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Chromium (Cr), due to its greater contamination in aquifers and distinct eco-toxic impacts, is of greater environmental concern. This study aimed to synthesize nanocomposites of almond shells biochar (BC) with zerovalent bismuth and/or copper (Bi0/BC, Cu0/BC, and Bi0–Cu0/BC) for the removal of Cr from aqueous solution. The synthesized nanocomposites were investigated using various characterization techniques such as XRD, FTIR spectroscopy, SEM, and EDX. The Cr removal potential by the nanocomposites was explored under different Cr concentrations (25–100 mg/L), adsorbent doses (0.5–2.0 g/L), solution pH (2–8), and contact time (10–160 min). The above-mentioned advanced techniques verified successful formation of Bi0/Cu0 and their composite with BC. The synthesized nanocomposites were highly effective in the removal of Cr. The Bi0–Cu0/BC nano-biocomposites showed higher Cr removal efficiency (92%) compared to Cu0/BC (85%), Bi0/BC (76%), and BC (67%). The prepared nanocomposites led to effective Cr removal at lower Cr concentrations (25 mg/L) and acidic pH (4.0). The Cr solubility changes with pH, resulting in different degrees of Cr removal by Bi0–Cu0/BC, with Cr(VI) being more soluble and easier to adsorb at low pH levels and Cr(III) being less soluble and more difficult to adsorb at high pH levels. The experimental Cr adsorption well fitted with the Freundlich adsorption isotherm model (R2 > 0.99) and pseudo-second-order kinetic model. Among the prepared nanocomposites, the Bi0–Cu0/BC showed greater stability and reusability. It was established that the as-synthesized Bi0–Cu0/BC nano-biocomposite showed excellent adsorption potential for practical Cr removal from contaminated water. [ABSTRACT FROM AUTHOR]

Batch scale removal of arsenic (As) from aqueous media was explored using nano-zero valent iron (Fe0) and copper (Cu0) particles. The synthesized particles were characterized using a Brunauer-Emmett–Teller (BET) surface area analyzer, a scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR). The BET result showed that the surface area (31.5 m2/g) and pore volume (0.0415 cm3/g) of synthesized Fe0 were higher than the surface area (17.56 m2/g) and pore volume (0.0287 cm3/g) of Cu0. The SEM results showed that the morphology of the Fe0 and Cu0 was flowery microspheres and highly agglomerated with thin flakes. The FTIR spectra for Fe0 showed broad and intense peaks as compared to Cu0. The effects of the adsorbent dose (1–4 g/L), initial concentration of As (2 mg/L to 10 mg/L) and solution pH (2–12) were evaluated on the removal of As. Results revealed that effective removal of As was obtained at pH 4 with Fe0 (94.95%) and Cu0 (74.86%). When the dosage increased from 1 to 4 g L−1, the As removal increased from 70.59 to 93.02% with Fe0 and from 67 to 70.59% with Cu0. However, increasing the initial As concentration decreased the As removal significantly. Health risk indices, including estimated daily intake (EDI), hazard quotient (HQ), and cancer risk (CR) were employed and a significant decline (up to 99%) in risk indices was observed in As-treated water using Fe0/Cu0. Among the adsorption isotherm models, the values of R2 showed that isothermal As adsorption by Fe0 and Cu0 was well explained by the Freundlich adsorption isotherm model (R2 > 0.98) while the kinetic experimental data was well-fitted with the Pseudo second order model. The Fe0 showed excellent stability and reusability over five sorption cycles, and it was concluded that, compared to the Cu0, the Fe0 could be a promising technology for remediating As-contaminated groundwater. [ABSTRACT FROM AUTHOR]

