Identification and Characterization of Rotigotine Degradation Products by HPLC Coupled DAD and CAD Detectors and HRMS Through Q-Orbitrap and Electrospray Ionization.

Rotigotine (RTG) is a dopamine agonist used in the treatment of Parkinson's disease. As it is susceptible to oxidation, stability studies must be carefully designed for the identification and characterization of all possible degradation products. Here, RTG degradation was evaluated according to the International Conference on Harmonization guidelines under various stress conditions, including acidic and basic hydrolysis, oxidative, metallic, photolytic, and thermal conditions. Additionally, more severe stress conditions were applied to induce RTG degradation. Significant degradation was only observed under oxidative and photolytic conditions. The samples were analyzed by high performance liquid chromatography coupled to photodiode array detectors, charged aerosol, and high-resolution mass spectrometry. Chromatographic analyses revealed the presence of eight substances related to RTG, four of which were already described and were qualified impurities (impurities B, C, K and E) and four new degradation products (DP-1 - DP-4), whose structures were characterized by high-resolution mass spectrometry through Q-Orbitrap and electrospray ionization. In the stress testing of the active pharmaceutical ingredient in solid form, significant RTG degradation was observed in the presence of the oxidative matrix. The results corroborate the literature that confirm the high susceptibility of RTG to oxidation and the importance of using different detectors to detect degradation products in forced degradation studies.

Synergistic photocatalysis of a hydrochar/CeO2 composite for dye degradation under visible light.

The synthesis and characterization of a hydrochar/CeO2 composite along with its evaluation in methylene blue degradation under visible light are presented. The methodology consisted of a single-pass hydrothermal method, having as synthesis conditions 9 h of reaction time, 210 °C, autogenous pressure, and a biomass/CeO2 ratio of 100:1. The composite characterization revealed good dispersion of CeO2 in the carbonaceous matrix and significant synergy in the composite activation using visible irradiation. The photodegradation experiments showed an efficiency of 98% for white LED light, 91% for UV light, 96% for solar irradiation, and 85% for blue LED light using as conditions pH 7.0, 50 mg of composite, 50 mL of solution, 10 mg/L of dye initial concentration, and 120 min of contact time. Meanwhile, the reusability experiments evidenced a reuse capacity of up to five times with a constant photodegradation efficiency (99%); moreover, it was determined that the presence of electrolytes at pH below 7.0 during degradation negatively affected methylene blue degradation. Finally, the results of this work demonstrate that the hydrochar/CeO2 composite can be synthesized by a green method and used for the efficient treatment of water contaminated with methylene blue.

Photocatalytic activity of silver nanoparticles@cellulose nanocomposites, from pistachio husk, in the toxic azo commercial dye degradation.

In this work, an over-the-counter commercial dye, containing direct blue 151 in its composition, which is also discarded without any environmental regulation, was efficiency photodegraded using a green chemistry-synthesized nanocomposites type silver nanoparticles (AgNPs) supported on pistachio husk (PH). The green synthesis (GS) of the nanocomposites was carried out using the Anemopsis californica leaf extract (ExAc) as a reducing-stabilizing agent (AgNPs/ExAc-PH), for the first time. The presence of AgNPs on the nanocomposite surface was corroborated by field emission transmission electron microscope (FE-TEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The synthesized AgNPs/ExAc-PH has a bimodal size of 24 and 25 nm (4.86 % each) and a 0.72 % of AgNPs on its surface. AgNPs were adhered to the PH surface, through secondary bonds between the Ag and the cellulose of the PH. The optimum conditions, for efficient photocatalytic degradation, were 5 mg of nanocomposite, 3.18 × 10-2 M of NaBH4, natural sunlight, and stirring; this results in a photodegradation efficiency of 100 % almost instantaneously. Furthermore, it was shown that the dye degradation process is primarily due to the photocatalytic degradation of the dye, which occurs almost instantaneously.

Influence of UV exposure time and simulated marine environment on different microplastic degradation.

