Application of multivariate data techniques in photochemical study of polycyclic aromatic hydrocarbons (PAHs) and transformed PAH products in road dust.

Road dust is a key repository for PAHs and transformed PAH products (TPPs) generated from natural and anthropogenic sources in the urban environment. Eventhough PAHs and TPPs are prone to post-emission photochemical processes, very limited studies exist on the subject for road dust. This knowledge gap is of particular concern since some of the resultant TPPs are notably more carcinogenic than their precursor PAHs. This study evaluated the role of 254 nm ultraviolet (UV) photons on the photochemistry of PAHs and TPPs in road dust. The findings show that UV irradiation had varying effects on the fate of analytes, particularly naphthalene (NAP), phenanthrene (PHE), 7, 12-dimethylbenz(a)anthracene (DMBA), 1-hydroxypyrene (HPY), 1-nitropyrene (1NPY), pyrene (PYR) and 5-nitroacenaphthene (5NAC). Photochemical relationship was identified between PYR, 1NPY and HPY, and DMBA and benzo(a)anthracene. Unlike carbonyl-PAHs, parent PAHs, nitro-PAHs and hydroxy-PAHs can originate from photolysis. Photon irradiation durations of 3, 6 and 7.5 h had the most intense influence on the photolytic process with 7.5 h as optimum. The photochemical rate at optimum irradiation duration shows an increasing trend of NAP < PHE < 1NPY < DMBA < 5NAC < HPY with respective estimates of 0.08, 0.11, 0.21, 0.22, 0.43, and 0.59 mg kg-1 hr-1. Physicochemical properties of analytes such as index of refraction and vapour pressure (in logarithmic form) had an inverse effect on photolysis. The knowledge generated is significant for the in-depth understanding of the fate of PAHs and TPPs on urban road surfaces and contributes to the greater protection of human health and the environment.

Photodecomposition properties of brominated flame retardants (BFRs).

This study investigates the geometric and electronic properties of selected BFRs in their ground (S0) and first singlet excited (S1) states deploying methods of the density functional theory (DFT) and the time-dependent density functional theory (TDDFT). We estimate the effect of the S0→ S1 transition on the elongations of the C-Br bond, identify the frontier molecular orbitals involved in the excitation process and compute partial atomic charges for the most photoreactive bromine atoms. The bromine atom attached to an ortho position in HBB (with regard to C-C bond; 2,2',4,4',6,6'-hexabromobiphenyl), TBBA (with respect to the hydroxyl group; 2,2',6,6'-tetrabromobisphenol A), HBDE and BTBPE (in reference to C-O linkage; 2,2',4,4',6,6'-hexabromodiphenylether and 1,2-bis(2,4,6-tribromophenoxy)ethane, respectively) bears the highest positive atomic charge. This suggests that, these positions undergo reductive debromination reactions to produce lower brominated molecules. Debromination reactions ensue primarily in the aromatic compounds substituted with the highest number of bromine atoms owing to the largest stretching of the C-Br bond in the first excited state. The analysis of the frontier molecular orbitals indicates that, excitations of BFRs proceed via π→π*, or π→σ* or n→σ* electronic transitions. The orbital analysis reveals that, the HOMO-LUMO energy gap (EH-L) for all investigated bromine-substituted aromatic molecules falls lower (1.85-4.91 eV) than for their non-brominated analogues (3.39-8.07 eV), in both aqueous and gaseous media. The excitation energies correlate with the EH-L values. The excitation energies and EH-L values display a linear negative correlation with the number of bromine atoms attached to the molecule. Spectral analysis of the gaseous-phase systems reveals that, the highly brominated aromatics endure lower excitation energies and exhibit red shifts of their absorption bands in comparison to their lower brominated congeners. We attained a satisfactory agreement between the experimentally measured absorption peak (λmax) and the theoretically predicted oscillator strength (λmax) for the UV-Vis spectra. This study further confirms that, halogenated aromatics only absorb light in the UV spectral region and that effective photodegradation of these pollutants requires the presence of photocatalysts.

Sequential Process Combination of Photocatalytic Oxidation and Dark Reduction for the Removal of Organic Pollutants and Cr(VI) using Ag/TiO2.

