We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

The fate of fuel releases largely depends on the poorly-understood response in microbial community structure and function. Here, we evaluate the impacts to the microbial community resulting from a pilot-scale continuous release (10 months) of a 10% v:v ethanol solution mixed with benzene and toluene (50 mg/L each). Microbial population shifts were characterized by pyrosequencing-based 16S rRNA analysis and by quantitative PCR targeting Bacteria, Archaea, and functional genes for methanogenesis (mcrA), acetogenesis (fhs) and aerobic degradation of aromatic hydrocarbons (PHE), which could occur in hypoxic micro-environments. The release stimulated microbial growth, increased species richness and diversity, and selected for genotypes involved in fermentative degradation (the relative abundance of mcrA and fhs increased 18- and 6-fold, respectively). The growth of putative hydrocarbon degraders and commensal anaerobes, and increases in microbial diversity and in degradation rates suggest an adaptive response that increases the potential for natural attenuation of ethanol blend releases.

To investigate the chemical components, sources, and interactions of particulate matter (PM) and volatile organic compounds (VOCs), a field campaign was implemented during the spring of 2018 in nine cities in northwestern (NW) China. PM was mainly contributed by organic matter and water-soluble inorganic ions (41% for PM₁₀ and approximately 60% for PM₂.₅ and PM₁). Two typical haze patterns were observed: anthropogenic pollution type (AP-type), wherein contributions of sulfate, nitrate, and ammonium (SNA) increased, and dust pollution type (DP-type), wherein contributions of Ca²⁺ increased and SNA decreased. Source appointment suggested that regional sources contributed close to half to PM₂.₅ pollution (40% for AP-type and 50% for DP-type). Thus, sources from regional transport are also important for haze and dust pollution. The ranking of VOC concentrations was methanol > acetaldehyde > formic acid + ethanol > acetone. Compared with other cities, there are higher oxygenated VOCs (OVOCs) and lower aromatics in NW China. The relationships between VOCs and PM were discussed. The dominating secondary organic aerosols (SOA) formation potential precursors were C₁₀–aromatics, xylene, and styrene under low–nitrogen oxide (NOx) conditions, and benzene, C₁₀–aromatics, and toluene dominated under high–NOx conditions. The quadratic polynomial was the most suitable fitting model for their correlation, and the results suggested that VOC oxidations explained 6.1–10.8% and 9.9–20.7% of SOA formation under high–NOx and low–NOx conditions, respectively.

Perfluoroalkyl acids (PFAAs) are widely used in industrial production and daily life because of their unique physicochemical properties, such as their hydrophobicity, oleophobicity, surface activity, and thermal stability. Perfluorosulfonic acids (PFSAs) and perfluorocarboxylic acids (PFCAs) are the most studied PFAAs due to their global occurrence. PFAAs are environmentally persistent, toxic, and the long-chain homologs are also bioaccumulative. Exposure to PFAAs may arise directly from emission or indirectly via the environmental release and degradation of PFAA precursors. Precursors themselves or their conversion intermediates can present deleterious effects, including hepatotoxicity, reproductive toxicity, developmental toxicity, and genetic toxicity. Therefore, exposure to PFAA precursors constitutes a potential hazard for environmental contamination. In order to comprehensively evaluate the environmental fate and effects of PFAA precursors and their connection with PFSAs and PFCAs, we review environmental biodegradability studies carried out with microbial strains, activated sludge, plants, and earthworms over the past decade. In particular, we review perfluorooctyl-sulfonamide-based precursors, including perfluroooctane sulfonamide (FOSA) and its N-ethyl derivative (EtFOSA), N-ethyl perfluorooctane sulfonamido ethanol (EtFOSE), and EtFOSE-based phosphate diester (DiSAmPAP). Fluorotelomerization-based precursors are also reviewed, including fluorotelomer alcohols (FTOH), fluorotelomer sulfonates (FTSA), and a suite of their transformation products. Though limited information is currently available on zwitterionic PFAS precursors, a preliminary review of data available for 6:2 fluorotelomer sulfonamide betaine (FTAB) was also conducted. Furthermore, we update and refine the recent knowledge on biotransformation strategies with a focus on metabolic pathways and mechanisms involved in the biotransformation of PFAA precursors. The biotransformation of PFAA precursors mainly involves the cleavage of carbon-fluorine (C–F) bonds and the degradation of non-fluorinated functional groups via oxidation, dealkylation, and defluorination to form shorter-chained PFAAs. Based on the existing research, the current problems and future research directions on the biotransformation of PFAA precursors are proposed.

