Efficient treatment of oily wastewater, antibacterial activity, and photodegradation of organic dyes using biosynthesized Ag@Fe3O4 nanocomposite.

A significant waste (e.g., high oil content and pollutants such as heavy metals, dyes, and microbial contaminants) in water is generated during crude oil extraction and industrial processes, which poses environmental challenges. This study explores the potential of Ag@Fe3O4 nanocomposite (NC) biosynthesized using the aqueous leaf extract of Laurus nobilis for the treatment of oily wastewater. The NC was characterized using ultraviolet-visible (UV-Vis) spectrophotometry, Scanning Electron Microscopy (SEM), Fourier Transformed Infrared (FTIR) and X-Ray Diffraction (XRD) spectroscopies. The crystalline structure of the NC was determined to be face-centered cubic with an average size of 42 nm. Ag@Fe3O4 NC exhibited significant degradation (96.8%, 90.1%, and 93.8%) of Rose Bengal (RB), Methylene Blue (MB), and Toluidine Blue (TB), respectively, through a reduction reaction lasting 120 min at a dye concentration of 10 mg/L. The observed reaction kinetics followed a pseudo-first-order model, with rate constants (k-values) of 0.0284 min-1, 0.0189 min-1, and 0.0212 min-1 for RB, MB, and TB, respectively. The fast degradation rate can be attributed to the low band gap (1.9 eV) of Ag@Fe3O4 NC. The NC elicited an impressive effectiveness (99-100%, 98.0%, and 91.8% within 30 min) in removing, under sunlight irradiation, several heavy metals, total petroleum hydrocarbons (TPH), and total suspended solids (TSS) from the oily water samples. Furthermore, Ag@Fe3O4 NC displayed potent antibacterial properties and a good biocompatibility. These findings contribute to the development of efficient and cost-effective methods for wastewater treatment and environmental remediation.

Optoacoustic monitoring of bilirubin photodegradation.

Hematomas resulted from trauma are very common, and the efficacy of existing treatment techniques is limited. Phototherapy can be used to expedite healing and improve the appearance of the damaged tissue. Efficient phototherapy requires determination of chromophore composition in hematoma, which can be provided by the optoacoustic (OA) technique, as it combines high spatial resolution and optical contrast. Here, we conducted experiments on photodegradation of bilirubin in gelatin slin phantoms. We have demonstrated that the OA technique allows monitoring of bilirubin concentration during photodegradation, and also distinguishing bilirubin concentration in depth. The obtained results suggest that OA monitoring may be used for efficient hematoma phototherapy.

Optimized photodegradation of palm oil agroindustry waste effluent using multivalent manganese-modified black titanium dioxide.

This article presents a methodological approach to use manganese (Mn3+Mn7+)-modified black titanium dioxide (Mn/BTiO2) as a photocatalyst to optimize and improve visible-light-driven photodegradation of treated agro-industrial effluent (TPOME). A modified wet chemical process was used to prepare BTiO2. The BTiO2 was then wet impregnated with Mn and calcined at 300 °C for 1 h to produce Mn/BTiO2. The activity of Mn/BTiO2 was investigated in terms of photo-assisted elimination of chemical oxygen demand (COD), phenolic compounds (PCs), color, and total organic carbon (TOC). Using the design of experiments (DOE), the conditions of the photocatalytic process, including photocatalyst loading, Mn concentration, hydrogen peroxide (H2O2) dose, and irradiation time, were optimized. Under the optimum conditions (0.85 g/L photocatalyst loading, 0.048 mol/L H2O2 dose, 0.301 wt.% Mn concentration, and 204 min irradiation time) COD, PCs, color, and TOC removal efficiencies of 88.87%, 86.04%, 62.8%, and 84.66%, respectively, were obtained. Statistical analysis showed that the response variable's removal from TPOME estimation had high R2 and low RMSE, MSE, MAD, MAE, and MAPE values, indicating high reliability. This study demonstrated the significant potential of the developed photocatalytic system for the treatment of waste effluent generated by the palm oil industry and other agro-industries, with the ability to simultaneously reduce a number of organic pollution indicators (OPIs).