We investigated a sequential photocatalysis-dark reaction, wherein organic pollutants were degraded on Ag/TiO2 under UV irradiation and the dark reduction of hexavalent chromium (Cr(VI)) was subsequently followed. The photocatalytic oxidation of 4-chlorophenol (4-CP), a test organic substrate, induced the generation of degradation intermediates and the storage of electrons in Ag/TiO2 which were then utilized for reducing Cr(VI) in the postirradiation period. The dark reduction efficiency of Cr(VI) was much higher with Ag/TiO2 (87%), compared with bare TiO2 (27%) and Pt/TiO2 (22%). The Cr(VI) removal by Ag/TiO2 (87%) was contributed by adsorption (31%), chemical reduction by intermediates of 4-CP degradation (26%), and reduction by electrons stored in Ag (30%). When formic acid, humic acid or ethanol was used as an alternative organic substrate, the electron storage effect was also observed. The postirradiation removal of Cr(VI) on Ag/TiO2 continued for hours, which is consistent with the observation that a residual potential persisted on the Ag/TiO2 electrode in the dark whereas little residual potential was observed on bare TiO2 and Pt/TiO2 electrodes. The stored electrons in Ag/TiO2 and their transfer to Cr(VI) were also indicated by the UV-visible absorption spectral change. Moreover, the electrons stored in the preirradiated Ag/TiO2 reacted with O2 with showing a sign of low-level OH radical generation in the dark period.

Rapid reduction of lead leachate from hazardous fly ash using microwave treatment with acid combination.

The novelty of this study is to rapidly reduce hazardous lead leachates from solid waste using microwave digestion treatment, which is an energy-saving and low greenhouse gas emission technology. The article presents the reduction of toxic characteristic leaching procedure-extractable lead concentration in the municipal solid waste incineration fly ash by the microwave digestion treatment in HNO3/H2SO4 combination, and focuses on the effects of treatment time and temperature. The results obtained from this study indicated a significant reduction efficiency of toxic characteristic leaching procedure-extractable lead concentration and showed sufficient reduction in leaching levels to render the treated fly ash safe in lead compound leaching characteristics. The reduction efficiency of toxic characteristic leaching procedure-extractable lead concentration can reach 98% in 15 minutes of treatment time. This is equivalent to the original toxic characteristic leaching procedure-extractable lead concentration of 46.2 mg L(-1) in raw fly ash being reduced down to less than 1.0 mg L(-1). Based on the experimental data obtained in this study, a useful correlation between reduction efficiency and treatment conditions is proposed. For engineering applications, the necessary minimum treatment time is solved using a graphic illustration method, by which the minimum treatment time (t(min)) is obtained if the desired reduction efficiency (η) and treatment temperature (T) are known. The effects of treatment time and temperature are discussed. Some problems caused by the microwave digestion treatment method are also delineated in this article.

Photocatalytic Performances of Ag3PO4 Polypods for Degradation of Dye Pollutant under Natural Indoor Weak Light Irradiation.

It is still a big challenge for Ag3PO4 to be applied in practice mainly because of its low stability resistant to photo corrosion, although it is an efficient photocatalyst. Herein, we have mainly investigated its activity and stability under indoor weak light for the degradation of dye pollutants. It is amazing that under indoor weak light irradiation, rhodamine B (RhB) can be completely degraded by Ag3PO4 polypods after 36 h, but only 18% of RhB by N-doped TiO2 after 120 h. It is found that under indoor weak light irradiation, the degradation rate (0.08099 h(-1)) of RhB over Ag3PO4 polypods are 46 times higher than that (0.00173 h(-1)) of N-doped TiO2. The high activity of Ag3PO4 polypods are mainly attributed to the three-dimensional branched nanostructure and high-energy {110} facets exposed. After three cycles, surprisingly, Ag3PO4 polypods show a high stability under indoor weak light irradiation, whereas Ag3PO4 have been decomposed into Ag under visible light irradiation with an artificial Xe light source. This natural weak light irradiation strategy could be a promising method for the other unstable photocatalysts in the degradation of environmental pollutants.

Controllable synthesis of Cu2O/Cu composites with stable photocatalytic properties.

Here we reported a facile approach to synthesize Cu2O/Cu composite particles by one-step sono-chemical process. The content of Cu in the Cu2O/Cu composites can be easily controlled by adjusting the synthesis time. Phase, morphology and optical properties of the products were carried out by X-ray diffraction (XRD), field-emission scanning electron microscopy (FSEM), transmission electron microscope (TEM), ultraviolet-visible (UV-vis) spectroscopy and nitrogen adsorption apparatus. Using photocatalytic degradation of Methyl orange (MeO) dye under visible-light illumination, we have investigated the influence of Cu on the photocatalytic activity of Cu2O, to find out its potential application in waste water treatment. Especially, the stability of the photocatalyst was confirmed using reclaimed Cu2O/Cu in ten successive runs. Results demonstrated clearly that Cu2O/Cu were stable and resistant to photocorrosion during the photocatalytic oxidation of organic compounds, indicating that these Cu2O/Cu composites are promising candidates for pollutant processing.