Removal of dissolved sulfide contaminants from aqueous model solution using bio-derived porous graphitic carbon (PGC) impregnated with δ-MnO₂ was investigated. The composite adsorbent was synthesized using the chemical wet deposition method wherein MnO₂ was deposited on carbon walls through an in-situ reaction between permanganate and ethanol. Formation of transition metal oxide of manganese in the form of birnessite nanoparticles on interconnected PGC cell structure was confirmed by transmission electron microscopy, scanning electron microscopy, elemental analysis, and X-Ray diffraction characterization studies. The composite nanomaterial was tested for sulfide removal from aqueous solution at various conditions, including the pH, adsorbent dosage, initial solution concentration, and contact time. Adsorption results demonstrated an excellent adsorption capacity of ca. 90% within 20 min of contact time at 298 K. Equilibrium data collected from batch adsorption experiments fitted well with the Langmuir isotherm model (KL = 190 L/mg; R² = 0.99). The maximum adsorption capacity of the composite was estimated as 526.3 mg S²⁻/g at highly alkaline conditions compared to ca. 340 mg/g for a δ-MnO₂ adsorbent. Adsorptive oxidation of sulfides on composite MnO₂-PGC adsorbent was found to be controlled by the chemisorption process in accordance with the pseudo-second-order reaction model. Characterization of spent adsorbents revealed that sulfide was removed through adsorptive oxidation resulting in the formation of agglomerated particles of metal sulfate complexes and elemental sulfur. Analysis of reaction mechanism revealed that both MnO₂ and PGC played a role in the adsorptive oxidation of sulfides to CaSO₄ and elemental sulfur.

Airborne particulate matter (PM) has become a serious health issue causing pulmonary diseases such as asthma. Due to the side effects and non-specificity of conventional drugs, there is a need to develop natural-product-based alternative treatments. Sargassum horneri is a brown alga shown to have anti-oxidant, anti-inflammatory, and anti-allergic effects. Thus, we sought to determine whether ethanol extract of Sargassum horneri (SHE) mitigates the effect of PM exposure on asthma development. To establish a mouse model of asthma, BALB/c mice were sensitized with ovalbumin (OVA, 10 μg) and challenged with PM (5 mg/m³) for 7 days consecutively. SHE (200, 400 mg/kg), Prednisone (5 mg/kg), or PBS was daily administrated orally before PM exposure. SHE mitigated PM exacerbated dendritic cell activation. More importantly, SHE restrained Th2 polarization by attenuating transcription factors GATA3 and STAT5, which further mitigated the expression of Th2 cytokines interleukin (IL)-4, IL-5, and IL-13 in the lung homogenates of PM-exacerbated asthmatic mice. SHE further attenuated PM-exacerbated eosinophil infiltration in the lung, trachea, and BALF. In addition, SHE markedly mitigated the activation of mast cells and the IgE level in serum. Concomitantly, SHE further restrained the Th17 cell response in PM-exposed allergic mice through attenuating expression of transcription factors RORγT, STAT3 and expression of relevant effector cytokines IL-17a. This resulted in mitigated neutrophil infiltration in the lung. Taken together, SHE significantly suppressed PM-exacerbated hypersecretion of mucus in asthmatic mice. These results suggest that SHE has therapeutic potential for treating PM-exacerbated allergic asthma through concomitantly inhibiting Th2/Th17 responses.

Common solvents are frequently used as carriers to dissolve chemicals with a hydrophobic property that is extensively applied in the industrial and biomedical fields. In this study, we aimed to systematically study the sub-chronic effect of ten common solvents at low concentration exposure in adult zebrafish and perform neurobehavioral assessments for mechanistic exploration. After exposed to ten common solvents, including methanol, ethanol (EtOH), dimethyl sulfoxide (DMSO), isopropanol, acetone, polyethylene glycol-400 (PEG-400), glycerol, butanol, pentane, and tetrahydrofuran for continuous 10 day at 0.1% concentration level, adult zebrafish were subjected to perform a serial of behavioral tests, such as novel tank, mirror biting, predator avoidance, social interaction and shoaling. Later, 20 behavioral endpoints obtained from these five tests were transformed into a scoring matrix. Principal component analysis (PCA) and hierarchy clustering were performed to evaluate and compare the zebrafish behavior profiling. By using this phenomic approach, we were able to systematically evaluate the toxicity of the common solvents in zebrafish at a neurobehavioral level for the first time and found each common solvent-induced unique behavioral alteration to produce fingerprint-like patterns in hierarchy clustering and heatmap analysis. Among all tested common solvents, acetone and PEG-400 displayed better biocompatibility and less toxicity since they triggered less behavioral and biochemical alterations while methanol and DMSO caused severe behavior alterations in zebrafish after chronic exposure of these solvents. We conclude the behavioral phenomic approach conducted in this study providing a powerful tool to a systematical exploration of the common solvent toxicity at the whole organism level.