Identification and characterization of forced degradation products of 5-hydroxymethyl-2-furaldehyde (5-HMF) by HPLC, LC-LTQ/Orbitrap and NMR studies.

5-Hydroxymethyl-2-furaldehyde (5-HMF) is a kind of aldehyde compound with highly active furan ring, which is generated by dehydration of glucose, fructose, and other monosaccharides. It widely exists in drugs, foods, health products, cosmetics, and traditional Chinese medicine preparations with high sugar content. Due to the toxicity, the concentration of 5-HMF was always monitored to identify non-conformities and adulteration, as well as ensure the process efficiency, traceability and safety in foods or drugs in the pharmacopoeias of various countries. Herein, a comprehensive forced degradation study was performed to characterize the degradation products (DPs) of 5-HMF under hydrolytic (neutral, acidic, and alkaline) degradation, oxidative, thermal, humidity, and photolytic degradation conditions. A total of five degradants were identified, and two of them (DP-3 and DP-5) were novel DPs first reported in our study. Major DPs (i.e., DP-1 and DP-2) with relatively high peak areas were isolated using semi-preparative HPLC and characterized by LC-LTQ/Orbitrap and NMR. 5-HMF was only stable in alkaline hydrolysis condition. In addition, the degradation pathways and mechanism of these DPs were also explained using LC-LTQ/Orbitrap. In silico toxicity and metabolism behavior of the DPs were evaluated using Derek Nexus and Meteor Nexus software, respectively. The predicted toxicity data indicated that both the drug 5-HMF and its DPs bear the potential of hepatotoxicity, mutagenicity, chromosome damage, and skin sensitisation. Our research may be beneficial for the quality control and suitable storage conditions of 5-HMF.

New insights into the mechanism of phosphate release during particulate organic matter photodegradation based on optical and molecular signatures.

Phosphate release from particulate organic matter (POM) dominates phosphorus (P) cycling in aquatic ecosystems. However, the mechanisms underlying P release from POM remain poorly understood because of complex fractionation and analytical challenges. In this study, the release of dissolved inorganic phosphate (DIP) during POM photodegradation was assessed using excitation-emission matrix (EEM) fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). POM in suspension was significantly photodegraded under light irradiation, concomitantly with the production and release of DIP in the aqueous solution. Chemical sequential extraction revealed that organic phosphorus (OP) in POM participated in photochemical reactions. Moreover, FT-ICR MS analysis revealed that the average molecular weight of P-containing formulas decreased from 374.2 to 340.1 Da. Formulas containing P with a lower oxidation degree and unsaturation were preferentially photodegraded, generating oxygen-enriched and saturated formula compounds, such as protein- and carbohydrate-like P-containing formulas, benefiting further utilization of P by organisms. Reactive oxygen species played an important role in the photodegradation of POM, and excited triplet state chromophoric dissolved organic matter (3CDOM*) was mainly responsible for POM photodegradation. These results provide new insights into the P biogeochemical cycle and POM photodegradation in aquatic ecosystems.

Noninvasive, continuous fluorescence monitoring of bilirubin photodegradation.

Nowadays phototherapy is widely used for treatment of various diseases. However, efficient application of phototherapy requires an understanding of light interactions with main endogenous chromophores (e.g., hemoglobin, bilirubin, and water) in tissue. In particular, bilirubin is the target chromophore in the treatment of neonatal jaundice, which is the most common disease affecting up to 80% of preterm infants. The most frequently recommended treatment technique for this disease is phototherapy with blue light in combination with conventional drug therapy. To follow threshold total serum bilirubin (TSB) concentration guidelines, it is essential to estimate TSB concentration accurately. The gold standard biochemical analysis is invasive and bulky. Moreover, noninvasive methods do not provide sufficient reproducibility and accuracy. In this research, the fluorescence sensing of bilirubin with human serum albumin complexes was studied. The fluorescence time course during light irradiation (central wavelength: 467 nm and power density: 12.13 mW cm-2) was demonstrated to depend on the initial concentration. Specifically, for the bilirubin concentration C = 18.65 µM, an insignificant fluorescence signal increase was observed during the first 30 minutes of light irradiation, while for bilirubin concentration C = 373 µM, the fluorescence signal did not reach maximum during 2.5 hours of light irradiation. Thus, fluorescence sensing might show increased accuracy when used with other noninvasive bilirubin sensing methods.

