Removal of endocrine disruptors and pharmaceuticals by graphene oxide-based membranes in water: A review.

Membrane-based water treatment has emerged as a promising solution to address global water challenges. Graphene oxide (GO) has been successfully employed in membrane filtration processes owing to its reversible properties, large-scale production potential, layer-to-layer stacking, great oxygen-based functional groups, and unique physicochemical characteristics, including the creation of nano-channels. This review evaluates the separation performance of various GO-based membranes, manufactured by coating or interfacial polymerization with different support layers such as polymer, metal, and ceramic, for endocrine-disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs). In most studies, the addition of GO significantly improved the removal efficiency, flux, porosity, hydrophilicity, stability, mechanical strength, and antifouling performance compared to pristine membranes. The key mechanisms involved in contaminant removal included size exclusion, electrostatic exclusion, and adsorption. These mechanisms could be ascribed to the physicochemical properties of compounds, such as molecular size and shape, hydrophilicity, and charge state. Therefore, understanding the removal mechanisms based on compound characteristics and appropriately adjusting the operational conditions are crucial keys to membrane separation. Future research directions should explore the characteristics of the combination of GO derivatives with various support layers, by tailoring diverse operating conditions and compounds for effective removal of EDCs and PhACs. This is expected to accelerate the development of surface modification strategies for enhanced contaminant removal.

Synthesis, performance, and mechanisms of strontium ferrite-incorporated zeolite imidazole framework (ZIF-8) for the simultaneous removal of Pb(II) and tetracycline.

In this study, strontium ferrite (SF)-incorporated zeolite imidazole framework (ZIF-8) (SFZIF-8) that can simultaneously uptake Pb(II) and tetracycline (TC) in solution was synthesized and characterized. The physicochemical properties of the as-prepared SFZIF-8 were characterized by various functional groups, higher average pore diameter (3.414 nm), and stronger negative charge (-30.5 mV). Adsorption kinetics, isotherms, effect of various water conditions including solution pH and temperature, and reusability were studied to evaluate its adsorption performance. The adsorption capacity of SFZIF-8 was compared with that of commonly used adsorbents (powder and granular activated carbon). SFZIF-8 showed much higher adsorption performance (429.6 mg/g and 433.4 mg/g for Pb(II) and TC, respectively) than powder activated carbon (129.9 mg/g and 142.0 mg/g for Pb(II) and TC, respectively) and granular activated carbon (249.3 mg/g and 263.0 mg/g for Pb(II) and TC, respectively) in Pb(II) and TC binary solutions. The SFZIF-8 adsorption behaviors for the removal of Pb(II) and TC were explained by the pseudo-first-order and Langmuir models from the adsorption kinetics and isotherm experiments, respectively. The regenerated SFZIF-8 exhibited a competitive performance even after the third cycle. These results indicate that Pb(II) and TC can be removed with SFZIF-8 via electrostatic attraction, surface complexation, hydrogen bonding, and π-π interactions. Therefore, by exhibiting effective and efficient adsorption performance, SFZIF-8 nanocomposites can be utilized as alternative and promising adsorbents for the simultaneous removal of both Pb(II) and TC.

A simple reagent-less approach using electrical discharge as a substitution for chelating agent in addressing genomic assay inhibition by divalent cations.

Electrical discharge treatment was shown to be a viable substitution for chelating agent in genomic assays. Divalent cation Mg2+ inhibits the performance of DNA hybridization based genomic assays by binding to the DNA and disrupting DNA hybridization. Until now, chelating agents such as ethylenediaminetetraacetic acid (EDTA) was the only option to address the presence of Mg2+ in samples. However, EDTA is a well-known environmental contaminant. In this work, we successfully employed electrical discharge instead of EDTA to render Mg2+ insipid. Its preliminary efficacy was first observed via circular dichroism (CD) and zeta potential analyses. After electrical discharge treatment, the reduction in CD shift at 280 nm was significant for samples with 10-3 and 10-8 M Mg2+. The zeta potential of Mg2+ laden samples were also restored from -4.71 ± 1.38 to -20.59 ± 6.37 mV after electrical discharge treatment. Both CD shift and change in zeta potential suggested that 2 min of electrical discharge treatment could prevent Mg2+ from binding to DNA. The complete efficacy of electrical discharge treatment was demonstrated with the performance recovery (within ∼15% of the control) of a genomic assay variant (NanoGene assay) while analyzing Mg2+ laden samples (10-5-10-3 M). Assuming 10 million samples are analyzed annually, the proposed electrical discharge treatment (∼50 mW per sample) would allow us to trade environmental contamination by ∼50 kg of hazardous EDTA with a single 250 W STC (standard test conditions) solar panel.