Binary composite of zerovalent iron and titanium dioxide (Fe0/TiO2) was synthesized for the catalytic removal of dichlorophene (DCP) in the presence of peroxymonosulfate (PMS). The as-prepared composite (Fe0/TiO2) exhibits synergistic effect and enhanced properties like improved catalytic activity of catalyst and greater magnetic property for facile recycling of catalyst. The results showed that without addition of PMS at reaction time of 50 min, the percent degradation of DCP by TiO2, Fe0, and Fe0/TiO2 was just 5%, 11%, and 12%, respectively. However, with the addition of 0.8 mM PMS, at 10 min of reaction time, the catalytic degradation performance of Fe0, TiO2, and Fe0/TiO2 was significantly improved to 82%, 18%, and 88%, respectively. The as-prepared catalyst was fully characterized to evaluate its structure, chemical states, and morphology. Scanning electron microscopy results showed that in composite TiO2 causes dispersion of agglomerated iron particles which enhances porosity and surface area of the composites and X-ray diffraction (XRD), energy dispersive X-ray (EDX), and Fourier-transform infrared (FTIR) results revealed successful incorporation of Fe0, and oxides of Fe and TiO2 in the composite. The adsorption–desorption analysis verifies that the surface area of Fe0/TiO2 is significantly larger than bare Fe0 and TiO2. Moreover, the surface area, particle size, and crystal size of Fe0/TiO2 was surface area = 85 m2 g−1, particle size = 0.35 μm, and crystal size = 0.16 nm as compared to TiO2 alone (surface area = 22 m2 g−1, particle size = 4.25 μm, and crystal size = 25.4 nm) and Fe0 alone (surface area = 65 m2 g−1, particle size = 0.9 μm, and crystal size = 7.87 nm). The as-synthesized material showed excellent degradation performance in synthesized wastewater as well. The degradation products and their toxicities were evaluated and the resulted degradation mechanism was proposed accordingly. The toxicity values decreased in order of DP1 > DP5 > DP2 > DP3 > DP4 and the LC50 values toward fish for 96-h duration decreased from 0.531 to 67.2. This suggests that the proposed technology is an excellent option for the treatment of antibiotic containing wastewater. [ABSTRACT FROM AUTHOR]

In this study, activated carbon (AC) and nano-zerovalent copper (nZVCu) functionalized hydroxyapatite (HA) and alginate beads were synthesized and used for the removal of As3+ from aqueous solution. The characterization by X-ray diffraction, scanning electron microscopy, X-ray energy dispersive spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, high resolution transmission electron microscopy, BET surface area analysis, thermogravimetric analysis, and Fourier transform infrared spectroscopy revealed successful formation of the AC/nZVCu/HA-alginate, nZVCu/HA-alginate, AC/HA-alginate, and HA-alginate beads. The scanning electron microscopy and surface analysis revealed the prepared beads to be highly mesoporous which led to the maximum adsorption of As3+, i.e., 13.97, 29.33, 30.96, and 39.06 mg/g by HA-alginate, AC/HA-alginate, nZVCu/HA-alginate, and AC/nZVCu/HA-alginate beads, respectively. The thermogravimteric analysis showed the nZVCu/HA-alginate beads to be highly stable while the AC composite beads as the least stable to heat treatment. The HA-alginate beads achieved 39% removal of As3+, however, removal efficiency was promoted to 95% by coupling AC and nZVCu with HA-alginate beads at a reaction time of 120 min. The removal of As3+ by the prepared AC & nZVCu coupled HA-alginate beads was promoted with increasing [As3+] 0 and [AC/nZVCu/HA-alginate] 0. The pH of aqueous solution significantly influenced the removal of As3+ by AC/nZVCu/HA-alginate beads and maximum removal was achieved at pH 5.8. Freundlich adsorption isotherm and pseudo-second-order kinetic models were found to best fit the removal of As3+ by the synthesized beads. The high performance of AC/nZVCu/HA-alginate beads in the removal of As3+ even after seven cyclic treatment as well as least leaching of Cu ions into aqueous solution suggest enhanced reusability and stability of HA-alginate beads by coupling with AC and nZVCu. The results suggest that the synthesized beads have good potential for the removal of As3+ from aqueous solutions. Image 1 • Characterization techniques proved nZVCu and AC coupled HA-Alginate beads formation. • Coupling AC and nZVCu enhanced performance and reusability of HA-Alginate beads. • Removal of As3+ best fitted Freundlich isotherm and pseudo-second-order models. • Removal of As3+ was significantly affected by the pH of aqueous solution. [ABSTRACT FROM AUTHOR]