Sunlight promoted self-fenton photodegradation and pathway of doxycycline: Interactive effects of nanomaterial on bean plant and its genotoxicity against Allium cepa.

Photocatalytic induction of electron/hole recombination, surface property and light response ability effectively enhance the photocatalytic activity of nanomaterial. In this work, the effective charge carrier separating Sn/Mn-ZnFe2O4-CdFe2O4-Ag3PO4 Quantum dots (M/SZFO-CFO-AP QDs) was fabricated for photocatalytic degradation of doxycycline (doxy) antibiotic. The result showed enhanced photocatalytic activity of doxy and the degradation efficiency of doxy was about 98.8% in short span of time. The calculated WH plot and urbach energy of prepared photocatalyst exhibited evidence for the prevalence of point defects and its contribution to efficient charge separation and transferability. The total organic carbon (TOC) removal was found to be 98.9%, which depicts the complete mineralization of doxy. The synergetic charge transfer of n-p-n heterojunction enables the effective removal of doxy under visible light irradiation. Further, the genotoxicity study was determined by interacting the SZFO-CFO-AP QDs with Allium Cepa. The results depict that SZFO-CFO-AP QDs show lower toxicity level and there were no trace of defective mitotic phases and micro nuclei. Further, the progression and development of bean plant was determined after treating with prepared nanomaterials and the result showed the enhanced growth in SZFO-CFO-AP QDs treated bean plant compared to the counterparts. Therefore, the prepared SZFO-CFO-AP QDs was can be used as an environmental friendly photocatalyst for effective treatment of antibiotic present in the water bodies.

Suspect screening strategy for pesticide application history based on characteristics of trace metabolites.

Pesticides are widely used to protect crops but can also threaten public health as they can remain in the environment for a long time. Additionally, some transformation products (TPs) of unknown toxicity, stability, or bioaccumulation properties can further be formed from the hydrolysis, photolysis and biodegradation of pesticides. The identification and quantification of those TPs can be challenging for environmental regulation and risk assessment due to a limited understanding about them. In this study, a suspect screening strategy for pesticide application history was developed and then used to organic products (tea). Liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) was used to screen and identify the TPs in crops and their toxicity was subsequently predicted with the open-source software (ECOSAR and admetSAR). Finally, the SIRIUS software was applied and 142 TPs from 20 pesticides were identified in tea plants based on the fragmentation-degradation relationship. Of these, standards (level 1) and 53 were considered as tentatively identified (levels 2a and 2b). Some TPs were also found to be present in tea plants and soil after 65 days, thus indicating higher persistency or stability than parent pesticides. While others from diafenthiuron and neonicotinoids had higher predicted toxicity of daphnid, and demonstrated positive for honeybee toxicity. Suspect screening is a powerful tool to screen pesticide TPs on the complex matrix of crops. Such screening can provide potential evidence of pesticide application, especially in cases of illegal practices in organic farming.

A green approach for the preparation of ZnO@C nanocomposite using agave americana plant extract with enhanced photodegradation.