This study investigated the influence of environmental factors (UV radiation and salinity) in the degradative process of microplastics (MPs). MPs derived from polypropylene (PP), polystyrene (PS), and ethylene-vinyl acetate (EVA) were subjected to accelerated photodegradation while being submerged in distilled water or artificial seawater. Depending on the polymer, changes in surface properties, new functional chemical group formation and oxidative index, and thermal characteristics of samples were observed. After photodegradation experiments, EVA-MPs samples showed an increase in their thermal resistance, besides the changes in their surface. PP-MPs crystallinity index increased upon exposure to UV radiation. PS samples showed a higher carbonyl and hydroxyl index after 30 h of UV exposure. The methodology exploited applies to any location in the world and can be comparable once considering the total ultraviolet index (UVI). The saline medium increases the crystallinity index of PP and EVA-MPs samples and intensifies the formation of new carbonyl and hydroxyl bonds in EVA-MPs samples. The results showed that several environmental factors should be considered in interpreting MPs photodegradation.

Degradation of xanthene-based dyes by photoactivated persulfate: experimental and computational studies.

Dyes are naked-eye detectable even at low concentration levels and can cause environmental damage when released into aquatic effluents; therefore, methods for removing the residual color from the aquatic media are always a current issue. In this paper, degradation of three xanthene dyes, Rhodamine B, Eosin Y, and Sodium Fluorescein, using photoactivated persulfate was evaluated at pH 3.0 and 11.0. The dyes' degradation followed a pseudo-first-order reaction. Although the solution is completely decolorized in 40 min at pH 3.0, achieving 75% mineralization requires a longer reaction time of 180 min. Furthermore, GC-MS analyses indicate that degradation products are mainly low-molecular weight acids, CO2 and H2O. Experiments carried out in dark and under UV irradiation showed substantial contribution of radical (SO4•- and HO•) and non-radical pathways to dye degradation in both pH. Additionally, to get more insights into the degradation pathways, HOMO-LUMO energy gaps of the dyes were calculated by DFT using MPW1PW91/MidiXo level of theory and, in general, the lower the bandgap, the faster the degradation. Fukui functions revealed that the preferential sites to radical attack were the xanthene or the benzoate portion depending on the pH, wherein attack to the xanthene ring provided better kinetic and mineralization results.

Effects of the Solvent Vapor Exposure on the Optical Properties and Photocatalytic Behavior of Cellulose Acetate/Perylene Free-Standing Films.

The search to deliver added value to industrialized biobased materials, such as cellulose derivatives, is a relevant aspect in the scientific, technological and innovation fields at present. To address these aspects, films of cellulose acetate (CA) and a perylene derivative (Pr) were fabricated using a solution-casting method with two different compositions. Consequently, these samples were exposed to dimethylformamide (DMF) solvent vapors so that its influence on the optical, wettability, and topographical properties of the films could be examined. The results demonstrated that solvent vapor could induce the apparent total or partial preferential orientation/migration of Pr toward the polymer-air interface. In addition, photocatalytic activities of the non-exposed and DMF vapor-exposed films against the degradation of methylene blue (MB) in an aqueous medium using light-emitting diode visible light irradiation were comparatively investigated. Apparently, the observed improvement in the performance of these materials in the MB photodegradation process is closely linked to the treatment with solvent vapor. Results from this study have allowed us to propose the fabrication and use of the improved photoactivity "all-organic" materials for potential applications in dye photodegradation in aqueous media.

Photooxidative Behavior of Polystyrene Nanocomposites Filled with Two-Dimensional Molybdenum Disulfide.

This study aimed to investigate how an ultralow content of a molybdenum disulfide (MoS2) two-dimensional particle affects the photodegradation mechanism of polystyrene (PS). Here, an accelerated weathering study was presented on neat polystyrene and its nanocomposites produced with 0.001, 0.002, 0.003 and 0.005 wt% of molybdenum disulfide (MoS2) exposed for various irradiation intervals (up to 8 weeks). The polymer photo-transformations were monitored using size exclusion chromatography (SEC), infrared spectroscopy (FTIR), and UV-Vis spectroscopy. The FTIR and UV/Vis results indicate that the PS degradation mechanism was not altered by the presence of MoS2 particles; however, the degradation reactions were slowed down at higher MoS2 contents (>0.003%). The SEC results proved the stabilizer effect due to MoS2 particles, where M¯n, M¯w, and M¯w/M¯n values after 8 weeks were less modified when compared with the neat PS results. The MoS2 acted as a UV stabilizer, and these two-dimensional particles acted by deactivating the free radicals generated by the PS matrix, even considering the low amount of the filler (<0.005 wt%).

Effects of UV sensitivity and accelerated photo-aging on stab resistance of ρ-aramid fabrics impregnated with shear thickening fluids (STFs).