Bromate, a potential carcinogen, is a well known highly persistent and environmentally recalcitrant contaminant. UV-254/sulfite-based advanced reductive pathways (ARPs) were proposed to eliminate bromate successfully from water. Experiments with N 2 , N 2 O, 2-chlorophenol, inorganic ions, and different pH (highly acidic to highly basic) proved that UV-254/sulfite successfully provides aqueous electron that effectively participate in bromate removal from water. Significant removal, 86%, of initially 39.0 µM bromate was achieved by UV-254/sulfite under conditions that dominate aqueous electron based pathways. The high second-order rate constant of 5.3 × 10 9 M −1 s −1 determined proved high reactivity of aqueous electron with bromate. The kinetic and removal efficiency of bromate showed linear relationship with the rate of aqueous electron formation. An increase in kinetic and removal efficiency of bromate was observed with increasing initial sulfite concentration and decreasing bromate concentration. The impacts of different initial concentrations of the typical ions commonly found in water were studied in detail to extend the UV-254/sulfite-based process for potential practical applications. The lower molar absorptivity of bromate at 254 nm determined proved insignificant removal of bromate under direct photolysis. The impacts of initial sulfite concentration on removal of bromate in UV-254/sulfite-based process also minimized role of direct photolysis. The cost evaluation and rapid decomposition of bromate into bromide proved UV-254/sulfite-based ARPs to be economical and highly rewarding in efficient decomposition of bromate and other inorganic oxyhalides. [ABSTRACT FROM AUTHOR]

This study reports the radiation-induced degradation of an extensively used carcinogenic, endocrine disrupting and persistent herbicide, atrazine, in aqueous solution. The atrazine degradation rate was directly proportional whereas the dose constant was inversely proportional to the irradiation dose rate and initial atrazine concentration. The second-order rate constant of atrazine with e aq − and H were found to be 3.70 × 10 9 and 4.84 × 10 8 M −1 s −1 , respectively. Humic acid has synergistic whereas hydrogen peroxide and chloroform have an inhibitory impact on atrazine degradation. Atrazine degradation was reduced in the presence of 1 mM of each of NO 3 − , NO 2 − , Br − , SO 4 2− , HCO 3 − and CO 3 2− due to their competition for reactive radicals with atrazine. The attack of e aq − and OH on atrazine successfully mineralized the organic chlorine and nitrogen to chloride, nitrate and ammonium ions, in addition to the formation of acetate ions from carbon atoms of side chains. Potential detoxification of atrazine solution could be revealed from 83% loss of chloride ion at an absorbed dose of 4000 Gy. The findings of this study suggested that atrazine can efficiently be removed from water by gamma-ray irradiation even in the presence of organic and inorganic radical scavengers commonly found in natural water. [ABSTRACT FROM AUTHOR]

This study investigated iron-mediated oxidative processes for the photochemical degradation of endosulfan, a chlorinated insecticide and central nervous system disruptor. At UV fluence of 360 mJ/cm 2 , 52.4% and 32.0% removal of 2.45 μM initial endosulfan was observed by UV/Fe 3+ and UV/Fe 2+ processes, respectively, at an initial concentration of 17.8 μM iron. The degradation of endosulfan by UV/Fe 3+ or UV/Fe 2+ was dramatically enhanced by adding peroxide (i.e., H 2 O 2 , S 2 O 8 2− or HSO 5 − ). Among the UV/peroxide/Fe processes, the highest degradation efficiency of 99.0% at UV fluence of 360 mJ/cm 2 was observed by UV/HSO 5 − /Fe 2+ with 2.45 μM [endosulfan] 0 , 17.8 μM [Fe 2+ ] 0 , and 49.0 μM [HSO 5 − ] 0 . The observed degradation rate constant of endosulfan was promoted either by increasing [Fe 2+ ] 0 and/or [peroxide] 0 or by decreasing [endosulfan] 0 , while the initial degradation rate of endosulfan increased with increasing [Fe 2+ ] 0 , [peroxide] 0 , or [endosulfan] 0 . At UV fluence of 6000 mJ/cm 2 , 45.0% mineralization as represented by the decrease in total organic carbon content was observed by UV/HSO 5 − /Fe 2+ at 9.80 μM [endosulfan] 0 , 980 μM [HSO 5 − ] 0 , and 17.8 μM [Fe 2+ ] 0 . The major by-product of endosulfan was observed in all cases to be endosulfan ether which was further degraded with an extended reaction time. The results suggest that iron-mediated advanced oxidation processes (AOPs) have a high potential for the removal of endosulfan and its by-product from contaminated water. [ABSTRACT FROM AUTHOR]