The present study demonstrates the crucial role of agave americana extract in enhancing the optical properties of zinc oxide (ZnO) through thermal treatment method. Various analytical and surface science techniques have been used to identify the morphology, crystalline structure, chemical composition, and optical properties, including scanning electron microscopy, x-ray diffraction, high resolution transmission electron microscopy (HRTEM), x-ray spectroscopy (EDS) and UV-visible spectroscopy techniques. The physical studies revealed the transformation of ZnO nanorods into nanosheets upon addition of an optimized amount of agave americana extract, which induced large amount of amorphous carbon deposited onto ZnO nanostructures as confirmed by HRTEM analysis. The use of increasing amount of americana extract has significantly reduced the average crystallite size of ZnO nanostructures. The resultant hybrid system of C@ZnO has produced a significant effect on the ultraviolet light-assisted photodegradation of malachite green (MG) dye. The photocatalyst dose was fixed at 10 mg for each study whereas the amount of agave americana extract and MG dye concentration are varied. The functionality of hybrid system was greatly enhanced when the amount of agave americana extract increased while dye concentration kept at lower level. Ultimately, almost 100% degradation efficiency was achieved via the prepared hybrid material, revealing combined contribution from synergy, stabilization of ZnO due to excess of carbon together with the high charge separation rate. The obtained results suggest that the driving role of agave americana extract for surface modification of photocatalyst can be considered for other nanostructured photocatalysts.

Efficient green photocatalyst of silver-based palladium nanoparticles for methyle orange photodegradation, investigation of lipid peroxidation inhibition, antimicrobial, and antioxidant activity.

Nanotechnology is an interdisciplinary study that has been developing worldwide in recent years and has a serious impact on human life. The fact that the nanoparticles of plant origin are clean, non-toxic, and biocompatible has enabled new fields of study. The Hibiscus sabdariffa (H. sabdariffa) plant has been attracted by scientists because of its impact on health and many other areas. The lipid peroxidation inhibiting activity, antioxidant properties, and antimicrobial properties of H. sabdariffa plant with Ag-Pd metal was ditermined. For the total phenolic component, gallic acid was used as the standard and quarcetin was used for the total flavonoid. The lipid peroxidation inhibition activity of Ag-Pd NPs in ethanol extract was found to be very well compared to the positive control (BHA). The lowest and highest concentrations of DPPH radical scavenging activity were 82.178-97.357%, whereas for BHA these values were found to be 84.142-94.142%. The highest concentration of Ag-Pd NPs at 200 µg/mL the DPPH radical quenching activity was higher than BHA. Ag-Pd NPs showed a good antimicrobial activity against certain pathogenic microorganisms such as Bacillus subtilis, Enterococcus faecalis, Escherichia coli, Pseudomonas aeruginosa, Candida albicans, which are the causative agents of various diseases in humans. The photodegradation activity of Ag-Pd NPs also investigated against Methyl orange dye (MO) under sunlight irradiation for 120 min and was found to be as 67.88.

Enhanced photodegradation of rifampicin and co-trimoxazole by ZnO/ZnMn2O4/ZnS-PVA and its genotoxicity studies on Allium cepa.

Oxygen vacancies and its associated defect states have a great influence on the electronic and structural aspects of semiconductor photocatalysts, yet there is paucity of investigations about the influence of the defect states on their photocatalytic properties. Herein, this study reports the hierarchical fabrication of oxygen vacancy enriched ZnO/ZnMn2O4/ZnS-PVA nanocomposite (NCs) for the enhanced photodegradation of rifampicin and co-trimoxazole. The formation of lattice expansion induced oxygen vacancies and its associated Urbach tail energy, and n-p-n heterojunction-based S-scheme charge transfer path synergistically contributed to the boosted photocatalytic performance of the as prepared NCs. The photocatalytic performance of the nanomaterial towards rifampicin and co-trimoxazole has been determined to be 80% and 90% under visible light irradiation, respectively. Furthermore, various operating parameters including the concentration of NCs and drug, pH and interference of various ions have been evaluated. The degraded product intermediates have been elucidated by GC-MS analysis. The toxicity of the as-prepared nanomaterials has been evaluated by treating the samples with root tips of Allium cepa, where the NCs was found to be non-toxic. The study provides a new-fangled insight on the preparation and fabrication of non-toxic and defect rich nanomaterials which may help stimulate this area of research.

