine sources six-fold. Proposed sources for internal estuarine mercury contributions include atmospheric deposition to the large estuarine surface area and sediment re-mobilization, although sediment Hg concentrations were low (average 23 ± 2 μg kg⁻¹) typical of uncontaminated sediments. Soil mercury concentrations under vegetation, however, were ten times higher (average 200 ± 225 μg kg⁻¹) than in intertidal sediments suggesting that high soil Hg accumulation might drive lateral export of Hg to the ocean. Spatial transects of methylated Hg (MeHg) showed no concentration enhancements in estuarine water and no indication of internal MeHg sources or formation. Initial mass balance considerations suggest that atmospheric deposition may either be in similar magnitude, or possibly exceed lateral tidal export which would be consistent with strong Hg accumulation observed in salt marsh soils sequestering Hg from current and past atmospheric deposition.

Microplastics debris in the marine environment have been widely studied across the globe. Within these particles, the most abundant and prevalent type in the oceans are anthropogenic microfibers (MFs), although they have been historically overlooked mostly due to methodological constraints. MFs are currently considered omnipresent in natural environments, however, contrary to the Northern Hemisphere, data on their abundance and distribution in Southern Oceans ecosystems are still scarce, in particular for sub-Antarctic regions. Using Niskin bottles we've explored microfibers abundance and distribution in the water column (3–2450 m depth) at the Burdwood Bank (BB), a seamount located at the southern extreme of the Patagonian shelf, in the Southwestern Atlantic Ocean. The MFs detected from filtered water samples were photographed and measured using ImageJ software, to estimate length, width, and the projected surface area of each particle. Our results indicate that small pieces of fibers are widespread in the water column at the BB (mean of 17.4 ± 12.6 MFs.L⁻¹), from which, 10.6 ± 5.3 MFs.L⁻¹ were at the surface (3–10 m depth), 20 ± 9 MFs.L⁻¹ in intermediate waters (41–97 m), 24.6 ± 17.3 MFs.L⁻¹ in deeper waters (102–164 m), and 9.2 ± 5.3 MFs.L⁻¹ within the slope break of the seamount. Approximately 76.1% of the MFs were composed of Polyethylene terephthalate, and the abundance was dominated by the size fraction from 0.1 to 0.3 mm of length. Given the high relative abundance of small and aged MFs, and the oceanographic complexity of the study area, we postulate that MFs are most likely transported to the BB via the Antarctic Circumpolar Current. Our findings imply that this sub-Antarctic protected ecosystem is highly exposed to microplastic pollution, and this threat could be spreading towards the highly productive waters, north of the study area.

Targeting the removal of Pb²⁺ in wastewater, cellulosic materials were carbonized in an aerobic environment and activated via ion exchange. The maximum adsorption capacity reached 243.5 mg/g on an MCC-derived adsorbent activated with sodium acetate. The modified porous properties improved the adsorption capacity. The capacity could be completely recovered five times through elution with EDTA. Because of the negative effects of Ni, Mg, and Ca elements, the adsorption capacities of activated carbonized natural materials were lower than that of pure cellulose. N₂ adsorption measurement showed that the adsorbent had a large specific surface area as well as abundant micropores and 4-nm-sized mesopores. FTIR and surface potential results proved that carboxyl group was generated in the aerobic carbonization, and was deprotonated during ion exchange. This adsorbent consisted of C–C bonds as the building blocks and hydrophilic groups on the surface. XPS results demonstrated that the Pb 4f binding energies were reduced by 0.7–0.8 eV due to the interaction between Pb²⁺ and the activated adsorbent, indicating that the carboxylate groups bonded with Pb²⁺ through coordination interactions. Pseudo-second-order and Elovich kinetic models were well fitted with the adsorption processes on the pristine and activated carbonized adsorbents, indicative of chemisorption on heterogeneous surfaces. The Freundlich expression agreed well with the data measured, and the pristine and activated adsorbents had weak and strong affinities for Pb²⁺, respectively. The Pb²⁺ adsorption process was exothermic and spontaneous, and heat release determined the spontaneity. The adsorption capacity is attributed to the carboxylate groups and pores generated in the aerobic oxidation and ion exchange procedures.

The objective of this work was to evaluate the adsorption capacity of alkylated modified porous biochar prepared by esterification and etherification (PSAC-2) for low concentrate volatile organic compounds (VOCs, toluene and ethyl acetate) in high humidity environment by experiments and theoretical calculations. Results showed that PSAC-2 has a large specific surface area and weak surface polarity, at 80% relative humidity, its capacities for toluene and ethyl acetate adsorption could be maintained at 92% and 87% of the initial capacities (169.9 mg/g and 96.77 mg/g). The adsorption behaviors of toluene, ethyl acetate, and water vapor were studied by adsorption isotherms, and isosteric heat was obtained. The desorption activation energy was obtained by temperature programmed desorption experiment. The outcomes manifested that the PSAC-2 can achieve strong adsorption performance for weakly polar molecules. Through density functional theory (DFT) simulations, owing to the interaction of hydrogen bonds, oxygen-containing groups became a significant factor influencing the adsorption of VOCs in humid environments. These results could provide an important reference for VOCs control in a high humidity environment.