The degradation of atrazine was investigated in aqueous solution by gamma-ray irradiation. 8.11 μM initial atrazine concentration could be completely removed in N 2 saturated solution by applying 3500 Gy radiation dose at a dose rate of 296 Gy h −1 . Significant removal of atrazine (i.e., 39.4%) was observed at an absorbed dose of 1184 Gy in air saturated solution and the removal efficiency was promoted to 50.5 and 65.4% in the presence of N 2 O and N 2 gases, respectively. The relative contributions of hydrated electron, hydroxyl radical and hydrogen radical toward atrazine degradation were determined as ratio of observed dose constant ( k obs ) and found to be 5: 3: 1 for k eaq − : k OH : k H , respectively. The degradation efficiency of atrazine was 69.5, 55.6 and 37.3% at pH 12.1, 1.7 and 5.7, respectively. A degradation mechanism was proposed based on the identified degradation by-products by gas chromatography–mass spectrometry. Taking the relative contributions of oxidative and reductive species to atrazine degradation into account, reductive pathway proved to be a better approach for the radiolytic treatment of atrazine contaminated water. [ABSTRACT FROM AUTHOR]

The removal of endosulfan, an emerging water pollutant, from water was investigated using gamma irradiation based advanced oxidation and reduction processes (AORPs). A significant removal, 97% of initially 1.0 µM endosulfan was achieved at an absorbed dose of 1020 Gy. The removal of endosulfan by gamma-rays irradiation was influenced by an absorbed dose and significantly increased in the presence of aqueous electron (eaq-). However, efficiency of the process was inhibited in the presence of eaq- scavengers, such as N2O, NO3-, acid, and Fe3+. The observed dose constant decreased while radiation yield (G-value) increased with increasing initial concentrations of the target contaminant and decreasing dose-rate. The removal efficiency of endosulfan II was lower than endosulfan I. The degradation mechanism of endosulfan by the AORPs was proposed showing that reductive pathways involving eaq- started at the chlorine attached to the ring while oxidative pathway was initiated due to attack of hydroxyl radical at the SO bond. The mass balance showed 95% loss of chloride from endosulfan at an absorbed dose of 1020 Gy. The formation of chloride and acetate suggest that gamma irradiation based AORPs are potential methods for the removal of endosulfan and its by-products from contaminated water. [ABSTRACT FROM AUTHOR]

• The nZVMn/PBC showed high activity in adsorptive and oxidative removal of Congo-red. • The physical properties of biochar were improved with the coupling of nZVMn. • The nZVMn/PBC-catalyzed H2O2 into ●OH that caused oxidative removal of Congo-red. • Congo-red removal was promoted with the high dose of adsorbent and H2O2. • Degradation pathways of Congo-red in ●OH-mediated oxidative system were proposed. Congo-red (CR), a precursor of textile products and a contaminant of great concern, has contaminated aquatic environments. Here, we explored the synthesis of mesoporous nano-zerovalent manganese (nZVMn) and Phoenix dactylifera leaves biochar (PBC) composite for the removal of CR from water. The nZVMn/PBC adsorbed 117.647 mg/g of CR versus 25.316 mg/g by PBC at [CR] 0 = 20 mg/L and [PBC] 0 = [nZVMn/PBC] 0 = 500 mg/L. Variation of [nZVMn/PBC] 0 , [CR] 0 and pH influenced the adsorption of CR. Freundlich adsorption isotherm and pseudo-first-order kinetic models best fitted CR adsorption. The H 2 O 2 coupling with nZVMn/PBC promoted removal of CR possibly due to the formation of hydroxyl radical (●OH) and caused 95 % removal of CR versus 77 % by nZVMn/PBC alone. The ●OH scavengers inhibited the removal of CR. The nZVMn/PBC showed a good reusability and efficient removal of CR up to the seventh cycle of treatment. Results reveal that nZVMn improved performance, thermal stability and reusability of biochar. Degradation products from ●OH-mediated degradation of CR were studied by ultraperformance liquid chromatography with mass spectrometric detector to establish degradation pathways. The ion-chromatographic analysis showed the formation of non-toxic inorganic acetate product, which suggests high potential of the newly fabricated adsorbent in the removal of CR. [ABSTRACT FROM AUTHOR]