Mechanisms of biochar enhanced Cu2O photocatalysts in the visible-light photodegradation of sulfamethoxazole.

Cu2O nanoparticles are decorated with biochars derived from spent coffee grounds (denoted as Cu2O/SCG) and applied as visible-light-active photocatalysts in the sulfamethoxazole (SMX) degradation. The physicochemical properties of Cu2O/SCG are identified by various spectral analysis, electrochemical and photochemical techniques. As a result, the Cu2O/SCG exhibits the higher removal efficiency of SMX than the pristine Cu2O under visible light irradiation. We can observe that Cu2O could be incorporated onto the SCG biochars with rich oxygen vacancies/adsorbed hydroxyl groups. In addition, the Cu2O/SCG has the lower charge transfer resistance, faster interfacial electron transfer kinetics, decreased recombination of charge carriers and superior absorbance of visible light. The construction of band diagrams for Cu2O/SCG and pristine Cu2O via UV-vis spectra and Mott-Schottky plots suggest that the band energy shifts and higher carrier density of Cu2O/SCG may be responsible for the photocatalytic activity enhancements. From the radical scavenger experiments and electron paramagnetic resonance spectra, the aforementioned energy shifts could decrease the energy requirement of transferring photoinduced electrons to the potential for the formation of active superoxide radicals (·O2-) via one and two-electron reduction routes in the photocatalytic reaction. A proposed degradation pathway shows that ·O2- and h+ are two main active species which can efficiently degrade SMX into reaction intermediates by oxidation, hydroxylation, and ring opening. This research demonstrates the alternative replacement of conventional carbon materials for the preparation of biochar-assisted Cu2O photocatalysts which are applied in the environmental decontamination by using solar energy.

Treatment of synthetic dye containing textile raw wastewater effluent using UV/Chlorine/Br photolysis process followed by activated carbon adsorption.

This study investigated the efficiency and feasibility of ultraviolet (UV)-assisted photolysis of synthetic dye containing textile raw wastewater effluent. For a said purpose, in-house developed UV/Chlorine/Br process was followed in the presence of activated carbon (AC) which additionally facilitate the dye adsorption. In UV/Chlorine process Cl•, Cl2•-, and HO• are generated in the solution and destroyed compounds that cannot be oxidized by the conventional oxidant. In this process, free bromine is formed and photolyzed by UV radiation and generate Br• and Br2•- that can enhance the rate of pollutant degradation. In the present study, the dye removal efficiency was contributed by dark bromide (7.18%), UV irradiation (26.8%), dark chlorination (78.67%), and UV/Chlorine/Br (87.01%), respectively. With increasing pH from 3.0 to 8.30, the dye removal efficiency was enhanced but decreased by further increasing pH values. In addition, magnetized activated carbon from pomegranate husk using dual-stage chemical activation was used for post-adsorption of the residual dye and its degradation byproducts. The adsorption of the dye residues by AC followed the second-order kinetics with the rate constant of 1.7 × 10-3. The phytotoxicity of the treated textile wastewater by UV irradiation, dark chlorination, and UV/Chlorine/Br was assessed by seed germination of Lepidium sativum seeds. The highest inhibition effect on seed germination was related to treated wastewater by UV irradiation (more than 90% inhibition) that alleviated to less than 10% when this effluent diluted to 5% v/v. The highest germination was observed when the seeds were irrigated by the effluent of the UV/Chlorine/Br process. The significant reduction in the toxicity of the treated wastewater revealed that the UV/Chlorine/Br process has a considerable potential to effectively detoxify textile wastewater. Graphical abstract.

Contrasting Impacts of Photochemical and Microbial Processing on the Photoreactivity of Dissolved Organic Matter in an Adirondack Lake Watershed.

