Polycyclic aromatic hydrocarbons (PAHs) in soil can be recalcitrant to solvent extraction after aging. We showed in this study that mixing a small amount of water in the extracting solvent during microwave-assisted extraction (MAE) can release recalcitrant PAHs, resulting in significant improvement in the analyzed concentrations. The improvement factor (F) for the total of 16 priority PAHs (∑PAH16) listed by the United States Environmental Protection Agency was 1.44–1.55 for field soils. By comparing the F values for different soil organic components, we demonstrated that the recalcitrant PAHs were primarily associated with biochar, humic acid (HA), and humin (HM), with the F values for ∑PAH16 of 1.94, 6.62, and 4.59, respectively. The results showed that the recalcitrant PAHs comprised a sequestered fraction and a desorption-limited fraction. NMR spectra showed that water worked alone at elevated temperature to promote hydrolysis of biochar and destroy the macromolecular structure, thus causing the release of the otherwise sequestered PAHs during MAE. The substantial reduction in F values for HA and HM after demineralization indicated sequestration of PAHs in organic-mineral complexes, which can be destroyed by hot water treatment. The release of the sequestered fraction was nonselective and independent of compound hydrophobicity. In comparison, the release of the desorption-limited fraction was positively affected by the hydrophobicity of PAHs and was facilitated by the presence of water in the extracting solvent. The results of this study provide important insights into the sequestration and release of recalcitrant PAHs in soil.

In this critical review, we explored the most recent advances about the fate of antibiotics on biological wastewater treatment plants (WWTP). Although the occurrence of these pollutants in wastewater and natural streams has been investigated previously, some recent publications still expose the need to improve the detection strategies and the lack of information about their transformation products. The role of the antibiotic properties and the process operating conditions were also analyzed. The pieces of evidence in the literature associate several molecular properties to the antibiotic removal pathway, like hydrophobicity, chemical structure, and electrostatic interactions. Nonetheless, the influence of operating conditions is still unclear, and solid retention time stands out as a key factor. Additionally, the efficiencies and pathways of antibiotic removals on conventional (activated sludge, membrane bioreactor, anaerobic digestion, and nitrogen removal) and emerging bioprocesses (bioelectrochemical systems, fungi, and enzymes) were assessed, and our concern about potential research gaps was raised. The combination of different bioprocess can efficiently mitigate the impacts generated by these pollutants. Thus, to plan and design a process to remove and mineralize antibiotics from wastewater, all aspects must be addressed, the pollutant and process characteristics and how it is the best way to operate it to reduce the impact of antibiotics in the environment.

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.

The unified bioaccessibility method (UBM) was harnessed to assess in vitro oral bioaccessibility pools of dialkyl phthalate congeners (with methyl, –ethyl, –butylbenzyl, –n-butyl, –2-ethylhexyl, and –n-octyl moieties) and bisphenol A at the 17 μg g⁻¹ level in beach sand contaminated with polyethylene microplastics. A variety of sample preparation approaches prior to the analysis of the UBM gastrointestinal extracts, including traditional methods (protein precipitation, liquid-liquid extraction, and solid-phase extraction) and dispersive liquid-liquid microextraction (DLLME) were comprehensively evaluated for clean-up and analyte enrichment. DLLME was chosen among all tested approaches on account of the high extraction efficiency (73–95%, excluding bis(2-ethylhexyl)phthalate and di-n-octyl phthalate), high sample throughput (∼7 min per set of samples), and environmental friendliness as demonstrated by the analytical eco-scale score of 83, and the green analytical procedure index pictogram with green/yellow labeling. The release of the less hydrophobic plastic-laden compounds (dimethyl phthalate, diethyl phthalate and bisphenol A) from the contaminated sample into the body fluids was significant, with bioaccessibility values ranging from 30 to 70%, and from 43 to 74% in gastric and gastrointestinal fluids, respectively, and with relative standard deviation < 17% in all cases. The majority of the compounds were leached during gastric digestion, likely as the combined action of the low pH and the gastric enzymes. The risk exposure analysis revealed that accumulation/concentration in the body fluids is potentially relevant for dimethyl phthalate, diethyl phthalate and bisphenol A, with relative accumulation ratios ranging from 1.1 ± 0.1 to 2.6 ± 0.4. The average daily intake values for the suite of compounds, corrected with the bioaccessibility fraction, ranged from 60 to 430 ng kg of body weight⁻¹·day⁻¹, in all cases, far below the tolerable daily intakes, thus indicating the lack of children health risk by ingestion of microplastic-laden sand with elevated concentrations of plasticizers.

