During chlorine disinfection process, reactions between the disinfectant and 17β-estradiol (E2) lead to the formation of halogenated disinfection byproducts (DBPs) which can be a risk to both ecosystem and human health. The degradation and transformation products of E2 in sodium hypochlorite (NaClO) disinfection processes of different water samples were investigated. The reaction kinetics research showed that the degradation rates of E2 were considerably dependent on the initial pH value and the types of water samples. In fresh water, synthetic marine aquaculture water and seawater, the reaction rate constant was 0.133 min−1, 2.067 min−1 and 2.592 min−1, respectively. The reasons for the above phenomena may be due to the different concentrations of bromide ions (Br−) in these three water samples which could promote the reaction between NaClO and E2. Furthermore, Br− could also cause the formation of brominated DBPs (Br-DBPs). The main DBPs, reaction centers and conceivable reaction pathways were explored. Seven halogenated DBPs have been observed including three chlorinated DBPs (Cl-DBPs) and four Br-DBPs. The active sites of E2 were found to be the pentabasic cyclic ring and the ortho position of the phenol moiety as well as C9-C10 position. The identified Cl/Br-DBPs were also confirmed in actual marine aquaculture water from a shrimp pond. The comparison of bio-concentration factors (BCF) values based on calculation of EPI-suite showed that the toxicities of the Br-DBPs were stronger than that of their chloride analogues. The absorbable organic halogens (AOX) analysis also suggested that the DBPs produced in the marine aquaculture water were more toxic than that in the fresh water system.

Heavy metal pollution of water sources has raised global environmental sustainability concerns, calling for the development of high-performance materials for effective pollution treatment. Herein, we report a facile approach to synthesize carbonaceous nanofiber/NiAl layered double hydroxide (CNF/LDH) nanocomposites for high-efficiency elimination of heavy metals from aqueous solutions. The CNF/LDH nanocomposites were characterized by three-dimensional architectures formed by the gradual self-assembly of flower-like LDH on CNF. The nanocomposites exhibited excellent hydrophilicity and high structural stability in aqueous solutions, guaranteeing the high availability of active sites in these environments. High-efficiency elimination of heavy metal ions by the CNF/LDH nanocomposites was demonstrated by the high uptake capacities of Cu(II) (219.6 mg/g) and Cr(VI) (341.2 mg/g). The sorption isotherms coincided with the Freundlich model, most likely because of the presence of heterogeneous binding sites. The dominant interaction mechanisms consisted of surface complexation and electrostatic interaction, as verified by a combination of X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy analyses and density functional theory calculations. The results presented herein confirm the importance of CNF/LDH nanocomposites as emerging and promising materials for the efficient removal of heavy metal ions and other environmental pollutants.

Bisphenol A (BPA) is a widely concerned endocrine disrupting chemical and hard to be removed through conventional wastewater treatment processes. In this study, we developed a TiO2 decorated titanate nanotubes composite (TiO2/TNTs) and used for photocatalytic degradation of BPA. TEM and XRD analysis show that the TiO2/TNTs is a nano-composite of anatase and titanate, with anatase acting as the primary photocatalytic site and titanate as the skeleton. TiO2/TNTs exhibited excellent photocatalytic reactivity and its easy-settling property leaded to good reusability. After 5 reuse cycles, TiO2/TNTs also could photo-degrade 91.2% of BPA with a high rate constant (k1) of 0.039 min⁻¹, which was much better than TiO2 and TNTs. Higher pH facilitated photocatalysis due to more reactive oxygen species produced and less material aggregation. The presence of NaCl and CaCl2 showed negligible effects on BPA degradation, but NaHCO3 caused an inhibition effect resulting from consumption of ·OH. Humic acid inhibited degradation mainly due to blockage of the active sites of TiO2/TNTs. Degradation pathway was well interpreted through theoretical calculation. Hydroxyl radical played the dominate role in BPA photodegradation, and the atoms of BPA with high Fukui index based on density-functional theory (DFT) calculation are the radical easy-attacking (f⁰) sites. Considering the good photocatalytic reactivity, reusability, stability and settle property, TiO2/TNTs promises to be an efficient alternative for removal of organic compounds from wastewaters.

The implications of humic acid (HA) regarding surface properties of graphene materials and their interactions with phthalic acid esters (PAEs) are not vivid. We report the role of HA on graphene oxide (GO) and reduced graphene oxide (RGO) for sorption-desorption behavior of PAEs. Besides higher surface area and pore volume, the hydrophobic π-conjugated carbon atoms on RGO ensured prominent adsorption capacity towards PAEs in comparison to hydrophilic GO, highlighting the hydrophobic effect. After adjusting for the hydrophobic effect by calculating the hexadecane-water partition coefficient (KHW) normalized adsorption coefficient (Kd/KHW), the dimethyl phthalate (DMP) molecule portrayed a higher adsorption affinity towards RGO by π-π electron donor–acceptor (EDA) interaction for active sites on graphene interface via sieving effect. In contrast to RGO, the weak π-π EDA interactions and H-bonding was observed between the carbonyl groups of PAEs and oxygen containing functional groups on GO. There was no obvious change in morphologies of GO and RGO before and desorption as revealed by SEM and TEM images, as desorption hysteresis did not occur in all conditions. The presence of HA also resulted in shielding effect thereby decreasing the adsorption rate and capacity of diethyl phthalate (DEP) on GO and RGO, while it had little effect on DMP, probably due to the adsorbed HA as new active sites. The desorption of DMP and DEP on RGO in presence of HA was quick and enhanced. These results should be important for evaluating the fate and health risk of graphene materials and PAEs in the environment.