Photochemical and microbial processing are the prevailing mechanisms that shape the composition and reactivity of dissolved organic matter (DOM); however, prior research has not comparatively evaluated the impacts of these processes on the photoproduction of reactive intermediates (RIs) from freshly sourced terrestrial DOM. We performed controlled irradiation and incubation experiments with leaf and soil samples collected from an acid-impacted lake watershed in the Adirondack Mountain region of New York to examine the effects of DOM processing on the apparent quantum yields of RIs (Φapp,RI), including excited triplet states of DOM (3DOM*), singlet oxygen (1O2), and hydroxyl radicals (•OH). Photodegradation led to net reductions in Φapp,1O2, Φapp,3DOM*, and Φapp,•OH, whereas (photo-)biodegradation resulted in increases in Φapp,1O2 and Φapp,3DOM*. Photodegradation and (photo-)biodegradation also shifted the energy distribution of 3DOM* in different directions. Multivariate statistical analyses revealed the potential relevance of photo-biodegradation in driving changes in Φapp,1O2 and Φapp,3DOM* and prioritized five bulk DOM optical and redox properties that best explained the variations in Φapp,1O2 and Φapp,3DOM* along the watershed terrestrial-aquatic continuum. Our findings highlight the contrasting impacts of photochemical and microbial processes on the photoreactivity of freshly sourced terrestrial DOM and invite further studies to develop a more holistic understanding of their implications for aquatic photochemistry.

An environmental approach for the photodegradation of toxic pollutants from wastewater using Pt-Pd nanoparticles: Antioxidant, antibacterial and lipid peroxidation inhibition applications.

BACKGROUND: Green synthesis is an effective and friendly method for the environment, especially in recent years has been used in many areas. It finds application opportunities in many fields such as physics, chemistry, electronics, food, and especially health and is the subject of intensive studies in this field. OBJECTIVES: The synthesized Pt-Pd NPs were aimed to be used as a bio-based photocatalyst under sunlight to prevent wastewater pollution. In addition, it is aimed to use Pt-Pd NPs as biological agents in different applications in the future. METHODS: In this study, the platinum-palladium nanoparticles were synthesized by the extract of Hibiscus sabdariffa, the characterization of the nanoparticles was carried out by different methods (ultraviolet-visible spectroscopy (UV-vis), transmission electron microscopy (TEM), infrared transform spectroscopy atomic force microscopy (AFM), and ray diffraction (XRD) analysis). And we discussed several different parameters related to human health by obtaining platinum-palladium bimetallic nanoparticles (Pt-Pd NPs) with a green synthesis method. These parameters are antioxidant properties (total phenolic, flavonoid, and DPPH scavenging activity), antibacterial activity, and lipid peroxidation inhibition activity. Gallic acid was used as standard phenolic, and quercetin was used as standard flavonoid reagents. The newly synthesized Hibiscus sabdariffa mediated green synthesized Pt-Pd NPs were compared with gram-positive and gram-negative bacteria, the high antibacterial activity was shown by gram-positive bacteria. The photodegradation of Pt-Pd NPs was carried out against MB dye for 180 min. RESULTS: TEM results show that the average size of Pt-Pd NPs is around 4.40 nm. The total amount of phenolic compounds contained in 0.2 mg/ml of Pt-Pd NPs was equivalent to 14.962 ± 7.890 µg/ml gallic acid and the total amount of flavonoid component was found to be equal to 28.9986 ± 0.204 µg/ml quercetin. Hibiscus sabdariffa mediated green synthesized Pt-Pd NPs was found to have very effective for lipid peroxidation inhibition activity in the FeCl2-H2O2 system. The maximum DPPH scavenging activity was determined as 97.35% at 200 µg/ml. The photocatalytic activity of Pt-Pd NPs was analysed against Methylene blue (MB) and the maximum degradation percentage was observed to be 83.46% at 180 min. CONCLUSIONS: The biogenic Pt-Pd NPs showed a high effective photocatalytic and biological activity.

Photodegradation of modified petroleum impregnated bentonite mulch under the effects of solar radiation simulating the outdoor condition.