Adsorption of Ba2+ and Sr2+ on Ti3C2Tx MXene in model fracking wastewater.

Wastewater from hydraulic fracking contains both organic and inorganic pollutants; the latter include radioactive nuclides such as Ba2+ and Sr2+. We explored whether MXene (Ti3C2Tx), a novel adsorbent, could remove Ba2+ and Sr2+ from model wastewater. Zeta potential analysis showed that MXene had a high negative surface charge. MXene adsorbed Ba2+ and Sr2+ via electrostatic attraction, as confirmed by the adsorption at different solution pH values and in the presence of various concentrations of other ions (NaCl and CaCl2). MXene exhibited outstanding adsorption of Ba2+ and Sr2+, to approximately 180 and 225 mg g-1, respectively, when 1 g L-1 MXene was admixed with adsorbates at 2 g L-1. MXene exhibited very rapid adsorption kinetics, attaining equilibrium within 1 h. X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy revealed that MXene adsorbed Ba2+ and Sr2+, respectively, via ion exchange and inner-sphere complex formation. Finally, we performed MXene reusability tests; reusability was excellent over at least four cycles. Thus, MXene removed Ba2+ and Sr2+ from model fracking wastewater.

Heterogeneous sonocatalytic degradation of an anionic dye in aqueous solution using a magnetic lanthanum dioxide carbonate-doped zinc ferrite-reduced graphene oxide nanostructure.

We report herein the sonochemical synthesis of a lanthanum dioxide carbonate (La2O2CO3) and zinc ferrite (ZnFe2O4)-loaded reduced graphene oxide (LZF-rGO) nanoheterostructure for ultrasound (US)-assisted degradation of methyl orange (MO) from water. The MO was chosen as a model organic dye due to its toxicological and biodegradable-resistant properties. The LZF-rGO catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The results of characterizations confirmed successful synthesis of sonocatalyst. Among different removal systems, US/LZF-rGO displayed outstanding sonodegradation performance for degradation of MO. The maximum removal efficiency of 75.9% was achieved using 0.2 g/L sonocatalyst, 20 mg/L MO, and 0.71 W/cm2 US power intensity for 65 min. MO can be partially adsorbed on LZF-rGO but mostly sonodegraded by reactive radical species. The reaction conditions were optimized by investigating the effect of key operating parameters, including the sonocatalyst dosage, initial MO concentration, US power intensity, presence of inorganic salts, and use of an enhancer, on the decolorization of MO. The degradation intermediates produced from MO during the sonocatalytic process were identified by UPLC®/MS-MS, and possible mechanism and pathway for the degradation of MO in the US/LZF-rGO system were also proposed. Reusability experiments with this sonocatalyst revealed a less than 10% drop in the degradation efficiency after four adsorption-desorption cycles.

Removal of lead and bisphenol A using magnesium silicate impregnated palm-shell waste powdered activated carbon: Comparative studies on single and binary pollutant adsorption.

In this work, palm shell waste powder activated carbon coated by magnesium silicate (PPAC-MS) were synthesized by the impregnation of magnesium silicate (MgSiO3) using economical material (silicon dioxide powder) via mild hydrothermal approach for the first time. As an effective adsorbent, PPAC-MS simultaneously removes BPA and Pb(II) in single and binary mode. Surprisingly, PPAC-MS exhibited a homogeneous thin plate mesh-like structure, as well as meso- and macropores with a high surface area of 772.1m2g-1. Due to its specific morphological characteristics, PPAC-MS had adsorption capacities of Pb(II) as high as 419.9mgg-1 and 408.8mgg-1 in single mode and binary mode based on Freudliuch isotherm model while those for BPA by PPAC-MS were 168.4mgg-1 and 254.7mgg-1 for single mode and binary modes corresponding to Langmuir isotherm model. Experiment results also indicated that the synergistic removal of BPA occurred because the precipitation process of Pb(II) leads to the co-precipitation of BPA with Pb(OH)2 compound. PPAC-MS showed a good reusability for 5 regeneration cycles using Mg(II) solution followed by thermal treatment. Overall, PPAC-MS has a high potential in the treatment process for wastewater containing both toxic heavy metals and emerging pollutants due to its high sorption capacities and reusability.

