The predominance of natural organic matter (NOM) in nonlinear sorption of nonionic organic compounds (NOCs) is a fundamental behavior that controlling the fate, transfer and bioavailability of NOCs in natural environment. There is a debate, i.e., whether the nonlinear sorption is captured by nonlinear partition mechanism or adsorption mechanism. The debate has been going on for decades because characteristics of nonlinear partition are still unknown due to the lack of an adsorbent that can partition NOCs nonlinearly. We find a resin ADS-21, with specific surface area undetectable (<0.5 m² g⁻¹) but high sorption capacity for NOCs (up to 1000 mg g⁻¹ for phenol as an example), is an ideal adsorbent for examining characteristics of nonlinear partitioning. This resin has nonlinear isotherms for phenols and anilines but linear isotherms for polycyclic aromatic hydrocarbons and nitrobenzenes. The observed positively linear relationship of sorption capacities of NOCs with NOCs solubility in water or octanol, could be one of the characteristics of nonlinear partition. Moreover, competitive sorption and no desorption hysteresis could be observed for the nonlinear partition. Hydrogen-bonding of phenols and anilines with ADS-21 is responsible for nonlinear partition, competitive sorption and isotherm nonlinearity. These evidences would be supportive for understanding nonlinear partition and the nonlinear sorption of NOCs by NOM.

This article gives an overview of nanotechnologies applied in remediation of water contaminated by poly- and perfluoroalkyl substances (PFASs). The use of engineered nanomaterials (ENMs) in physical sorption and photochemical reactions offers a promising solution in PFAS removal because of the high surface area and the associated high reactivities of the ENMs. Modification of carbon nanotubes (CNTs) (e.g., oxidation, applying electrochemical assistance) significantly improves their adsorption rate and capacity for PFASs removal and opens a new door for use of CNTs in environmental remediation. Modified nanosized iron oxides with high adsorption capacity and magnetic property have also been demonstrated to be ideal sorbents for PFASs with great recyclability and thus provide an excellent alternative for PFAS removal under various conditions. Literature shows that PFOA, which is one of the most common PFASs detected at contaminated sites, can be effectively decomposed in the presence of either TiO₂-based, Ga₂O₃-based, or In₂O₃-based nano-photocatalysts under UV irradiation. The decomposition abilities and mechanisms of different nano-photocatalysts are reviewed and compared in this paper. Particularly, the nanosized In₂O₃ photocatalysts have the best potential in PFOA decomposition and the decomposition performance is closely related to the specific surface area and the amount of photogenerated holes on the surfaces of In₂O₃ nanostructures. In addition to detailed review of the published studies, future prospects of using nanotechnology for PFAS remediation are also discussed in this article.

Light-absorbing organic carbon (OC), also referred to as “brown carbon” (BrC), has been intensively investigated in atmospheres impacted by biomass burning. However, other BrC sources (e.g., secondary formation in the atmosphere) are rarely studied in ambient aerosols. In the current work, forty-five PM₂.₅ filter samples were collected in Research Triangle Park (RTP), NC, USA from June 1st to July 15th, 2013. The bulk carbonaceous components, including OC, elemental carbon (EC), water soluble OC (WSOC), and an array of organic molecular markers were measured; an ultraviolet/visible spectrometer was used to measure the light absorption of methanol extractable OC and WSOC. The average light absorption per OC and WSOC mass of PM₂.₅ samples in summer RTP are 0.36 ± 0.16 m² gC⁻¹ and 0.29 ± 0.13 m² gC⁻¹, respectively, lower than the ambient aerosol samples impacted by biomass burning and/or fossil fuel combustion (0.7–1.6 m² gC⁻¹) from other places. Less than 1% of the aqueous extracts absorption is attributed to the light-absorbing chromophores (nitroaromatic compounds) identified in this work. To identify the major sources of BrC absorption in RTP in the summer, Positive Matrix Factorization (PMF) was applied to a dataset containing optical properties and chemical compositions of carbonaceous components in PM₂.₅. The results suggest that the formation of biogenic secondary organic aerosol (SOA) containing organosulfates is an important BrC source, contributing up to half of the BrC absorption in RTP during the summertime.