The use of Kevlar in the field of ballistic and stabbing protection has been studied by researchers in polymeric composites for this purpose. This study presents complementary knowledge on energy absorption and dissipation in ρ-aramid fabric impregnated with shear thickening fluids (STFs), especially aiming to obtain better protection against impacts that are deeply associated with STFs, as well as color change, accelerated aging (QUV), and penetration depth (drop tower test). In addition, Scanning Electron Microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) was performed. The research shows that there was a good distribution of STF particles on the ρ-Aramid fabric surface, promoting increased friction between the interfilament and the yarns, further increasing performance and, consequently, improving the energy absorption and dissipation mechanism and, also, the penetration effectiveness in relation to non-impregnated ρ-Aramid fabric. Regarding the protection efficiency against UV exposure (250-400 nm region), there was a significantly decreased compared to those non-impregnated Kevlar® woven with STFs. The FTIR analysis showed that the conditions of aging, after exposure to UV, did not produce new functional groups, that is, there was no chemical modification. Finally, Kevlar fabric impregnated with STFs improved penetration depth performance with the blades independent of the blade type with up to 81% increase in resistance. This result was improved due to interactions between the nanoparticles present in STFs, yarns, and even high-performance woven impregnated with shear-thickening fluids.

Study of degradation of norfloxacin antibiotic and their intermediates by natural solar photolysis.

In this work, the photolysis of the antibiotic norfloxacin (NOR) and the formation of its photodegradation products were studied using UV and solar radiation. Their extraction was also assessed in Milli-Q water and secondary effluents from a wastewater treatment plant. The photolysis of NOR was chromatographically monitored. The structure of each degradation product is related to the reaction of NOR with reactive oxygen species (ROS), as confirmed using radical quenchers and mass spectrometry. Additionally, the feasibility of extracting NOR and its degradation products was assessed using a commercial solid phase extraction system. Photolysis results showed the formation of five degradation products, generated under exposure to both types of radiation. The decays in NOR concentrations for the solar and UV treatments were adjusted to pseudo first-order kinetics with apparent constant values of ksolar = 1.19 × 10-3 s-1 and kUV = 3.84 × 10-5 s-1. Furthermore, the superoxide radical was the main participant species in the formation of the degradation products P3, P4, and P5. Species P1 and P2 do not need this radical for their formation. The presence of NOR in water opens the possibility of its photolysis by solar radiation. This work contributes to the understanding of the mechanisms that mediate its photodegradation, in addition to studying potential options for its determination and its photodegradation products in the sample treatment.

Degradation of amoxicillin applying photo-Fenton and acid hydrolysis processes with toxicity evaluation via antimicrobial susceptibility tests.

ABSTARCTThe antibiotic amoxicillin (AMX) is a semisynthetic aminopenicillin, classified as an ß-lactam antibiotic. This work aims to evaluate the AMX degradation (190 mg L-1), in aqueous medium, applying photo-Fenton ([TOC]0 = 100 mgC L-1; FH2O2 = 3.27 mmol min-1; [Fe2+] = 0.27 mmol L-1; pH = 3.0; T = 40°C) and acid hydrolysis processes. Along the experiments, samples were withdrawn and analyzed by a total organic carbon (TOC) analyzer and a liquid chromatography system coupled to diode array (HPLC-DAD) and mass spectrometry (HPLC-MS) detectors. The hydrolysis process proved to be less efficient, because AMX removals greater than 80% were observed only after 24 hours of reaction (pH 2). Conversely, the photo-Fenton process removed completely AMX in just 20 minutes, reaching 85% of TOC removal in 2 hours. Finally, the AMX aqueous solutions treated by the studied processes was also evaluated in respect of its toxicity to some microorganisms, applying two antimicrobial susceptibility tests: disk-diffusion and broth microdilution methods. It was observed that the AMX aqueous solutions, pretreated by the photo-Fenton process, for just 7.5 min of reaction time, did not inhibit the microorganisms growth. The obtained results show that the photo-Fenton process was able to degrade AMX, in a relatively short time, and that the generated degradation products did not inhibit the microorganisms growth, when compared to acid hydrolysis process. Thus, it was verified the potential application of the photo-Fenton system as a pretreatment step to conventional biological oxidation processes for the treatment of industrial wastewaters.

Environmentally Safe Photodynamic Control of Aedes aegypti Using Sunlight-Activated Synthetic Curcumin: Photodegradation, Aquatic Ecotoxicity, and Field Trial.