The objectives of this study were investigating the photodegradation of the polycyclic aromatic hydrocarbons (PAHs) in modified petroleum impregnated bentonite mulch through solar radiation, determining PAHs' translocation in the soils that underlay the mulch and finding a solution to prevent the uncontrolled release of petroleum into the environment. For this research, various formulated mulches were prepared: mulch no. 1 was a mixture of 5:1 sandy soil: natural bentonite + petroleum; mulch no. 2 composed a mixture of 5:1 sandy soil: modified bentonite + natural bentonite + petroleum; and mulch no. 3 composed a mixture of 5:1:0.5 ratio of sandy soil: natural bentonite: modified bentonite mixed with petroleum at a ratio of 1:1. PAHs in surface mulches and subsurface sandy soil were monitored over 5, 20, 40 and 80 days. The results demonstrated that PAHs undergo numerous changes over time because of sunlight. Photodegradation is the most dominant process for low molecular weight (LMW) PAHs (≤ 3 fused aromatic rings) and high molecular weight (HMW) PAHs (≥ 4 fused aromatic rings). HMW PAHs could be sequestrated strongly within the soil particles because of their higher aromaticity and lower polarity; they were more resilient in the soil matrices than LMW PAHs. Mulch no. 2 retained more PAHs compounds (p > 95%) than mulch nos. 1 and 3, which could be attributed to the retention of numerous PAHs in its interlayers, preventing its movement into the underlying soil, environment and atmosphere.

Encapsulation of spinel CuCo2O4 hollow sphere in V2O5-decorated graphitic carbon nitride as high-efficiency double Z-type nanocomposite for levofloxacin photodegradation.

In this study, spinel CuCo2O4 (CCO) with a hierarchical hollow sphere morphology was encapsulated in V2O5-decorated ultra-wrinkled graphitic carbon-nitride (VO-UCN) for the first time via a facile glycerol-assisted solvothermal method in the interest of developing a novel high-efficiency double Z-type nano-photocatalyst (denoted as VO-UCN@CCO). The remarkable physicochemical features of the as-prepared nano-photocatalysts were verified using diverse characterization techniques including TGA, XRD, FT-IR, FE-SEM, TEM, BET, UV-vis DRS, PL, EIS, and transient photocurrent techniques. Herein, VO-UCN@CCO nanocomposite was employed for the photodisintegration of levofloxacin (LVOF) antibiotic under visible-light irradiation and the impact of certain operative reaction system variables was explored in an effort to optimize the photocatalytic capability. The 40% loading of CCO in VO-UCN@CCO nanocomposite was found to display maximum photocatalytic performance (about 95%) for LVOF photodecomposition, which was 9.3, 6.6, and 13.8 times greater when compared with pristine VO, UCN, and CCO, respectively. A high capability was observed for as-prepared photocatalyst during reusability tests and near 90% degradation efficiency was obtained in the sixth run. The complete mineralization of LVOF was achieved by the VO-UCN@CCO photocatalyst process after 300 min of reaction. An excellent synergy factor towards the degradation of LVOF was obtained for VO-UCN@CCO compared to each of its components alone. This peculiar design is envisaged to provide new inspirations for ameliorating the photocatalytic decontamination of tenacious and non-biodegradable species present in real wastewater.

Separation and characterization of two series of unknown degradation impurities caused by light irradiation and autoclaving in xinfujunsu injection using liquid chromatography tandem mass spectrometry.

RATIONALE: A series of photodegradation impurities and a series of degradation impurities produced in autoclaving in xinfujunsu injection were discovered, and these unknown impurities were separated and characterized thoroughly using liquid chromatography tandem quadrupole time-of-flight mass spectrometry. METHODS: The column was a Platisil 5 µm ODS (4.6 × 250 mm, 5 µm). For the analysis of degradation impurities caused by light irradiation and autoclaving, the mobile phase was composed of 0.01 M ammonium formate aqueous solution and acetonitrile/isopropanol (90:10, V/V). Full scan LC-MS and LC-MS2 was carried out to obtain as much structural information as possible. The fragmentation behavior of actinomycin D, actinomycin S3 , and its impurities was studied and used to obtain information about the structures of these impurities. RESULTS: Based on MS2 spectral data and exact mass measurements, the chemical structures of two series of degradation impurities were characterized, among which five unknown impurities were photodegradation impurities and seven unknown impurities were degradation impurities produced in autoclaving of xinfujunsu injection. CONCLUSIONS: Based on characterization of impurities, this study also revealed the cause of impurity production and provided guidance for enterprises to improve the process and drug packaging material to reduce impurity content. Furthermore, this study also provided scientific basis for further improvement of official monographs in pharmacopoeias.