Bioaccessibility extractions are increasingly applied to measure the fraction of pollutants in soil, sediment and biochar, which can be released under environmentally or physiologically relevant conditions. However, the bioaccessibility of hydrophobic organic chemicals (HOCs) can be markedly underestimated when the sink capacity of the extraction medium is insufficient. Here, a novel method called “Membrane Enhanced Bioaccessibility Extraction” (MEBE) applies a semipermeable membrane to physically separate an aqueous desorption medium that sets the desorption conditions from an organic medium that serves as acceptor phase and infinite sink. The specific MEBE method combines HOC (1) desorption into a 2-hydroxypropyl-β-cyclodextrin solution, (2) transfer through a low-density polyethylene (LDPE) membrane and (3) release into ethanol, serving as analytical acceptor phase. The surface to volume ratio within the LDPE membrane is maximized for rapid depletion of desorbed molecules, and the capacity ratio between the acceptor phase and the environmental sample is maximized to achieve infinite sink conditions. Several experiments were conducted for developing, optimizing and pre-testing the method, which was then applied to four soils polluted with polycyclic aromatic hydrocarbons. MEBE minimized sample preparation and yielded a solvent extract readily analyzable by HPLC. This study focused on the proof-of-principle testing of the MEBE concept, which now can be extended and applied to other samples and desorption media.

In the present investigation seaweeds of macroalgae like Kappaphycus alvarezii, Gracilaria salicornia and Gracilaria edulis used as novel biosorbent in native (KA, GS, GE) and ethanol modified (EKA, EGS, EGE) for Rhodamine B (RB) removal from aqueous solution in batch process. Effect of various biosorption parameters such as pH, initial concentration of RB, biosorbent dosage and contact time were studied. The maximum biosorption capacity determined as 9.84 (KA), 11.03 (GS), 8.96 (GE), 112.35 (EKA), 105.26 (EGS) and 97.08 mg/g (EGE), respectively towards the removal of RB from aqueous solutions. Better removal of RB was observed using EKA, EGS, and EGE biosorbents at 2.0 pH. The characterizations of the biosorbents were performed using Scanning Electron microscope and Fourier Transform Infrared Spectroscopy. Biosorption equilibrium data evaluated using Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Jovanovic isotherm model. The Langmuir isotherm model best suited the equilibrium data for all the biosorbents studied. The rate of RB removal subjected to kinetic analysis using pseudo-first-order, pseudo-second-order, intra-particle diffusion and Elovich models. Pseudo-second-order kinetic model better described the experimental data of the RB biosorption. Desorption studies performed using 0.1 M sodium hydroxide as eluting agents for regeneration and recycle analysis. The recyclability of the six biosorbents showed consistent biosorption capacity towards RB removal up to the entire three cycles. The studied biosorbents sourced from large volume and easily available, further biosorption performance indicated that the KA, GS, GE, EKA, EGS and EGE could be used as efficient, alternative and eco-friendly biosorbents for the removal of harmful dyes in the environment.

The bioremediation potential of an aquifer contaminated with tetrachloroethene (PCE) was assessed by combining hydrogeochemical data of the site, microcosm studies, metabolites concentrations, compound specific-stable carbon isotope analysis and the identification of selected reductive dechlorination biomarker genes. The characterization of the site through 10 monitoring wells evidenced that leaked PCE was transformed to TCE and cis-DCE via hydrogenolysis. Carbon isotopic mass balance of chlorinated ethenes pointed to two distinct sources of contamination and discarded relevant alternate degradation pathways in the aquifer. Application of specific-genus primers targeting Dehalococcoides mccartyi species and the vinyl chloride-to-ethene reductive dehalogenase vcrA indicated the presence of autochthonous bacteria capable of the complete dechlorination of PCE. The observed cis-DCE stall was consistent with the aquifer geochemistry (positive redox potentials; presence of dissolved oxygen, nitrate, and sulphate; absence of ferrous iron), which was thermodynamically favourable to dechlorinate highly chlorinated ethenes but required lower redox potentials to evolve beyond cis-DCE to the innocuous end product ethene. Accordingly, the addition of lactate or a mixture of ethanol plus methanol as electron donor sources in parallel field-derived anoxic microcosms accelerated dechlorination of PCE and passed cis-DCE up to ethene, unlike the controls (without amendments, representative of field natural attenuation). Lactate fermentation produced acetate at near-stoichiometric amounts. The array of techniques used in this study provided complementary lines of evidence to suggest that enhanced anaerobic bioremediation using lactate as electron donor source is a feasible strategy to successfully decontaminate this site.