Evaluation of biochar-ultrafiltration membrane processes for humic acid removal under various hydrodynamic, pH, ionic strength, and pressure conditions.

The performance of an ultrafiltration (UF)-biochar process was evaluated in comparison with a UF membrane process for the removal of humic acid (HA). Bench-scale UF experiments were conducted to study the rejection and flux trends under various hydrodynamic, pH, ionic strength, and pressure conditions. The resistance-in-series model was used to evaluate the processes and it showed that unlike stirred conditions, where low fouling resistance was observed (28.7 × 1012 m-1 to 32.5 × 1012 m-1), higher values and comparable trends were obtained for UF-biochar and UF alone for unstirred conditions (28.7 × 1012 m-1 to 32.5 × 1012 m-1). Thus, the processes were further evaluated under unstirred conditions. Additionally, total fouling resistance was decreased in the presence of biochar by 6%, indicating that HA adsorption by biochar could diminish adsorption fouling on the UF membrane and thus improve the efficiency of the UF-biochar process. The rejection trends of UF-biochar and UF alone were similar in most cases, whereas UF-biochar showed a noticeable increase in flux of around 18-25% under various experimental conditions due to reduced membrane fouling. Three-cycle filtration tests further demonstrated that UF-biochar showed better membrane recovery and antifouling capability by showing more HA rejection (3-5%) than UF membrane alone with each subsequent cycle of filtration. As a result of these findings, the UF-biochar process may potentially prove be a viable treatment option for the removal of HA from water.

An efficient and economical treatment for batik textile wastewater containing high levels of silicate and organic pollutants using a sequential process of acidification, magnesium oxide, and palm shell-based activated carbon application.

Considering the chemical properties of batik effluents, an efficient and economical treatment process was established to treat batik wastewater containing not only high levels of Si and chemical oxygen demand (COD), but also toxic heavy metals. After mixing the effluents obtained from the boiling and soaking steps in the batik process, acidification using concentrated hydrochloric acid (conc. HCl) was conducted to polymerize the silicate under acidic conditions. Consequently, sludge was produced and floated. XRD and FT-IR analyses showed that wax molecules were coordinated by hydrogen bonding with silica (SiO2). The acidification process removed ∼78-95% of COD and ∼45-50% of Si, depending on the pH. In the next stage, magnesium oxide (MgO) was applied to remove heavy metals completely and almost 90% of the Si in the liquid phase. During this step, about 70% of COD was removed in the hydrogel that arose as a consequence of the crosslinking characteristics of the formed nano-composite, such as magnesium silicate or montmorillonite. The hydrogel was composed mainly of waxes with polymeric properties. Then, the remaining Si (∼300 mg/L) in the wastewater combined with the effluents from the rinsing steps was further treated using 50 mg/L MgO. As a final step, palm-shell activated carbon (PSAC) was used to remove the remaining COD to < 50 mg/L at pH 3. Overall, the sequential process of acidification and MgO/PSAC application developed could serve as an economical and effective treatment option for treating heavily polluted batik effluents.

Optimization of naproxen and ibuprofen removal in photolysis using a Box-Behnken design: effect of Fe(III), NO3-, and humic acid.