This study reports curcumin as an efficient photolarvicide against Aedes aegypti larvae under natural light illumination. Larval mortality and pupal formation were monitored daily for 21 days under simulated field conditions. In a sucrose-containing formulation, a lethal time 50 (LT50) of 3 days was found using curcumin at 4.6 mg L-1. This formulation promoted no larval toxicity in the absence of illumination, and sucrose alone did not induce larval phototoxicity. The photodegradation byproducts (intermediates) of curcumin were determined and the photodegradation mechanisms proposed. Intermediates with m/z 194, 278, and 370 were found and characterized using LC-MS. The ecotoxicity of the byproducts on non-target organisms (Daphnia, fish, and green algae) indicates that the intermediates do not exhibit any destructive potential for aquatic organisms. The results of photodegradation and ecotoxicity suggest that curcumin is environmentally safe for non-target organisms and, therefore, can be considered for population control of Ae. aegypti.

Photodegradation of Rituximab and Critical Evaluation of Its Sensibility to Electromagnetic Radiation.

Rituximab is a monoclonal antibody used in the treatment of lymphoma non-Hodgkin. This mAb is photosensitive as it is administrated to the patient by infusion/perfusion; therefore, photostability is a decisive factor in the efficacy of this biologic. To better understand the photodegradation mechanisms of Rituximab, this biologic was exposed to different irradiance conditions. We show in this study that this mAb photodegrade proportionally to irradiance intensities. The main modifications of Rituximab by irradiance correlate to the increase in aggregates, decrease in its Tm, acidic charge variants, oxidation of the Trp (36) in the heavy chain, and decrease in complement-dependent cytotoxicity (CDC) potency. To understand the relationship between real-life photo-exposition conditions and ICH standardized light tests, a full characterization was set up. Worst photo-stress cases were evaluated, 1 and 2 h under direct sunlight through a window, mimicking the ID65 electromagnetic radiation profile. Our results show that only exposition to direct sun irradiance during 2 h, (≈ 150 kluxes•h), increases critically soluble and insoluble aggregates, diminishing Tm, increasing acidic charge variants, and the photooxidation of the Trp (36) in the heavy chain measured by peptide mapping-RP-UPLC-MS. A decrease in CDC below 80% resulted under this condition, which correlates with physicochemical analyses. While inside light-room exposition (similar to ICH test) and ICH conditions do not have any contribution to the degradation of Rituximab measured by these physicochemical and biological analytical methods. These results indicate that exposition of Rituximab to below ≈ 75 kluxes•h of sun light cannot photodegrade critically this biologic inside of its primary container.

Diclofenac removal by the microalgae species Chlorella vulgaris, Nannochloropsis oculata, Scenedesmus acutus, and Scenedesmus obliquus.

In this work, we evaluated the removal efficiency of diclofenac by Chlorella vulgaris OW-01, Nannochloropsis oculata CCAP 849/7, Scenedesmus acutus UTEX 72, and Scenedesmus obliquus CCAP 276/2. Each microalga was grown in media with different concentrations (50 and 100% of the original formulation) of carbon, nitrogen, and phosphorus, to evaluate their effect on the removal of diclofenac. We also evaluated the photodegradation of diclofenac under the same conditions. The diclofenac removed from the media ranged from 59 to 92%, obtaining the highest removal with S. obliquus. The diclofenac adsorbed on the cell walls ranged from 12.2 to 26.5%, obtaining the highest adsorption with S. obliquus. The diclofenac degraded by light ranged from 15 to 28%. The nutrient deficit showed no influence on the removal of diclofenac in any of the microalgae under study. These results indicate that S. obliquus is the best alternative for the bioremediation of diclofenac. Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-022-03268-2.

Dose-responses for solar radiation exposure reveal high sensitivity of microbial decomposition to changes in plant litter quality that occur during photodegradation.

Plant litter decomposition is a key process for carbon (C) turnover in terrestrial ecosystems. Sunlight has been shown to cause and accelerate C release in semiarid ecosystems, yet the dose-response relationships for these effects have not been evaluated. We conducted a two-phase experiment where plant litter of three species was subjected to a broad range of cumulative solar radiation (CSR) exposures under field conditions. We then evaluated the relationships between CSR exposure and abiotic mass loss, litter quality and the subsequent biotic decomposition and microbial activity in litter. Dose-response relationships demonstrated that CSR exposure was modestly correlated with abiotic mass loss but highly significantly correlated with lignin degradation, saccharification, microbial activity and biotic decay of plant litter across all species. Moreover, a comparison of these dose-response relationships suggested that small reductions in litter lignin due to exposure to sunlight may have large consequences for biotic decay. These results provide strong support for a model that postulates a critical role for lignin photodegradation in the mechanism of photofacilitation and demonstrate that, under natural field conditions, biotic degradation of plant litter is linearly related with the dose of solar radiation received by the material before coming into contact with decomposer microorganisms.