ZnO nanocrystals anchored graphene: in situ solvothermal synthesis and enhanced photocatalytic performance.

ZnO nanocrystals anchored graphene composite (ZnO/G) was synthesized by a facile in situ solvothermal route. The nanocomposite was characterized by X-ray diffraction (XRD), scanning electron spectroscopy (SEM), transmission electron microscopy (TEM) and Raman spectra (RS). The results indicated that the ZnO particles with an average diameter of ca. 12.6 nm were well-dispersed on the surface of the graphene nanosheets. The optical properties were investigated by fluorescence (PL) and UV diffuse reflectance (UV-VIS). It showed that the nanocomposite displayed a fluorescence quenching property. Furthermore, the nanocomposite showed a remarkably enhanced photocatalytic activity to degrade organic pollutants (MB, MO, Rh-B) under visible light irradiation, with a percentage degradation of MB reaching as high as 99.8% in 60 min.

Irradiation-Enhanced Cytotoxicity of Zinc Oxide Nanoparticles.

Zinc oxide (ZnO) nanoparticles (NPs) are being widely utilized in industry due to their versatile properties. The in vitro cytotoxicity findings and the potential for exposures to ZnO NP from different sources via different routes of entry into the body have raised public health concerns. Although recent studies have shown the cytotoxic effects of these NPs, including oxidative stress, apoptosis and necrosis induction, genotoxicity, and others, irradiation-induced cytotoxicity has not been systematically studied. The goal of this study was to determine whether irradiation in the forms of visible light (approximately 400-600 nm), ultraviolet (UV) A (366 nm), and UVC (254 nm) would affect ZnO NPs-induced cytotoxicity. The results of this study demonstrated that the cytotoxicity of 60 to 80 nm ZnO NPs to A549 cells is dosage, time, and wavelength dependent. Nuclear decomposition by ZnO NPs, prior to membrane deformation, was found to be enhanced when exposed to irradiation. This study suggests that this phenomenon may be attributed to the irradiation-induced formation of positively charged sites on the ZnO NPs, which enhances nuclear affinity and generation of reactive oxygen species. Finally, the data demonstrated that while ZnO NPs act preferentially toward nuclear regions, destructions of cell membrane and the cytosol have also been observed. The photocatalytic properties of ZnO NPs play a critical role during the early stages of cell death, and their effects were reduced through the use of an antioxidant, N-acetylcysteine. In conclusion, both visible light and UV irradiations have been found to enhance the cytotoxic effect of ZnO NPs on the A549 cell line. This finding supports the need for further in vivo exposure studies relevant to actual conditions to confirm whether combined irradiation and ZnO NP exposure could enhance the nanotoxicity of ZnO NPs.

Structuring ß-Ga2O3 photonic crystal photocatalyst for efficient degradation of organic pollutants.

Coupling photocatalysts with photonic crystals structure is based on the unique property of photonic crystals in confining, controlling, and manipulating the incident photons. This combination enhances the light absorption in photocatalysts and thus greatly improves their photocatalytic performance. In this study, Ga2O3 photonic crystals with well-arranged skeleton structures were prepared via a dip-coating infiltration method. The positions of the electronic band absorption for Ga2O3 photonic crystals could be made to locate on the red edge, on the blue edge, and away from the edge of their photonic band gaps by changing the pore sizes of the samples, respectively. Particularly, the electronic band absorption of the Ga2O3 photonic crystal with a pore size of 135 nm was enhanced more than other samples by making it locate on the red edge of its photonic band gap, which was confirmed by the higher instantaneous photocurrent and photocatalytic activity for the degradation of various organic pollutants under ultraviolet light irradiation. Furthermore, the degradation mechanism over Ga2O3 photonic crystals was discussed. The design of Ga2O3 photonic crystals presents a prospective application of photonic crystals in photocatalysis to address light harvesting and quantum efficiency problems through manipulating photons or constructing photonic crystal structure as groundwork.

How redox conditions and irradiation affect sorption of PAHs by dispersed fullerenes (nC60).