In response to the growing worldwide plastic pollution problem, the field of nanoplastics research is attempting to determine the risk of exposure to nanoparticles amidst their ever-increasing presence in the environment. Since little is known about the attributes of environmental nanoplastics (concentration, composition, morphology, and size) due to fundamental limitations in detection and quantification of smaller plastic particles, researchers often improvise by engineering nanoplastic particles with various surface modifications as models for laboratory toxicological testing. Polystyrene and other commercially available or easily synthesized polymer materials functionalized with surfactants or fluorophores are typically used for these studies. How surfactants, additives, fluorophores, the addition of surface functional groups for conjugation, or other changes to surface attributes alter toxicological profiles remains unclear. Additionally, the limited polymers used in laboratory models do not mimic the vast range of polymer types comprising environmental pollutants. Nanomaterials are tricky materials to investigate due to their high surface area, high surface energies, and their propensity to interact with molecules, proteins, and biological probes. These unique properties can often invalidate common laboratory assays. Extreme care must be taken to ensure that results are not artefactual. We have gathered zeta potential values for various polystyrene nanoparticles with different functionalization, in different solvents, from the reported literature. We also discuss the effects of surface engineering and solvent properties on interparticle interactions, agglomeration, particle-protein interactions, corona formation, nano-bio interfaces, and contemplate how these parameters might confound results. Various toxicological exemplars are critically reviewed, and the relevance and shortfalls of the most popular models used in nanoplastics toxicity studies published in the current literature are considered.

Cadmium (Cd) is one dangerous and widespread heavy metal that of great environmental concern. To cost-efficiently adsorb aqueous Cd under influence of various factors, this study succeeded in fabricating goethite-modified biochar (GBC) derived from distillers’ grains (DGs) for Cd sorption of different concentrations (10–100 mg L⁻¹) at pH of 3, 6 and 8 with and without microcystin-LR (MC-LR). Sorption kinetics and isotherms data revealed that Cd sorption capacity of GBC and unmodified BC increased as pH elevated from 3 to 6 but stabilized when pH further elevated to 8. Pseudo-second-order and Langmuir models more accurately fitted to sorption data for both BCs, implying monolayer chemisorption of Cd onto BCs. GBC exhibited more robust sorption for each Cd concentration than unmodified BC, with the maximum sorption capacity of around 28 mg g⁻¹ at neutral and weak alkaline pH. Notably, goethite-modification obviously increased bulk polarity, specific surface area, porosity and surface oxygenic group abundance of BC, thus strongly enhancing Cd sorption by creating more sorption sites mainly via pore-filling, electrostatic attraction, and also via complexation and cation exchange. Co-existing MC-LR of 100 μg L⁻¹ did not obviously affect Cd sorption by both BCs for most Cd levels at each pH, mostly because sorption mechanisms diverged between MC-LR and Cd to largely avoid their competition for sorption sties. Thus, goethite could modify DG-BC as promising and cost-efficient sorbent for Cd even with co-existing MC-LR, especially at neutral and weak alkaline pH that common in the nature. This study was greatly implicated in modifying and applying DG-BC for Cd immobilization in MC-LR laden waters with various pH circumstances.

Biochar modification by metal/metal oxide is promising for improving its adsorption capability for contaminants, especially the anions. However, conventional chemical modifications are complicated and costly. In this study, novel Fe/Fe oxide loaded biochars (RMBCs) were synthesized from a one-step co-pyrolysis of red mud (RM) and shaddock peel (SP), and their potential application for removing anionic azo dye (acid orange 7, AO7) from the aqueous environment was evaluated. Fe from red mud was successfully loaded onto biochars pyrolyzed at 300–800 °C, which presented from oxidation form (Fe₂O₃) to the reduction forms (FeO and Fe⁰) with increasing pyrolysis temperature. The RMBC produced at 800 °C with RM:SP mass ratio of 1:1 (RMBC800₁:₁) exhibited the best capability for AO7 removal (∼32 mg/g), attributed to both adsorption and degradation. The higher surface area of RMBC800₁:₁ and its greater affinity for AO7 led to the higher adsorption. In addition, RMBC800₁:₁-induced degradation of AO7 was another key mechanism for AO7 removal. The reduction forms of Fe (FeO or Fe⁰) in RMBC800₁:₁ may provide electrons for breaking down the azo bond in AO7 molecules and result in degradation, which is further enhanced in acid conditions due to the participation of readily release of Fe²⁺ and the available H⁺ in AO7 degradation. Furthermore, RMBC800₁:₁ can be easily separated from the treated water by using magnetic field, which significantly benefits its separation in wastewater treatment.

Ni(II) and chelated Ni(II) in wastewater are of environmental concern. This study explores the sequestration potential of structural Fe(II) in solid phase (≡Fe(II)) on Ni(II) and EDTA-Ni(II) using freshly prepared ferrous hydroxyl complex (FHC) as the Fe(II)-bearing mineral. The 1 mM Ni(II) could be completely sequestrated in 20 min by 3 mM FHC, although the sequestrated Ni(II) was partially released after 20 min. It is calculated that up to 156 mg Ni(II)/g Fe(II) can be sequestrated by ≡Fe(II) under neutral pH and anaerobic condition. According to the characterizations of the solid products, the large surface area for Ni(II) adsorption and the high ≡Fe(II) reduction capacity for Ni(II) reduction are the main contributors to the Ni(II) sequestration. After the reaction, the FHC is transformed to stable Fe–Ni layered double hydroxides. The concomitant ions can be either promotional or inhibitory to the sequestration performance depending on the ion type. The combination of FHC and Fe(III) can effectively sequestrate EDTA-Ni(II), whereas FHC alone has a low efficiency. Fe(III) substitutes Ni(II) from the EDTA-Ni(II), benefiting the subsequent Ni(II) sequestration by ≡Fe(II). This study demonstrates that ≡Fe(II) suspension is an cost-effective option for remediating Ni(II)-containing wastewater.