Degradation of metolachlor in surface soil is extremely important to its potential mobility and overall persistence. In this study, the effects of earthworms (Eisenia fetida) on the degradation of metolachlor at two concentration levels (5 and 20 mg kg⁻¹) in soil were investigated via the column experiment. The degradation kinetics of metolachlor indicate that addition of earthworms enhances metolachlor degradation significantly (P < 0.05), with the enhanced degradation rate of 30% and 63% in the low and high concentration treatments at the 15th day, respectively. Fungi rather than bacteria are primarily responsible for metolachlor degradation in soil, and earthworms stimulate metolachlor degradation mainly by stimulating the metolachlor-degrading functional microorganisms and improving fungal community structure. Earthworms prefer to promote the possible fungal degraders like order Sordariales, Microascales, Hypocreales and Mortierellales and the possible bacteria genus Rubritalea and strengthen the relationships between these primary fungi. Two metabolites metolachlor oxanilic (MOXA) and moetolachlor ethanesulfonic acid (MESA) are detected in soil and earthworms in the high concentration treatments. Earthworms stimulate the formation of MOXA and yet inhibit the formation of MESA in soil. Another metabolite metolachlor-2-hydroxy (M2H) is also detected in earthworms, which is reported firstly. The study provides an important information for the remediation of metolachlor-polluted soil.

Endocrine disrupting chemicals (EDCs) include a wide array of pollutants, such as some metals and other toxic elements, which may cause changes in hormonal homeostasis. In addition to affecting physiology of individuals directly, EDCs may alter the transfer of maternal hormones to offspring, i.e. causing transgenerational endocrine disruption. However, such effects have been rarely studied, especially in wild populations. We studied the associations between environmental elemental pollution (As, Cd, Cu, Ni, Pb) and maternally-derived egg thyroid hormones (THs) as well as nestling THs in great tits (Parus major) using extensive sampling of four pairs of polluted and reference populations across Europe (Finland, Belgium, Hungary, Portugal). Previous studies in these populations showed that breeding success, nestling growth and adult and nestling physiology were altered in polluted zones compared to reference zones. We sampled non-incubated eggs to measure maternally-derived egg THs, measured nestling plasma THs and used nestling faeces for assessing local elemental exposure. We also studied whether the effect of elemental pollution on endocrine traits is dependent on calcium (Ca) availability (faecal Ca as a proxy) as low Ca increases toxicity of some elements. Birds in the polluted zones were exposed to markedly higher levels of toxic elements than in reference zones at the populations in Finland, Belgium and Hungary. In contrast to our predictions, we did not find any associations between overall elemental pollution, or individual element concentrations and egg TH and nestling plasma TH levels. However, we found some indication that the effect of metals (Cd and Cu) on egg THs is dependent on Ca availability. In summary, our results suggest that elemental pollution at the studied populations is unlikely to cause overall TH disruption and affect breeding via altered egg or nestling TH levels with the current elemental pollution loads. Associations with Ca availability should be further studied.

Harmful algal blooms have emerged as a worldwide issue. After concentrations of herbicides entering water, herbicides in water may pose ecological effects on them. The present study investigates the toxicity and environmental behavior of the herbicides, napropamide and acetochlor as enantiomers and as racemates on Microcystis aeruginosa which is the main specie known to produce hepatotoxins. S-napropamide/acetochlor are degraded faster than their corresponding isomer R-napropamide/acetochlor, with the latter more prone to accumulate in algal cells. Moreover, all the enantiomers did not undergo measurable racemization in the medium and algal cells. S-napropamide/acetochlor exhibited much higher toxicity than R-napropamide/acetochlor, with the S-enantiomer inducing a much greater production of antioxidant defense enzymes (superoxide dismutase (SOD) and malondialdehyde (MDA)) and microcystins (MC). SOD and MC increased after treatment with the herbicides and these increases were dependent on the exposure time, whereas MDA showed no apparent change. The information provided in this work will be useful for understanding the toxicity mechanism and environmental behaviors of different amide herbicides (napropamide and acetochlor) in aquatic environments at the enantiomeric level. Additionally, analysis of chiral herbicides in aquatic system needs more attention to aide in the environmental assessment of chiral herbicides.