This study investigated the roles and optimum conditions of four independent variables [ultraviolet (UV) intensity, Fe(III), NO3 (-), and humic acid (HA) concentration] in the photolytic removal of naproxen (NPX) and ibuprofen (IBP) in water using a response surface method based on the Box-Behnken design. Lab-scale experiments used analysis of variance and t-test statistics to test the significance of independent variables and their interactions. Predicted levels of NPX and IBP removals were found to be in good agreement with experimental levels (R(2) = 0.9891 for NPX and 0.9936 for IBP). UV intensity and HA were the most positively and negatively significant variables (P < 0.001), respectively. However, Fe(III) and NO3 (-) ions had a less significant impact (P > 0.05). This result implies that NPX was removed by both direct photolysis (photons) and indirect reaction (OH radical), while IBP was removed mainly by the OH radical. NPX was more susceptible to the OH radical than IBP (kOH/NPX = 8.24 × 10(9) M(-1)s(-1) and kOH/IBP = 7.51 × 10(9) M(-1)s(-1)). According to a quadratic regression model, the predicted maximum removal efficiencies for NPX and IBP were 71.66% and 63.58% when the predicted optimum ratio of UV (mW cm(-2)):Fe(III) (mg/L):NO3(-) (mg/L):HA (mg/L) was 6.3:0.94:0:0 and 6.3:0.94:20:0, respectively, which was similar to the respective experimental NPX and IBP removal values of 70.21% and 62.16%. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Environmental Science and Health, Part A, to view the supplemental file.

Determination of micropollutants in combined sewer overflows and their removal in a wastewater treatment plant (Seoul, South Korea).

The present study investigated the occurrence of 29 selected micropollutants such as endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in surface waters and wastewaters in Seoul (South Korea) during both dry and wet weather conditions. The study area was selected based on the lack of available information regarding the suspected contamination of rivers/creeks by EDCs and PPCPs in the Seoul region and the presence of a wastewater treatment plant (WWTP), which serves approximately 4.1 million inhabitants and has a design capacity of 1,297 × 10(3) m(3)/day. Many target compounds (83 %) were detected in samples collected from wastewater treatment influent/effluent, creek water, and combined sewer overflow (CSO). The total EDC/PPCP concentrations were as follows: WWTP influent (69,903 ng/L) > WWTP effluent (50,175 ng/L) >3 creek samples (16,035-44,446 ng/L) during dry weather, and WWTP influent (53,795 ng/L) > WWTP bypass (38,653 ng/L) >5 creek samples (15,260-29,113 ng/L) >2 CSO samples (11,109-11,498 ng/L) during wet weather. EDCs and PPCPs were found to be present at high daily loads (65.1 and 69.8 kg/day during dry and wet weather, respectively) in the WWTP effluent. Compound removal by the WWTP varied significantly by compound: caffeine, diclofenac, ibuprofen, naproxen, and propylparaben (>90 %), and acesulfame, DEET, iohexol, iopromide, and iopamidol (<5 %). These findings and literature information support the hypothesis that the efficiency of removal of EDCs and PPCPs is strongly dependent on both removal mechanism (e.g., biodegradation, adsorption to sludge, and oxidation by chlorine) and compound physicochemical properties (e.g., pK a and hydrophobicity).

Photocatalytic boron nitride-based nanomaterials for the removal of selected organic and inorganic contaminants in aqueous solution: A review.

Boron nitride (BN) coupled with various conventional and advanced photocatalysts has been demonstrated to exhibit extraordinary activity for photocatalytic degradation because of its unique properties, including a high surface area, constant wide-bandgap semiconducting property, high thermal-oxidation resistance, good hydrogen-adsorption performance, and high chemical/mechanical stability. However, only limited reviews have discussed the application of BN or BN-based nanomaterials as innovative photocatalysts, and it does not cover the recent results and the developments on the application of BN-based nanomaterials for water purification. Herein, we present a complete review of the present findings on the photocatalytic degradation of different contaminants by various BN-based nanomaterials. This review includes the following: (i) the degradation behavior of different BN-based photocatalysts for various contaminants, such as selected dye compounds, pharmaceuticals, personal care products, pesticides, and inorganics; (ii) the stability/reusability of BN-based photocatalysts; and (iii) brief discussion for research areas/future studies on BN-based photocatalysts.

Ultrasonic treatment of endocrine disrupting compounds, pharmaceuticals, and personal care products in water: An updated review.