The present work evaluates the action of nitroreductase enzyme immobilized on Tosylactivated magnetic particles (MP-Tosyl) on three disperse dyes which contain nitro and azo groups. The dyes included Disperse Red 73 (DR 73), Disperse Red 78 (DR 78), and Disperse Red 167 (DR 167). The use of a magnet enabled the rapid and easy removal of the immobilized enzyme after biotransformation; this facilitated the identification of the products generated using high-performance liquid chromatography with diode array detector (HPLC-DAD) and mass spectrometry (LC-MS/MS). The main products formed by the in vitro biotransformation were identified as the product of nitro group reduction to the correspondent amine groups, which were denoted as follows: 50% of 2-(2-(4-((2-cyanoethyl)(ethyl)amino)phenyl)hydrazinyl)-5-nitrobenzonitrile, 98% of 3-((4-((4-amino-2-chlorophenyl) diazenyl)phenyl) (ethyl)amino)propanenitrile and 99% of (3-acetamido-4 - ((4-amino-2-chlorophenyl) diazenyl) phenyl) azanediyl) bis (ethane-2,1-diyl) for DR 73, DR 78 and DR 167, respectively. Based on the docking studies, the dyes investigated were found to be biotransformed by nitroreductase enzyme due to their favorable interaction with the active site of the enzyme. Theoretical results show that DR73 dye exhibits a relatively lower rate of degradation; this is attributed to the cyanide substituent which affects the electron density of the azo group. The docking studies also indicate that all the dyes presented significant reactivity towards DNA. However, Disperse Red 73 was found to exhibit a substantially higher reactivity compared to the other dyes; this implies that the dye possesses a relatively higher mutagenic power. The docking results also show that DR 73, DR 78 and DR 167 may be harmful to both humans and the environment, since the mutagenicity of nitro compounds is associated with the products formed during the reduction of nitro groups. These products can interact with biomolecules, including DNA, causing toxic and mutagenic effects.

Cryptomelane-type octahedral molecular sieve manganese oxide (OMS-2) possesses high redox potential and has attracted much interest in its application for oxidation arsenite (As(III)) species of arsenic to arsenate (As(V)) to decrease arsenic toxicity and promote total arsenic removal. However, coexisting ions such as As(V) and phosphate are ubiquitous and readily bond to manganese oxide surface, consequently passivating surface active sites of manganese oxide and reducing As(III) oxidation. In this study, we present a novel strategy to significantly promote As(III) oxidation activity of OMS-2 by tuning K+ concentration in the tunnel. Batch experimental results reveal that increasing K+ concentration in the tunnel of OMS-2 not only considerably improved As(III) oxidation kinetics rate from 0.027 to 0.102 min−1, but also reduced adverse effect of competitive ion on As(III) oxidation. The origin of K+ concentration effect on As(III) oxidation was investigated through As(V) and phosphate adsorption kinetics, detection of Mn2+ release in solution, surface charge characteristics, and density functional theory (DFT) calculations. Experimental results and theoretical calculations confirm that by increasing K+ concentration in the OMS-2 tunnel not only does it improve arsenic adsorption on K+ doped OMS-2, but also accelerates two electrons transfers from As(III) to each bonded Mn atom on OMS-2 surface, thus considerably improving As(III) oxidation kinetics rate, which is responsible for counteracting the adverse adsorption effects by coexisting ions.

Bivalves use anti-oxidative enzyme systems to defend themselves against excessive reactive oxygen species, which are often catalyzed by environmental pollution. As a key member of anti-oxidative enzyme family, catalase plays a crucial role in scavenging the high level of reactive oxygen species to protect organisms against various oxidative stresses. In this study, a catalase homologue was identified from Mytilus coruscus (named McCAT, KX957929). The open reading frame of McCAT was 1844bp with a 5′ untranslated region of 341bp and a 3′ untranslated region of 927bp. The deduced amino acid sequence was 512 residues in length with theoretical pI/MW 8.02/57.91kDa. BLASTn and phylogenetic analyses strongly suggested that it was a member of catalase, also known as CAT family for its conserved catalytic site motif and proximal heme-ligand signature motif. Real-time fluorescence quantitative PCR showed that constitutive expression of McCAT was occurred, with increasing order in mantle, adductor, gill, hemocyte, gonad and hepatopancreas. It was observed that bacterial infection and heavy metals stimulation up-regulated McCAT mRNA expression in hepatopancreas with time-dependent manners. The maximum expression appeared at 8h after pathogenic bacteria injecting, with 15-fold in Vibrio parahemolyticus and 60-fold in Aeromonas hydrophila than that of 0h. The highest point of McCAT mRNA appeared at different times for exposure to heavy metals with copper at day 5 (0.1mg/L 30-fold, 0.5mg/L 15-fold, 1.5mg/L 6-fold) and plumbum at day 3 (3.0mg/L 20-fold). The enzymatic activity analysis found that McCAT activity in the gill of M. coruscus was affected by heavy metals concentration. The results suggested that McCAT plays a significant role in antioxidation and the expression of McCAT can be used as a biomarker for detection of marine environmental pollution.