Prospecting carbon-based nanomaterials for the treatment and degradation of endocrine-disrupting pollutants.

The presence of endocrine-disrupting chemicals (EDCs) in water resources has significant negative implications for the environment. Traditional technologies implemented for water treatment are not completely efficient for removing EDCs from water. Therefore, research on sustainable remediation has been mainly directed to novel decontamination approaches including nano-remediation. This emerging technology employs engineered nanomaterials to clean up the environment quickly, efficiently, and sustainably. Thus, nanomaterials have contributed to a wide variety of remediation techniques like adsorption, filtration, coagulation/flocculation, and so on. Among the vast diversity of decontamination technologies catalytic advanced oxidation processes (AOPs) outstand as simple, clean, and efficient alternatives. A vast diversity of catalysts has been developed demonstrating high efficiencies; however, the search for novel catalysts with enhanced performances continues. In this regard, nanomaterials used as nanocatalysts are exhibiting enhanced performances on AOPs due to their special nanostructures and larger specific surface areas. Therefore, in this review we summarize, compare, and discuss the recent advances on nanocatalysts, catalysts doped with metal-based nanomaterials, and catalysts doped with carbon-based nanomaterials on the degradation of EDCs. Finally, further research opportunities are identified and discussed to achieve the real application of nanomaterials to efficiently degrade EDCs from water resources.

High-pressure microfluidization of whey proteins: Impact on protein structure and ability to bind and protect lutein.

Dynamic high-pressure homogenization microfluidization (DHPM) is a versatile emerging technology that may be applied to food processing to achieve several goals. DHPM may, depending on nature of the molecules and the working parameters, induce changes in protein structure, which may improve or impair their techno-functional properties and ability to bind other molecules. In this context, DHPM (12 passes, 120 MPa), coupled or not to a cooling device, was applied to ß-lactoglobulin (ß-lg) and whey protein isolate (WPI) dispersions. Minor changes in the structure of whey proteins were induced by DHPM with sample cooling; although, when sample cooling was not applied, aggregation and increases of around 30% of protein surface hydrophobicity were noticeable for the WPI dispersion. The association constant between the proteins and lutein was in the magnitude of 104 M-1, and lutein photodegradation constant diminished about 3 times in the presence of proteins, compared to in their absence.

In Situ Photochemical Transformation of Hg Species and Associated Isotopic Fractionation in the Water Column of High-Altitude Lakes from the Bolivian Altiplano.

Photochemical reactions are major pathways for the removal of Hg species from aquatic ecosystems, lowering the concentration of monomethylmercury (MMHg) and its bioaccumulation in foodwebs. Here, we investigated the rates and environmental drivers of MMHg photodegradation and inorganic Hg (IHg) photoreduction in waters of two high-altitude lakes from the Bolivian Altiplano representing meso- to eutrophic conditions. We incubated three contrasting waters in situ at two depths after adding Hg-enriched isotopic species to derive rate constants. We found that transformations mostly occurred in subsurface waters exposed to UV radiation and were mainly modulated by the dissolved organic matter (DOM) level. In parallel, we incubated the same waters after the addition of low concentrations of natural MMHg and followed the stable isotope composition of the remaining Hg species by compound-specific isotope analysis allowing the determination of enrichment factors and mass-independent fractionation (MIF) slopes (Δ199Hg/Δ201Hg) during in situ MMHg photodegradation in natural waters. We found that MIF enrichment factors potentially range from -11 to -19‰ and average -14.3 ± 0.6‰ (1 SE). The MIF slope diverged depending on the DOM level, ranging from 1.24 ± 0.03 to 1.34 ± 0.02 for the low and high DOM waters, respectively, and matched the MMHg MIF slope recorded in fish from the same lake. Our in situ results thus reveal (i) a relatively similar extent of Hg isotopic fractionation during MMHg photodegradation among contrasted natural waters and compared to previous laboratory experiments and (ii) that the MMHg MIF recorded in fish is characteristic for the MMHg bonding environment. They will enable a better assessment of the extent and conditions conducive to MMHg photodegradation in aquatic ecosystems.