Surface properties, dispersion state, and sorption behavior of carbon-based nanomaterials will change after being released into the environment. To study these processes, five different scenarios were considered to probe the impact of changes in surface properties of dispersed fullerenes (nC60) on their sorption potential due to irradiation and presence of oxygen. Sorption isotherms of pyrene by nC60 were determined at environmentally relevant concentrations applying a passive sampling method. Isotherms of all dispersion scenarios were best fit with the Dubinin-Ashthakov model. Sorption was strongest for nC60 kept under anoxic condition. Both the presence of oxygen and irradiation significantly decreased the sorption capacity of nC60, while commercially available polyhydroxy fullerenes had the smallest sorption. In addition, competition for sorption sites was never observed in multiple sorbate experiments with four polycyclic aromatic hydrocarbons at small concentration. A strong relationship between sorption coefficients and hydrophobic properties of sorbates suggests that hydrophobic interactions are of major importance. The results emphasize that aging of released fullerenes results in a reduced strength of interactions with nonpolar compounds and, thus, reduces the impact on the environmental transport of hydrophobic pollutants.

Response surface methodology (RSM) analysis of photodegradation of sulfonated diazo dye Reactive Green 19 by UV/H2O2 process.

A central composite design was used to investigate the influence of the main process parameters on the degradation of Reactive Green 19 (RG19) azo dye by the UV/H2O2 treatment. The combined use of UV radiation and H2O2 resulted in the decolorization and dearomatization of the dye. They were monitored by measuring the spectral changes occurring, respectively, in the visible and UV regions of the dye spectrum. RG19 degradation was found to be practically complete over a time of 15-60 min, for decolorization, and 50-200 min, for dearomatization, depending on the applied conditions. Both processes followed apparent first-order kinetics. The associated rate constants were used as the response variables and their dependence on initial dye and H2O2 concentrations, pH and reaction time was investigated by the response surface methodology. Response surface plots for the decolorization and dearomatization processes were very similar in shape. For both processes, the initial dye and H2O2 concentrations were the key factors controlling dye degradation.

The photoconversion of gamma-hexachlorocyclohexane under UV irradiation in water, snow and ice.

The photochemistry of organic pollutants has received increasing attention in ice and snow. In this work, the photoconversion of gamma-hexachlorocyclohexane (γ-HCH) under UV irradiation was investigated in water, snow and ice. The photoconversion rate, products and mechanisms were inspected, and the effect of inorganic ions (NO2(-), NO3(-), HCO3(-) and Fe(2+)) was discussed. The results showed that γ-HCH could be photoconverted in water, snow and ice, with the photoconversion rate being fastest in snow, and slowest in ice. All photoconversion could be described by the first-order kinetics model. In water, snow and ice, the common photoproducts of γ-HCH were alpha-hexachlorocyclohexane (α-HCH) and pentachlorocyclohexene. α-HCH was generated by a change in the bonding of a chlorine atom in γ-HCH; pentachlorocyclohexene was generated by the removal of a molecule of chlorine hydride from a molecule of γ-HCH. Different concentrations of NO2(-), NO3(-) and HCO3(-) all inhibited the photoconversion of γ-HCH, and the inhibition effect decreased with increasing concentrations of NO2(-) and NO3(-), but increased with the increasing concentrations of HCO3(-). Different concentrations of Fe(2+) promoted the photoconversion of γ-HCH in water and ice, but had little effect in snow.

Synthesis of surface sulfated BiWO with enhanced photocatalytic performance.

Sulfated BiWO (SBiWO) was synthesized by an impregnation method to enhance the visible-light-driven photoactivities of BiWO (BiWO). The characterization results verified that sulfate anion mainly anchored on the catalyst surface greatly extended the visible-light-responsive range without destroying the crystal lattice. Moreover, the SBiWO-based photoactivities were evaluated with the removal of Malachite Green (MG) under UV-Vis irradiation emitted from two microwave-powered electrodeless discharge lamps (MPEDL2) and under visible light (lamda > 420 nm). The results demonstrated that the kinetic constant was increased 2.25 times, varying from 0.1478 (BiWO) to 0.3328 min(-1) (SBiWO-1). Similar results were also obtained for the visible light-driven reaction. Furthermore, radical scavengers such as t-butanol restricted the visible-light induced degradation of MG over BiWO and SBiWO-1. This indicated that the sulfating process increased the generation of reactive oxygen species, which was further verified by molecular probe with salicylic acid. Thus, more blue-shifting at lam = 618 nm was observed over SBiWO. On the basis of the above results, the photocatalytic mechanism over the sulfated catalyst was also discussed.

Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: adsorption, oxidation, and photocatalysis.