The investigation and development of technologies to remediate water contaminated with NO₃⁻ are constantly increasing. An economically and potentially effective alternative is based on the catalytic hydrogenation of NO₃⁻ to N₂. With this objective, bimetallic RhMo₆ catalysts based on Anderson-type heteropolyanion (RhMo₆O₂₄H₆)³⁻ were prepared and characteri3ed in order to obtain well-defined bimetallic catalyst. The catalysts were supported on Al₂O₃ with different textural properties and on silica. The heteropolyanion-support interaction was analysed by temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). The differences obtained in activity and selectivity to the different products can be assigned to the different interaction between the RhMo₆ Anderson phase and the supports. The RhMo₆/G, (G: γ-Al₂O₃) system showed the best catalytic performance. This catalyst exhibited the lowest reduction temperature of Rh and Mo in the TPR assay and a Rh/Mo surface ratio similar to that of the original phase, as observed by XPS analysis. These studies allowed us to verify a synergic effect between Rh and Mo, through which Mo reducibility was promoted by the presence of the noble metal. The catalytic activity was favoured by the active sites generated from the Anderson phase. This fact was confirmed by comparing the activity of RhMo₆/G with that corresponding to a conventional catalyst prepared through successive impregnation of both Rh (III) and Mo (VI) salts.

Aromatic substituted phenols and their by-products discharged from numerous industries are of environmental concern due to their toxic, carcinogenic, recalcitrant, and bioaccumulating properties. Therefore, their complete removal from waters by low-cost, efficient, environmentally friendly nanomaterial-based treatment techniques is desirable. Double metal cyanide complexes (DMCC) are the extremely useful heterogeneous and recoverable catalyst. Hence, green route has been developed for several DMCC and their photocatalytic efficiency was evaluated for degradation of toxic phenols. Herein, nanocubes for hexacyanocobaltate of iron (FeHCC ~ 200 nm), nickel (NiHCC < 10 nm), and zinc (ZnHCC ~ 500 nm) were synthesized after employing Aegle marmelos. Subsequently, at neutral pH and sunlight irradiation, 15 mg of catalysts were able to degrade the maximum extent of phenols (1 × 10⁻⁴ M) in the order: 3-aminophenol (96% ZnHCC > 94% FeHCC > 93% NiHCC) > phenol (94% ZnHCC > 92% FeHCC > 91% NiHCC) > 2,4-DNP (92% ZnHCC > 91% FeHCC > 90% NiHCC). This is attributed to highest basicity of 3-aminophenol containing excess of free electrons. Highest catalytic potential of ZnHCC (Xₘ = 0.54–0.43 mg/g) is because of its highest surface area and negative zeta potential along with sharp morphology and crystallinity. Adsorption of phenols over catalyst was statistically significant with Langmuir isotherms (R² ≥ 0.96; p value ≤ 0.05). Small and non-toxic by-products like oxalic acid, benzoquinone, (Z)-hex-3-enedioic acid, (Z)-but-2-enal, and (Z)-4-oxobut-2-enoic acid were identified in GC-MS. Degradation modes involving hydroxylation, oxidative skeletal rearrangement, and ring opening clearly supported enhanced oxidation of phenols by •OH. Overall, due to greater active sites, high surface activity, low band gap, and semiconducting nature, DMCC revealed promising potential for solar photocatalytic remediation of wastewater.

The potential to remove methylene blue (MB) basic dye and indigo carmine (IC) acidic dye, from wastewater treatment systems using corn stigmata through biosorption was investigated in batch experiments. The effects of contact time, solution pH, biosorbent dosage, initial dye concentration, salts, and temperature were sought. Results showed that the maximal uptakes of MB were 106.3 mg g⁻¹ at pH = 7 and 63.7 mg g⁻¹ for IC at pH = 2. In order to determine the properties and surface structure of the biomass physicochemical properties (pHₚzc, elemental analysis, Boehm’s titration, and chemical composition), spectral (FTIR analysis) and morphological characteristics (SEM) were investigated. Random distribution of the active sites was described by the new biosorption fractal model of Brouers–Sotolongo. The thermodynamic study demonstrated the favorable character of the biosorption of MB and of IC, which was inhibited by the presence of salts. The elucidation of the biosorption mechanism showed that the biosorption of MB onto corn stigmata was mainly controlled by chemisorption and the biosorption of IC was described by physisorption.