Time-dependent molecular progression and acute toxicity of oil-soluble, interfacially-active, and water-soluble species reveals their rapid formation in the photodegradation of Macondo Well Oil.

Photodegradation is a significant weathering process that transforms spilled oil, yet, the fate, degradation rate, and molecular transformations that occur through photoinduced pathways remain relatively unknown. The molecular complexity combined with the increased polarity of photoproducts challenges conventional analytical techniques. Here, we catalogue the molecular progression of photochemical transformation products of Macondo Well Oil by negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We track the molecular compositions of oil-soluble, interfacially-active, and water-soluble oil species formed at varying time intervals in photomicrocosm experiments. Short photoirradiation periods (<24 h), not previously reported, are included to reveal rapid photooxidation of native oil components. Surface oil films exposed to solar irradiation were shown to increasingly contribute to the dissolved organic carbon pool as a function of increased irradiation time. FT-ICR MS analysis of acidic species of each fraction identifies tens of thousands of oil-soluble, interfacially-active, and water-soluble phototransformation products, including Ox, NOx, and SOx species. Oil-soluble species incorporate oxygen as a function of irradiation periods. After 96 h of irradiation, ~14 wt% of the photooxidized oil film was interfacially active and contained phototransformed species with up to 12 oxygen atoms per molecule. Water-soluble species correspond to highly oxygenated compounds. Importantly, photochemical oxidation is shown to occur within the first hour. Beyond 24 h, photoproducts remain compositionally similar, highlighting the rapid effect of photodegradation to transform oil species into water-soluble compounds. Molecular fingerprints provided by FT-ICR MS highlight the oxygen dependence on oil/water solubility. Microtox® analysis indicates that the toxicity of water-soluble photoproducts rapidly increases at early irradiation time points (first 24 h) compared to the dark control and reaches a maximum at 6 h of irradiation. Results highlight the temporal, molecular progression of photoproducts as they partition from oil-soluble to oil-soluble interfacially-active, and finally to water-soluble species.

Photocatalytic Degradation of Palm Oil Mill Effluent (POME) Waste Using BiVO4 Based Catalysts.

Disposal of palm oil mill effluent (POME), which is highly polluting from the palm oil industry, needs to be handled properly to minimize the harmful impact on the surrounding environment. Photocatalytic technology is one of the advanced technologies that can be developed due to its low operating costs, as well as being sustainable, renewable, and environmentally friendly. This paper reports on the photocatalytic degradation of palm oil mill effluent (POME) using a BiVO4 photocatalyst under UV-visible light irradiation. BiVO4 photocatalysts were synthesized via sol-gel method and their physical and chemical properties were characterized using several characterization tools including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area analysis using the BET method, Raman spectroscopy, electron paramagnetic resonance (EPR), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of calcination temperature on the properties and photocatalytic performance for POME degradation using BiVO4 photocatalyst was also studied. XRD characterization data show a phase transformation of BiVO4 from tetragonal to monoclinic phase at a temperature of 450 °C (BV-450). The defect site comprising of vanadium vacancy (Vv) was generated through calcination under air and maxima at the BV-450 sample and proposed as the origin of the highest reaction rate constant (k) of photocatalytic POME removal among various calcination temperature treatments with a k value of 1.04 × 10-3 min-1. These findings provide design guidelines to develop efficient BiVO4-based photocatalyst through defect engineering for potential scalable photocatalytic organic pollutant degradation.