Manganese oxides are known as one type of semiconductors, but their photocatalysis characteristics have not been deeply explored. In this study, photocatalytic degradation of phenol using several synthesized manganese oxides, i.e, acidic birnessite (BIR-H), alkaline birnessite (BIR-OH), cryptomelane (CRY) and todorokite (TOD), were comparatively investigated. To elucidate phenol degradation mechanisms, X-ray diffraction (XRD), ICP-AES (inductively coupled plasma-atomic emission spectroscopy), TEM (transmission electronic microscope), N2 physisorption at 77 K and UV-visible diffuse reflectance spectroscopy (UV-Vis DRS) were employed to characterize the structural, compositional, morphological, specific surface area and optical absorption properties of the manganese oxides. After 12 hr of UV-Vis irradiation, the total organic carbon (TOC) removal rate reached 62.1%, 43.1%, 25.4%, and 22.5% for cryptomelane, acidic birnessite, todorokite and alkaline birnessite, respectively. Compared to the reactions in the dark condition, UV-Vis exposure improved the TOC removal rates by 55.8%, 31.9%, 23.4% and 17.9%. This suggests a weak ability of manganese oxides to degrade phenol in the dark condition, while UV-Vis light irradiation could significantly enhance phenol degradation. The manganese minerals exhibited photocatalytic activities in the order of: CRY > BIR-H > TOD > BIR-OH. There may be three possible mechanisms for photochemical degradation: (1) direct photolysis of phenol; (2) direct oxidation of phenol by manganese oxides; (3) photocatalytic oxidation of phenol by manganese oxides. Photocatalytic oxidation of phenol appeared to be the dominant mechanism.

Physical insight into the sonochemical degradation of 2,4-dichlorophenol.

In this study, we have attempted to reveal the physical or mechanistic features of the sonochemical degradation of 2,4-dichlorophenol (2,4-DCP). The principal physical phenomenon underlying sonochemical effects is radial motion of cavitation bubbles and production of radicals from transient collapse of these bubbles. We reveal some important physical facets of sonochemical degradation of 2,4-DCP by adopting dual approach of coupling experimental results with simulations of radial motion of cavitation bubble. First, the location of the degradation is predominantly the interfacial region between bubble and bulk medium, and secondly, the extent of degradation is controlled by conservation--and not the production--of oxidizing radicals that affects the probability of radical-pollutant interaction.

Abiotic and biotic degradation of five aromatic organosilicon compounds in aqueous media-Structure degradability relationships.

Silicones have many applications and are produced in large quantities. Despite their potential toxicity, information on their environmental mineralisation is scarce. Therefore, we investigated a group of five organosilicon compounds (o-MeOC6H4SiMe3 (1), p-MeOC6H4SiMe3 (2), (p-MeOC6H4)2SiMe2 (3), o-Me2NC6H4SiMe3 (4) and p-Me2NC6H4SiMe3 (5)), recently developed to be 'benign by design' based on their readily degradable core structure. Five different degradability tests were performed, one assessing hydrolytic and two analysing biological and photolytic stability, respectively. All substances, except (p-MeOC6H4)2SiMe2 (3), hydrolysed within 24 h to 50% indicating that this is one of the major pathways of their primary elimination. In agreement with previous research, none of the substances was readily biodegradable. In contrast, 100% of p-Me2NC6H4SiMe3 (5) was primarily eliminated by photolytic and hydrolytic processes. The elimination rates of the other substances ranged from 7% to 64%. Irradiation at shorter wavelengths increased both the extent and speed of photodegradation. Eleven transformation products of p-Me2NC6H4SiMe3 (5) were detected, all of which were completely eliminated within 64 min of irradiation with a Hg lamp (200-400 nm). The insertion of an electron-donating group on the benzene ring like in p-Me2NC6H4SiMe3 (5) clearly enhanced photolytic degradability but further research is necessary to achieve truly biodegradable silicones.

Investigation of the Potential Environmental Risks of Phthalate Derivatives Designed To Be Environmentally Friendly.