Pharmaceuticals, personal care products (PPCPs), and endocrine-disrupting compounds (EDCs) have seen a recent sustained increase in usage, leading to increasing discharge and accumulation in wastewater. Conventional water treatment and disinfection processes are somewhat limited in effectively addressing this micropollutant issue. Ultrasonication (US), which serves as an advanced oxidation process, is based on the principle of ultrasound irradiation, exposing water to high-frequency waves, inducing thermal decomposition of H2O while using the produced radicals to oxidize and break down dissolved contaminants. This review evaluates research over the past five years on US-based technologies for the effective degradation of EDCs and PPCPs in water and assesses various factors that can influence the removal rate: solution pH, temperature of water, presence of background common ions, natural organic matter, species that serve as promoters and scavengers, and variations in US conditions (e.g., frequency, power density, and reaction type). This review also discusses various types of carbon/non-carbon catalysts, O3 and ultraviolet processes that can further enhance the degradation efficiency of EDCs and PPCPs in combination with US processes. Furthermore, numerous types of EDCs and PPCPs and recent research trends for these organic contaminants are considered.

Ultrasonic treatment of dye chemicals in wastewater: A review.

The existence of pollutants, such as toxic organic dye chemicals, in water and wastewater raises concerns as they are inadequately eliminated through conventional water and wastewater treatment methods, including physicochemical and biological processes. Ultrasonic treatment has emerged as an advanced treatment process that has been widely applied to the decomposition of recalcitrant organic contaminants. Ultrasonic treatment has several advantages, including easy operation, sustainability, non-secondary pollutant production, and saving energy. This review examines the elimination of dye chemicals and categorizes them into cationic and anionic dyes based on the existing literature. The objectives include (i) analyzing the primary factors (water quality and ultrasonic conditions) that influence the sonodegradation of dye chemicals and their byproducts during ultrasonication, (ii) assessing the impact of the different sonocatalysts and combined systems (with ozone and ultraviolet) on sonodegradation, and (iii) exploring the characteristics-based removal mechanisms of dyes. In addition, this review proposes areas for future research on ultrasonic treatment of dye chemicals in water and wastewater.

Adsorption of uranyl ion on hexagonal boron nitride for remediation of real U-contaminated soil and its interpretation using random forest.

Acid leaching has been widely applied to treat contaminated soil, however, it contains several inorganic pollutants. The decommissioning of nuclear power plants introduces radioactive and soluble U(VI), a substance posing chemical toxicity to humans. Our investigation sought to ascertain the efficacy of hexagonal boron nitride (h-BN), an highly efficient adsorbent, in treating U(VI) in wastewater. The adsorption equilibrium of U(VI) by h-BN reached saturation within a mere 2 h. The adsorption of U(VI) by h-BN appears to be facilitated through electrostatic attraction, as evidenced by the observed impact of pH variations, acidic agents (i.e., HCl or H2SO4), and the presence of background ions on the adsorption performance. A reusability test demonstrated the successful completion of five cycles of adsorption/desorption, relying on the surface characteristics of h-BN as influenced by solution pH. Based on the experimental variables of initial U(VI) concentration, exposure time, temperature, pH, and the presence of background ions/organic matter, a feature importance analysis using random forest (RF) was carried out to evaluate the correlation between performances and conditions. To the best of our knowledge, this study is the first attempt to conduct the adsorption of U(VI) generated from real contaminated soil by h-BN, followed by interpretation of the correlation between performance and conditions using RF. Lastly, a. plausible adsorption mechanism between U(VI) and h-BN was explained based on the experimental results, characterizations, and a. comparison with previous adsorption studies on the removal of heavy metals by h-BN.

Photocatalytic and electrocatalytic degradation of bisphenol A in the presence of graphene/graphene oxide-based nanocatalysts: A review.