Chlorpyrifos (CPY), an organophosphate pesticide is largely used throughout the world on different crops for the control of pests and causes severe health and environmental issues. In this study, highly efficient, crystalline, and nm-rang sized zerovalent zinc (nZVZn) catalyst was synthesized and used for removal of chlorpyrifos at semi-pilot scale. The nZVZn showed high activity and caused 55% removal of CPY at 90 min time under the conditions of [CPY] 0 = 10 mg/L, [nZVZn] 0 = 1.0 g/L, and flow rate of the reactor = 0.2 L/min. Using identical conditions of [CPY] 0 , [nZVZn] 0 and flow rate, the use of peroxymonosulfate (PMS) promoted the performance of nZVZn and caused 99.5% removal of CPY at [PMS] 0 = 40 mg/L. The electron spin resonance (ESR) spectroscopy studies revealed that nZVZn catalyzed PMS reactions yield hydroxyl and sulfate radicals that degraded CPY and removal of CPY was suppressed by applying radical scavengers. The nZVZn catalyzed PMS based removal of CPY was optimum at high [PMS] 0 , [nZVZn] 0 and low pH of solution. The flow rate of the pilot plant reactor also influenced the degradation efficiency of CPY. High pH of solution, high [CPY] 0 as well as use of alcohols, NOM, and some inorganic ions inhibited removal of CPY by nZVZn catalyzed PMS. The analysis of degradation products (DPs) of CPY were used to propose degradation pathways of CPY. The high TOC removal of CPY, low leaching of Zn2+ from Zn0 into aqueous solution, and toxicity reduction of CPY suggest the nZVZn catalyzed PMS process to be highly effective and environmental benign for treatment of CPY. Image 1 • Nano zerovalent zinc was used for removal of chlorpyrifos at semi-pilot scale. • Removal of chlorpyrifos by zerovalent zinc was promoted by peroxymonosulfate. • Hydroxyl and sulfate radical rate constants with chlorpyrifos were calculated. • Proposed degradation pathways of chlorpyrifos were suggested. • Toxicities of treated chlorpyrifos solutions and zinc ion leaching were evaluated. [ABSTRACT FROM AUTHOR]

[Display omitted] • Nanocomposites of siltstone were prepared for Cr decontamination from water. • The composite BSS/FeO/ZnO showed better efficiency for Cr removal (87%). • Langmuir and pseudo-second-order kinetic models well explained Cr adsorption. • The BSS/ZnO, BSS/FeO, and BSS/ZnO/FeO showed excellent reusability and stability. • Difference in Cr removal was confirmed with characterization of the adsorbents. In this study, nanocomposites of Baghanwala Siltstone (BSS) with ZnO (BSS/ZnO), FeO (BSS/FeO), and BSS/ZnO/FeO were successfully prepared for the removal of hexavalent chromium [(Cr (VI)] from aqueous solutions via a batch adsorption process. The characterization studies by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) found successful synthesis of the composites and demonstrated the occurrence of different active functional groups that played an active role in Cr ion adsorption. The effect of Cr initial concentrations (25–100 mg/L), adsorbent dose (0.5–2 g/L), pH (2–8), and contact time (0–160 min) on Cr remediation from contaminated water was examined. The order of Cr ion removal was BSS/ZnO/FeO (77–87%) > BSS/ZnO (74–83%) > BSS/FeO (71–77%) > BSS (68–74%). The as-synthesized BSS/ZnO/FeO led to successful Cr removal (87%) at a 25 mg/L Cr concentration at pH 4.0. The Cr ion adsorption by the BSS/ZnO/FeO nanocomposite was well explained by the Langmuir adsorption isotherm model (R2 > 0.99), while the kinetic experimental data was well fitted with the pseudo-second-order model (R2 > 0.99). Among the as-synthesized adsorbents, the BSS/ZnO/FeO nanocomposite showed excellent stability and reusability in seven sorption cycles. The results showed that the as-synthesized BSS/ZnO/FeO nanocomposite had the greatest adsorption potential for removing Cr ions from contaminated water. [ABSTRACT FROM AUTHOR]

