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.

The use of lanthanum-anchored zinc oxide distorted hexagon (La@ZnO DH) nanoclusters as an active material for the photodegradation of rhodamine B (Rh–B) dye via hydrogen bonding, electrostatic, and π-π interactions is examined herein. The active photocatalyst is derived from porous zeolite imidazole frameworks (ZIF-8) via a combined ultrasonication and calcination process. The distorted hexagon nanocluster morphology with controlled surface area is shown to provide excellent catalytic activity, chemical stability and demarcated pore volume. In addition, the low bandgap (3.57 eV) of La@ZnO DH is shown to expand the degradation of Rh–B under irradiation of UV light as compared to the pristine ZIF-8-derived ZnO photocatalyst due to inhibited recombination of electrons and holes. The outstanding physicochemical stability and enhanced performance of La@ZnO DH could be ascribed to the synergistic interaction among La3+ particles and the ZnO nanoclusters and provide a route for their utilization as a promising catalyst for the detoxification of Rh–B.

Developing low-cost and high-performance biosorbent for water purification continues drawing more and more attention. In this study, cellulose-chitosan composite hydrogels were fabricated via a co-dissolution and regeneration process using a molten salt hydrate (a 60 wt% aqueous solution of LiBr) as a solvent. The addition of chitosan not only introduced functionality for metal adsorption but also increased the specific surface area and improved the mechanical strength of the composite hydrogel, compared to pure cellulose hydrogel. Batch adsorption experiments indicated that the composite hydrogel with 37% cellulose and 63% chitosan exhibited an adsorption capacity of 94.3 mg/g (1.49 mmol/g) toward Cu²⁺ at 23 °C, pH 5, and initial metal concentration of 1500 mg/L, which was 10 times greater than the adsorption capacity of pure cellulose hydrogel. Competitive adsorption from a mixed metals solution revealed that the cellulose-chitosan composite hydrogel exhibited selective adsorption of the metals in the order of Cu²⁺ > Zn²⁺ > Co²⁺. This study successfully demonstrated an innovative method to fabricate biosorbents from abundant and renewable natural polymers (cellulose and chitosan) for removing metal ions from water.

Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qₑ = 3.55·10⁻⁶ mol/m²), which could be explained by a higher surface area (600 m²/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100–500 m²/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qₑ = 1.72·10⁻⁶ mol/m²). However, the best experimental results of this study were obtained using synthesized graphenic materials.

Development of non-noble metal cluster catalysts, aiming at concurrently high activity and stability, for emission control systems has been challenging because of sintering and overcoating of clusters on the support. In this work, we reported the role of well-dispersed copper nanoclusters supported on TiO₂ in CO oxidation under industrially relevant operating conditions. The catalyst containing 0.15 wt% Cu on TiO₂ (0.15 CT) exhibited a high dispersion (59.1%), a large specific surface area (381 m²/gCᵤ), a small particle size (1.77 nm), and abundant active sites (75.8% Cu₂O). The CO oxidation activity measured by the turnover frequency (TOF) was found to be enhanced from 0.60 × 10⁻³ to 3.22 × 10⁻³ molCO·molCᵤ⁻¹·s⁻¹ as the copper loading decreased from 5 to 0.15 wt%. A CO conversion of approximately 60% was still observed in the supported cluster catalyst with a Cu loading of 5 wt% at 240 °C. No deactivation was observed for catalysts with low copper loading (0.15 and 0.30 CT) after 8 h of time-on-stream, which compares favorably with less stable Au cluster-based catalysts reported in the literature. In contrast, catalysts with high copper loading (0.75 and 5 CT) showed deactivation over time, which was ascribed to the increase in copper particle size due to metal cluster agglomeration. This study elucidated the size-activity threshold of TiO₂-supported Cu cluster catalysts. It also demonstrated the potential of the supported Cu cluster catalyst at a typical temperature range of diesel engines at light-load. The supported Cu cluster catalyst could be a promising alternative to noble metal cluster catalysts for emission control systems.