Bisphenol A (BPA), a widely recognized endocrine disrupting compound, has been discovered in drinking water sources/finished water and domestic wastewater influent/effluent. Numerous studies have shown photocatalytic and electrocatalytic oxidation to be very effective for the removal of BPA, particularly in the addition of graphene/graphene oxide (GO)-based nanocatalysts. Nevertheless, the photocatalytic and electrocatalytic degradation of BPA in aqueous solutions has not been reviewed. Therefore, this review gives a comprehensive understanding of BPA degradation during photo-/electro-catalytic activity in the presence of graphene/GO-based nanocatalysts. Herein, this review evaluated the main photo-/electro-catalytic degradation mechanisms and pathways for BPA removal under various water quality/chemistry conditions (pH, background ions, natural organic matter, promotors, and scavengers), the physicochemical characteristics of various graphene/GO-based nanocatalysts, and various operating conditions (voltage and current). Additionally, the reusability/stability of graphene/GO-based nanocatalysts, hybrid systems combined with ozone/ultrasonic/Fenton oxidation, and prospective research areas are briefly described.

Quantitative detection of single walled carbon nanotube in water using DNA and magnetic fluorescent spheres.

Carbon nanotubes (CNTs) possess unique properties that have led to an increase in their research and usage for a wide variety of fields. This growing demand of CNTs poses a major public health risk given its unregulated release into the environment. Unfortunately there is a significant information gap on the actual quantity of CNTs in the environment due to limitation of existing detection methods. This is mainly owing to the ubiquitous carbon chemistry of CNT. In response we developed a method (CNT-capture method) that is able to structurally differentiate CNT from other interference carbon materials in an aqueous medium. The affinity between single walled nanotubes (SWNTs) and specific single stranded DNA (ssDNA) was employed to capture SWNTs in water. SWNT-specific separation was obtained via magnetic separation. Dual fluorescent labels attached to sandwich ssDNA probes were used for quantification. The specific affinity between DNA and SWNTs was verified and no significant side-interactions were observed. With optimized incubation duration (30 min) and buffer composition (10(-7) % sodium dodecyl sulfate and pH 7.9), a calibration curve of quantification (R(2) = 0.90) was obtained with a range of SWNT concentration (0.05-10 µg/mL) against graphene as a planar analog. Comparison to other spectroscopy based methods was carried out to highlight the specificity and sensitivity of the presented method for CNT detection in aquatic sample.

Genetic localization and in vivo characterization of a Monascus azaphilone pigment biosynthetic gene cluster.

Monascus spp. produce several well-known polyketides such as monacolin K, citrinin, and azaphilone pigments. In this study, the azaphilone pigment biosynthetic gene cluster was identified through T-DNA random mutagenesis in Monascus purpureus. The albino mutant W13 bears a T-DNA insertion upstream of a transcriptional regulator gene (mppR1). The transcription of mppR1 and the nearby polyketide synthase gene (MpPKS5) was significantly repressed in the W13 mutant. Targeted inactivation of MpPKS5 also gave rise to an albino mutant, confirming that mppR1 and MpPKS5 belong to an azaphilone pigment biosynthetic gene cluster. This M. purpureus sequence was used to identify the whole biosynthetic gene cluster in the Monascus pilosus genome. MpPKS5 contains SAT/KS/AT/PT/ACP/MT/R domains, and this domain organization is preserved in other azaphilone polyketide synthases. This biosynthetic gene cluster also encodes fatty acid synthase (FAS), which is predicted to assist the synthesis of 3-oxooactanoyl-CoA and 3-oxodecanoyl-CoA. These 3-oxoacyl compounds are proposed to be incorporated into the azaphilone backbone to complete the pigment biosynthesis. A monooxygenase gene (an azaH and tropB homolog) that is located far downstream of the FAS gene is proposed to be involved in pyrone ring formation. A homology search on other fungal genome sequences suggests that this azaphilone pigment gene cluster also exists in the Penicillium marneffei and Talaromyces stipitatus genomes.

Adsorptive and photocatalytic performance of cobalt-doped ZnTiO3/Ti3C2Tx MXene nanohybrids towards tetracycline: Kinetics and mechanistic insight.