Phthalate derivatives with low estrogenic activity, high infrared spectrum signals, high Raman characteristic vibration spectrum, high fluorescence intensity, and high ultraviolet sensitivity were selected as precursors from our previous studies, so that the changes in their toxicity and estrogenic activity during biological metabolism, ozone oxidation, photocatalytic degradation, photodegradation, and microbial degradation could be studied.The transformation pathways of these derivatives were simulated, and the reaction energy barriers were calculated. To determine the potential environmental risks of these phthalate derivatives, the pharmacophore models of biotoxicity and estrogen activity of phthalates were used to predict the biotoxicity and estrogen activity of the transformed products. The results showed an increase in the biotoxicity and estrogen activity of the biometabolites, ozonation products, photocatalytic degradation products, and microbial degradation products; the only products that did not follow this trend were the photodegradation products. Notably, the pathways that produced more potentially toxic compounds were the less favorable paths. Our results indicate that the transformation products of the designed environmentally friendly phthalate derivatives potentially pose environmental risks. To avoid such risks, the environmental transformation pathway of these derivatives should be simulated to screen for environmentally friendly phthalate molecules. Environ Toxicol Chem 2020;39:1138-1148. © 2020 SETAC.

Integration of plasmonic effect into MIL-125-NH2: An ultra-efficient photocatalyst for simultaneous removal of ternary system pollutants.

Industrial effluents often contain mixed metal ions and dyes, and it is difficult to efficiently remove both types of contaminants simultaneously. Here, MIL-125-NH2@Ag/AgCl composites were for the first time developed through a facile deposition-photoreduction method for simultaneously removing Cr(VI)/Rhodamine B (RhB)/Malachite Green (MG) ternary system pollutants under visible-light irradiation. The capacities of Cr(VI) reduction dramatically increased to 98.4% in the coexistence of RhB and MG compared to that of binary (Cr(VI)/RhB (69.6%) or Cr(VI)/MG (67.5%)) and single Cr(VI) (29%) systems. In the meantime, the degradation efficiencies of dyes especially RhB in the ternary system were also improved compared to that of their individual systems. On the grounds of all the experimental results, it can be concluded that the efficient light-harvesting and electrons migration in MIL-125-NH2@Ag/AgCl and the synergistic effect of redox reactions between Cr(VI) and dyes hinder the recombination of photo-induced electron-hole pairs, which are responsible for their high photocatalytic activity to eliminate the mixed pollutants. This study provides a new route to construct high-performance photocatalysts for the practical treatment of wastewater containing mixed pollutants.

Photocatalytic degradation of paracetamol on Pd-BiVO4 under visible light irradiation.

In this study, Pd-BiVO4 bearing highly dispersed Pd nanoparticles was prepared from pure BiVO4 using an impregnation method. The pure BiVO4 and Pd-BiVO4 catalysts were characterized by X-ray diffraction, scanning electron microscopy, UV-visible diffuse reflection, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results showed that the prepared catalysts had a monoclinic scheelite structure and exhibited a flake-like morphology. Pd-BiVO4 showed a distinct response in the visible light region, with an extended absorption edge at 550 nm. According to the Scherrer formula, the nanocrystal particle sizes of the BiVO4 and Pd-BiVO4 catalysts were 35 and 28 nm, respectively. Highly dispersed Pd nanoparticles with sizes of 2.5 ±â€¯0.5 nm were observed on the BiVO4 surface. Two Pd valence states, Pd(II) and Pd(0), were identified in a 2:1 ratio. Pd-BiVO4 exhibited excellent activity for paracetamol (PCT) degradation, with 100% removal achieved in 1 h under visible light irradiation. During degradation, the mineralization ratio reached up to 40% total organic carbon removal. Two highly active species, namely, hydroxyl and superoxide radicals, were determined by electron spin resonance (ESR). Furthermore, the potential degradation of PCT in this system was proposed based on intermediate information obtained using HPLC-MS and Gauss analysis. The high dispersion and small size of Pd nanoparticles might favor the removal of emerging contaminants using the Pd-BiVO4 photocatalytic system.

Updated and validated solar irradiance reference spectra for estimating environmental photodegradation rates.

Irradiance reference spectra are used to calculate environmentally relevant photodegradation half-lives, but the currently used spectra were originally published in the 1980s with limited validation. The goal of this work is to provide updated irradiance reference spectra using the Simple Model of the Atmospheric Radiative Transfer of Sunshine (SMARTS). The SMARTS irradiance spectra were validated against measurements from several high-resolution spectroradiometers, and the updated irradiance reference spectra use current measurements for atmospheric species that can affect the irradiance that reaches the Earth's surface. These updated irradiance spectra are provided in 1 nm increments from 280 to 800 nm for 0° to 70° latitude at 10° increments in both the northern and southern hemisphere. Lastly, the influence of the input parameters on the modeled irradiance spectra was investigated. This work will allow users to calculate more accurate photodegradation half-lives using the updated irradiance reference spectra, and it also provides insight for users to calculate their own location- and time-specific irradiance spectra using SMARTS.