In this study, a novel immobilized TiO2/Ti film with exposed {001} facets was prepared via a facile one-pot hydrothermal route for the degradation of norfloxacin from aqueous media. The effects of various hydrothermal conditions (i.e., solution pH, hydrothermal time (HT) and HF concentration) on the growth of {001} faceted TiO2/Ti film were investigated. The maximum photocatalytic performance of {001} faceted TiO2/Ti film was observed when prepared at pH 2.62, HT of 3 h and at HF concentration of 0.02 M. The as-prepared {001} faceted TiO2/Ti films were fully characterized by field-emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM), and X-ray photoelectron spectroscopy (XPS). More importantly, the as-prepared {001} faceted TiO2/Ti film exhibited excellent photocatalytic performance toward degradation of norfloxacin in various water matrices (Milli-Q water, tap water, river water and synthetic wastewater). The individual influence of various anions (SO42-, HCO3-, NO3-, Cl-) and cations (K+, Ca2+, Mg2+, Cu2+, Na+, Fe3+) usually present in the real water samples on the photocatalytic performance of as-prepared TiO2/Ti film with exposed {001} facet was investigated. The mechanistic studies revealed that •OH is mainly involved in the photocatalytic degradation of norfloxacin by {001} faceted TiO2/Ti film. In addition, norfloxacin degradation byproducts were investigated, on the basis of which degradation schemes were proposed. [ABSTRACT FROM AUTHOR]

Abstract: The degradation of atrazine, a widely used endocrine disrupting, carcinogenic and persistent herbicide, was investigated by photo-Fenton and photo-Fenton-like advanced oxidation technologies (AOTs): UV/H2O2/Fe2+, UV//Fe2+ and UV//Fe2+. The study was carried out at two pH value conditions, i.e., pH 3.0 and pH 5.8. At pH 3.0, UV//Fe2+ was found to be the most efficient technology whereas UV//Fe2+ was observed to be the most effective at pH 5.8. The degradation of atrazine followed pseudo-first-order reaction with the highest observed rate constant of 2.00×10−2 cm2/mJ in UV//Fe2+ system at the initial concentrations of 4.64μM atrazine, 46.4μM (PMS) and 35.81μM Fe2+. The UV fluence required for the complete removal of 4.64μM atrazine at initially 92.80μM of oxidant and 8.95μM of Fe2+ concentrations at pH 3.0 was found to be 480, 720 and 960mJ/cm2 in UV//Fe2+, UV//Fe2+ and UV/H2O2/Fe2+ systems, respectively. Humic and fulvic acids were found to negatively impact the degradation of atrazine. The removal of TOC was not significant unless a high UV fluence was applied. At an initial concentration of 18.56μM atrazine, 1856.00μM oxidant and 17.91μM Fe2+, a 62.94%, 47.10% and 44.09% decrease in TOC was achieved at a UV fluence of 6000mJ/cm2 in UV/PS/Fe2+, UV/PMS/Fe2+ and UV/H2O2/Fe2+ systems, respectively. Nevertheless, it is suggested in this study that photo-Fenton and photo-Fenton-like technologies are capable of removing atrazine from water efficiently. [Copyright &y& Elsevier]