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River, São Paulo, Brazil).

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO●), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23 ± 0.07) × 10-2 and (7.99 ± 1.61) × 10-3 mol Einstein-1, respectively. In contrast, reactions with HO● radicals and 3CDOM* dominate their degradation, with 1O2 exhibiting rates three to five orders of magnitude lower. The values of kIMD,HO● and kAMT,HO● were (3.51 ± 0.06) × 109 and (4.97 ± 0.37) × 109 L mol-1 s-1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with kIMD,3AQ2S* = (1.02 ± 0.08) × 109 L mol-1 s-1 and kIMD,3CBBP* = (3.17 ± 0.14) × 108 L mol-1 s-1; on the contrary, the values found for AMT are close, kAMT,3AQ2S* = (8.13 ± 0.35) × 108 L mol-1 s-1 and kAMT,3CBBP* = (7.75 ± 0.80) × 108 L mol-1 s-1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO3-, NO2-, CO32-, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

Enhancing the visible-light photoactivity of silica-supported TiO2 for the photocatalytic treatment of pharmaceuticals in water.

Catalyst samples based on SiO2-supported TiO2 were prepared with the incorporation of Ag (metal), S (nonmetal), and ZnO@S (semiconductor and nonmetal). The materials were evaluated regarding their morphological, optical, and crystalline properties as well as their photoactivity under visible and ultraviolet light toward the degradation rate of a model emerging pollutant, acetaminophen (ACT). All modified materials exhibited improved performance over the undoped catalyst. The Ag-doped catalyst achieved the largest degradation under visible radiation (about 30% in 120 min), whereas under ultraviolet irradiation, the ZnO@S-doped sample exhibited the best performance (about 62% in 120 min). A Doehlert design was carried out to evaluate the influence of pH and temperature on the photoactivity of Ag-TiO2/SiO2. In addition, the role of each reactive species in the photodegradation reaction was investigated by radical scavenger experiments, and the superoxide radical anion O2•- was shown to be the predominant reactive species. The stability of the Ag-TiO2/SiO2 material under ultraviolet and visible light was confirmed after five successive operation cycles, showing a reasonable (about 50%) loss of activity under visible irradiation and a slight improvement (about 13%) under UV light, as a result of the photo-reduction of Ag+. Lastly, the effect of the initial pollutant concentration showed that ACT degradation using Ag-TiO2/SiO2 follows the Langmuir-Hinshelwood kinetics, with intrinsic reaction rate k = 2.71 × 10-4 mmol L-1 min-1 under visible-light radiation.

UV-Vis spectrophotometry coupled to chemometric analysis for the performance evaluation of atrazine photolysis and photocatalysis.

In this study, a spectrophotometric-chemometric (Spec-Chem) approach was applied as an alternative to chromatography to monitor ATZ and by-products after photolytic and photocatalytic oxidation aiming to unveil the ATZ degradation mechanism. Spec-Chem is an accessible, easy-to-operate, low-cost analytical approach to monitor atrazine (ATZ) and by-products, and its applicability was validated by HPLC, the reference technique for the evaluation of pollutant degradation mechanisms. The chromatographic (DChro) and spectrophotometric (DSpec) data found 95% and 57% ATZ removal after 30 min, respectively, proving that the DSpec erroneously induces a 38% loss in removal efficiency. When DSpec was treated by multivariate curve resolution (MCR) analysis for providing chemometric data (DChem), it found ATZ removal and hydroxyatrazine (HAT) formation statistically equal to DChro (t-test, p = 0.05). After unraveling the ATZ degradation mechanism using Spec-Chem, a new hypothesis for the kinetic calculation of ATZ degradation was presented, where the concentrations of ATZ and HAT were used to find k and R2 values representative for the ATZ degradation mechanism. The values found for k were compatible with the literature under similar conditions of ATZ degradation, and the linear correlation coefficients (R2 = 0.99) showed an optimal fit for the proposed hypothesis. Thus, Spec-Chem was successfully applied to unravel the mechanism of photocatalytic degradation of ATZ in the presence of TiO2, while k was obtained by the new hypothesis proposed that considered ATZ and HAT concentration as parameters of kinetic interest. Therefore, the importance of monitoring quantitatively ATZ and HAT were provided in this study, providing new information for the scientific community.