Tetracycline (TC) antibiotics are widely used in animal husbandry and can cause environmental risk due to its high ecological toxicity and persistence. In this study, cobalt doped/ZnTiO3 (ZTO)/Ti3C2Tx MXene (ZCxTM, x indicates wt% of Co loading) was synthesized and explored to remove TC by adsorption and photocatalysis under visible light irradiation. The as-prepared ZC5TM was characterized using various analytical techniques, and key operating parameters such as solution pH, background ions, and temperature were systematically investigated. Interestingly, ZC5TM (14.9 mg/g) showed excellent adsorption capacity for TC, which was higher than activated carbon (7.7 mg/g), ZTO (4.9 mg/g), ZC3T (5.2 mg/g), ZC5T (5.3 mg/g), MXene (12.1 mg/g), ZTOM (12.5 mg/g), and ZC3TM (12.9 mg/g). The pseudo-second-order kinetics and Langmuir isotherm models well explained the effect of contact time and initial concentrations on the adsorption of TC. The adsorption process was primarily through the electrostatic attraction, surface complexation, and hydrogen bonding. In addition, MXene and Co doped on ZTO served as co-catalyst and reduced recombination rate of photo-generated e--h+ pairs by the intimate interface of its heterojunction. Thus, ZC5TM was highly effective for the photocatalytic degradation of residual TC after adsorption by showing 18% TC degradation rate, compared to 8% and 9% degradation rate for ZTO and MXene, respectively. There results finally support the feasible use of ZC5TM as efficient adsorbent and photocatalyst in removal of TC in wastewater.

Enhanced catalytic oxidation of naproxen via activation of peroxymonosulfate by Fe-based metal-organic framework aerogels functionalized with Ag nanoparticles.

In this study, Ag3PO4 and Fe-based metal-organic frameworks (MOFs)-functionalized three-dimensional (3D) porous gelatin aerogels (Ag/Fe@GMA) were fabricated and used as adsorbents and catalysts for the activation of peroxymonosulfate (PMS) for naproxen (NPX) removal from water. The morphology, crystallinity, surface functional groups, and surface chemical element compositions of the fabricated Ag/Fe@GMA was evaluated using various analytical techniques. Our results showed that as an adsorbent, Ag/Fe@GMA showed a 18.0 % higher NPX adsorption capacity compared with the pristine aerogels. This can be attributed to the well-embedded Ag3PO4 and MOFs, indicating a stronger interaction between functionalized aerogels and NPX. After adsorption, 99.9 % of total NPX removal was achieved within 15 min by activating PMS and effectively generating •OH and •SO4- in water. The PMS/Ag/Fe@GMA aerogel system also showed high removal performance for rhodamine B (99.5 %) and tetracycline (93.7 %). Moreover, the Ag/Fe@GMA aerogels showed excellent reusability to achieve 95.7 % NPX removal efficiency after six times of recycling. This study revealed that the Ag/Fe@GMA aerogels had good potential for PMS activation and NPX removal. In particular, as an alternative to powdery materials, 3D shape of Ag/Fe@GMA with excellent reusability facilitates its application in the treatment of water contaminated with organic contaminants.

Hydrophilic sulfurized nanoscale zero-valent iron for enhancing in situ biocatalytic denitrification: Mechanisms and long-term column studies.

The aim of this study was to investigate the effects of hydrophilic sulfur-modified nanoscale zero-valent iron (S-nZVI) as a biocatalyst for denitrification. We found that the denitrifying bacteria Cupriavidus necator (C. necator) promoted Fe corrosion during biocatalytic denitrification, reducing surface passivation and sulfur species leaching from S-nZVI. As a result, S-nZVI exhibited a higher synergistic factor (fsyn = 2.43) for biocatalytic NO3- removal than nanoscale zero-valent iron (nZVI, fsyn = 0.65) at an initial nitrate concentration of 25 mg L-1-N. Based on kinetic profiles, SO42- was the preferred electron acceptor over NO3- when using C. necator and S-nZVI for biocatalytic denitrification. Up-flow column experiments demonstrated that biocatalytic denitrification using S-nZVI achieved a total nitrogen removal capacity of up to 2004 mg L-1 for 127 d. Notably, microbiome taxonomic profiling showed that the addition of S-nZVI to the groundwater promoted the growth of Geobacter, Desulfosporosinus, Streptomyces, and Simplicispira spp in the column experiments. Most of those microbes can reduce sulfate, promote denitrification, and match the batch kinetic profile obtained using C. necator. Our results not only discover the great potential of S-nZVI as a biocatalyst for enhancing denitrification via microbial activation but also provide a deep understanding of the complicated abiotic-biotic interaction.