Plastic pollution is a new, pressing, environmental topic. Microplastics are considered contaminants of emerging concern and, consequently, microplastic research has grown exponentially in the last decade. Here, current knowledge regarding the impacts of micro- and nanoplastics on terrestrial plants and aquatic macrophytes is discussed, with a special focus on adsorption, uptake and toxicological effects. Our review reveals that a range of plants and macrophytes can adsorb or internalise plastic particles. Both processes depend on particle characteristics such as size and charge, as well as plant features including a sticky or hydrophobic surface layer. This finding is of concern given that plants and aquatic macrophytes are at the bottom of food webs and are a crucial component of the human diet. Therefore, there is a critical need for improved understanding of adsorption, uptake and impacts of micro- and nanoplastics, and the consequences thereof for trophic transfer, food safety and security. Also, a range of stress responses have been observed for many plant and macrophyte species after both short and long-term exposures to plastic particles. Given that some plastic particles can affect plant productivity, we surmise that plastic particles may potentially impact ecosystem productivity and function. Here we present a synthesis and a critical evaluation of the state of knowledge of micro- and nanoplastics and plants and macrophytes, identifying key questions for future research.

Direct utilization of waste polyethylene terephthalate (PET) from the environment to form highly porous aerogel technology for oil absorption is an attractive approach from the view point of green chemistry. However, the oil absorption reaction is limited by low oil absorption capacity and less stability. For now, silica aerogel are used to solve these problem. Our goal is to substitute to these silica aerogel with PET aerogel technology. Herein, we have prepared an environmental waste PET based aerogel with 1.0:0.5 wt% PET, polyvinyl alcohol (PVA), and glutaraldehyde (GA) 0.2% v/v were dispersed in 10 mL DI water, followed by homogenization (30 min), sonication (10 min), and ageing (2 h) at 70 °C. To escape macroscopic cracking, cooling (8 h) at 4 °C was followed by freezing (6 h), freeze drying at −80 °C, and 5 mTorr for 18 h. The hybrid PET aerogel displays excellent performance towards oil absorption. Notably it showed high absorption capacity towards the different oils about 21–40 times its own weight, depending on the viscosity and density of the oil and solvents within 15–35 s, 25 °C, and 2 × 2 cm aerogel size. In addition, the aerogel shows there is no change in structure after several recycles due to high mechanical strength. Furthermore, because of the PET aerogel's high porosity (99.74%) and low density (0.0311 g/cm³), close bonding between PET-PVA occurs. Therefore, aerogel shows hydrophobic nature, good mechanical strength, high thermal stability, arrangement of the interconnected fibrillar pore network offers a high surface to volume ratio, low surface energy, high surface roughness, and more reusability. All these parameters are responsible for high oil absorption.

Discharged carbon nanotubes (CNTs) likely interact with co-existing organic contaminants (OCs) and pose joint toxicity to environmental microbes. Herein, hydrophobic pentachlorophenol (PCP) and hydrophilic ciprofloxacin (CIP) were used as representative OCs and their joint toxicities with CNTs to Bacillus subtilis were systematically investigated at cellular, biochemical, and omics levels. The 3-h bacterial growth half inhibitory concentrations of CNTs, PCP, and CIP were 12.5 ± 2.6, 3.5 ± 0.5, and 0.46 ± 0.03 mg/L, respectively, and they all could damage cell membrane, increase intracellular oxidative stress, and alter bacterial metabolomics and transcriptomics; while CNTs-PCP and CNTs-CIP binary exposures exhibited distinct additive and synergistic toxicities, respectively. CNTs increased bacterial bioaccumulation of PCP and CIP via destabilizing and damaging cell membrane. PCP reduced the bioaccumulation of CNTs, while CIP had no significant effect; this difference could be owing to the different effects of the two OCs on cell-surface hydrophobicity and CNTs electronegativity. The additive toxicity outcome upon CNTs-PCP co-exposure could be a result of the balance between the increased toxicity from increased PCP bioaccumulation and the decreased toxicity from decreased CNTs bioaccumulation. The increased bioaccumulation of CIP contributed to the synergistic toxicity upon CNTs-CIP co-exposure, as confirmed by the increased inhibition of topoisomerase Ⅳ activity and interference in gene expressions regulating ABC transporters and lysine biosynthesis. The findings provide novel insights into environmental risks of CNTs.