To better understand the toxicological activities of perfluorooctanoic acid (PFOA), we examined the effects of PFOA on apoptosis and its molecular mechanism in SMMC-7721 hepatoma cells. Cell viability was evaluated by MTT assay and apoptosis was determined by flow cytometry. Western blot and quantitative real-time PCR were used to examine the protein and gene expressions of Bax and Bcl-2. Our results showed that PFOA inhibited SMMC-7721 cell growth and induced apoptosis. PFOA treatment increased Bax expression and increased Bcl-2 expression at both gene and protein levels. Our study demonstrated that PFOA had toxic effects on SMMC-7721 cells, such as inhibiting cell proliferation and inducing apoptosis. Furthermore, we showed that PFOA-mediated induction of apoptosis involved inducing Bax and decreasing Bcl-2 expression as a molecular mechanism of its toxicological effects.

Fifty-six groundwater samples were taken from the island of Favignana to evaluate the interaction between the groundwater and seawater, as well as the deterioration factors for the aquifers, using the combined hydrogeochemical and multivariate statistical approaches. Results show that the order of the groundwater chemistry in the study area was Na+> Ca2+>Mg2+>K+ and Cl->HCO3−>SO42->NO3−. The groundwater samples were in the moderate saline zone to highly saline zone and indicate that the groundwater of the island of Favignana was recharged with seawater. The spatial distribution maps of Cl− and NO3− show that most of the groundwater samples had high concentrations of Cl− and NO3− in the study area. The ionic ratio diagrams, such as Na+/Cl− versus Cl−, Mg2+/Ca2+ versus Cl− and Ca2+/HCO3− versus Cl−, and other hydrogeochemical plots reveal that the groundwater chemistry of the study was primarily controlled by the seawater intrusion and reverse ion exchange process, with a small contribution from carbonate dissolution. Additionally, the NO3−/Cl− versus Cl− diagram and principal component analysis (PCA) show that the contamination of nitrate in the study area was due to human activities (i.e. agriculture and domestic sewage disposal). The outcome of the present research could be helpful for groundwater resource management in coastal environments.

Aiming at realizing heavy metal recycling and resource utilization, a carbon-based iron catalyst (Fe@C) was synthesized through a resin carbonization method, and adopted for peroxymonosulfate (PMS) activation to remove bisphenol S (BPS), an emerging aquatic contaminant. This study demonstrated that Fe@C exhibited excellent catalytic potential for BPS degradation with a relatively low activation energy (Ea = 29.90 kJ/mol). Kinetic factors affecting the activation performance were thoroughly investigated. The obtained results indicated that Fe@C composite exhibited the superior uniformity with carbon as the framework and granular iron oxide as the coverage. pH increase could cause the inhibitive effect on BPS degradation, while the increasing catalyst loading (0.05–0.5 g/L) was conducive for the catalytic performance of Fe@C, with an optimal PMS concentration at 1.0 mM. A negative influence on BPS degradation was obtained in the presence of SO42−, HCO3− and lower concentration of Cl− (0–20 mM), compared to the promotion at higher concentration of Cl− (>50 mM). Based on the electron spin resonance (ESR) monitoring and radical scavenging results, it is demonstrated that singlet oxygen, a non-radical species, emerged together with ·SO4− and ·OH for BPS degradation. A three-channel catalytic mechanism was verified through typical characterizations. Furthermore, the degradation pathway of BPS was proposed based on the identified intermediates. This novel carbon-based activator for PMS showed notable potential for the waste resin recycling and water decontamination.A novel Fe-based activator carbonized from a saturated resin exhibits excellent performance for Bisphenol S degradation with activated peroxymonosulfate.