In this study, water and sediment samples from the Jiaozhou Bay and surrounding rivers were collected to analyze the seasonal occurrence and allocation of 12 organophosphate esters (OPEs) and the associated ecological risk. The higher contamination of OPEs in the adjacent rivers indicated the impact of terrestrial input. Tris(1-chloropropan-2-yl) phosphate (TCIPP) was the predominant OPE in the four environmental sample groups investigated. The spatial distribution of OPEs in seawater varied greatly seasonally and was mainly affected by terrestrial input, with OPEs being redistributed under the influence of tidal currents. The partition coefficients (log Kₒc) of the OPEs were calculated, and their strong correlation with the log Kₒw (octanol-water) values suggested that the water-sediment allocation was significantly affected by hydrophobicity. The homologous relationships among the 7 OPEs with detection frequencies greater than 40% were identified by principal component analysis (PCA). The partial least squares regression (PLSR) model explicated that ∑OPEs cycling dynamics and principal controlling factors were dissimilar in the bay versus surrounding rivers. The risk quotient (RQ) faced by typical organisms in seawater and river water indicated that short-term OPEs exposure was safe for green algae, daphnia and fish. The organisms in rivers faced the higher ecological risk of OPEs in spring than in summer and winter. Therefore, the terrestrial transport of OPEs in spring should be controlled.

Recently, the adsorption-based environmental remediation techniques have gained a considerable attention, due to their economic viability and simplicity over other methods. Hence, detailed presentation and analysis were herein focused on describing the role of biochar in oil spill removal. Oil removal by utilizing biochar is assumed as a green-oriented concept. Biochar is a carbon-rich low-cost material with high porosity and specific surface chemistry, with a tremendous potentiality for oil removal from aqueous solutions. Oil sorption properties of biochar mainly depend on the biochar production/synthesis method, and the biomass feedstock type. In order to preserve the stability of functional groups in the structure, biochar needs to be produced/activated at low temperatures (<700 ᵒC). In general, biochar derived from biomass containing high lignin content via slow pyrolysis is more favorable for oil removal. Exceptional characteristics of biochar which intensify the oil removal capability such as hydrophobicity, oleophilicity or/and specific contaminant-surface interaction of biochar can be enhanced and be tuned by chemical and physical activation methods. Considering all the presented results, future perspectives such as the examination of biochar efficacy on oil removal efficiency in multi-element contaminated aqueous solutions to identify the best biomass feedstocks, the production protocols and large-scale field trials, are also discussed.

Algal organic matter (AOM) is an important source for the dissolved organic matter (DOM) pool in aquatic systems, particularly in eutrophic waters. In this study, we reported the dynamic pattern of AOM hydrophobicity during the growth cycle of Microcystis aeruginosa using the partition coefficients of AOM in the aqueous two-phase system (KATPS) as a simple quantitative measure. AOM hydrophobicity had significant and non-monotonic changes during the growth cycle. It increased in the lag and early exponential phases, then decreased in the late exponential and stationary phases, and rebounded in the decline phase. AOM hydrophobicity determined using the resin fractionation, SUVA₂₅₄, and nuclear magnetic resonance methods shared similar non-monotonic pattern. Nevertheless, the correlations among these indicators were poor. The partition behavior of polycyclic aromatic hydrocarbons and chlorobenzenes to AOM was assessed based the KATPS dataset and the two-phase system (TPS) model. The TPS model showed good prediction power for the partition behavior of AOM with an RMSE of 0.23, suggesting that it was applicable to AOM from Microcystis aeruginosa. Our results indicate that algae activity will influence the overall hydrophobicity of the DOM pool depending on the growth phase, resulting in changes in the bioavailability of hydrophobic organic compounds in aquatic systems.