The compound 2,4,6-trichlorophenol poses significant risks to both the aquatic environment and human health. Its inherent persistence and stability present challenges in achieving complete purification, thus warranting its inclusion as a priority pollutant. The present study reports the development of an amphiphilic small-molecule compound that self-assembles into nanovesicles exhibiting remarkable adsorption and photodegradation capabilities. Through the synergistic effects of hydrogen bonding, van der Waals forces, π-π interactions, and electrostatic interactions, these vesicles efficiently adsorb 2,4,6-trichlorophenol from aqueous solutions within 1 min while demonstrating exceptional environmental stability and broad applicability. Upon self-assembly into vesicles, not only are more adsorption sites exposed, but charge separation and migration within the vesicles are also facilitated. Through the synergistic effects of adsorption and photodegradation, complete removal of 2,4,6-trichlorophenol in aqueous solution can be achieved within 8 h while exhibiting excellent recycling capability. This approach offers a viable strategy for designing and synthesizing pure organic photodegradable materials.

Olive oil production is one of the most developed Europe\'s sectors, producing olive oil and undesirable by-products, such as olive mill wastewater (OMWW) and organic waste. OMWW, containing large amounts of compounds (mainly polyphenols, phenols, and tannins), represents a problem. In fact, polyphenols have dual nature: i) antioxidant beneficial properties, useful in many industrial fields, ii) biorefractory character making them harmful in high concentrations. If not properly treated, polyphenols can harm biodiversity, disrupt ecological balance, and degrade water quality, posing risks to both environment and human health. From a circular economy viewpoint, capturing large quantities of polyphenols to reuse and removing their residuals from water is an open challenge. This study proposes, for the first time, a new path beyond the state-of-the-art, combining adsorption and degradation technologies by novel, eco-friendly and easily recoverable bismuth-based materials to capture large amounts of two model polyphenols (gallic acid and 3,4,5-trimethoxybenzoic acid), which are difficult to remove by traditional processes, and photodegrade them under solar light. The coupled process gave rise to collect 98% polyphenols, and to rapidly and effectively photodegrade the remaining portion from water.

The influences of the positive Fe3+ and the negative Cr2O72- on the tetracycline (TC) photodegradation by N-doped dissolved black carbon (NDBC) have been investigated in this work. A series of samples (NDBC300, NDBC400 and NDBC500) have been extracted from the corresponding biochar. NDBC400 has the best photodegradation performance (79%) for TC under visible light irradiation. Adding Cr2O72- and Fe3+ can reduces TC photodegradation efficiency into 37% and 53%, respectively. This maybe from that Cr2O72- has stronger interaction with NDBC400 than Fe3+ since it can quench more fluorescence intensity of NDBC400 than Fe3+. Furthermore, Cr2O72- can reduce the steady-state concentration of 3NDBC400*, 1O2 and •OH, whereas Fe3+can just reduce the steady-state concentration of 3NDBC400* and increase the concentration of •OH. This may explain why Cr2O72- has stronger inhibit performance of TC photodegradation by NDBC400 than Fe3+. The band structures of NDBC400, NDBC400-Fe3+ and NDBC400-Cr2O72- are constructed. And the VB of NDBC400-Fe3+ has a stronger ability to produce •OH than NDBC400. In summary, coupling interaction and band structure characterization of NDBC400, NDBC400-Fe3+ and NDBC400-Cr2O72- can explain well why Cr2O72 has stronger inhibition effect than Fe3+ and Fe3+ can increase the concentration of •OH. This work provides a deep insight for the photochemical behavior of dissolved black carbon and the transformation behavior of the co-existed metal ions and antibiotics.

Tylosin tartrate, a macrolide antibiotic, is one of a class of emerging contaminants that have been detected in natural bodies of water since they are not easily removed by conventional treatment processes. In this study, the direct and indirect photodegradation of tylosin tartrate was analyzed to understand the role of reactive oxygen species and organic matter that may be present in surface waters. While direct photolysis caused negligible degradation (k = (9.4 ± 1.8) × 10-5 s-1), the addition of 0.4 M hydrogen peroxide (k = (2.18 ± 0.01) × 10-4 s-1) or usage of the photo-Fenton process (k = (2.96 ± 0.02) × 10-4 s-1) resulted in greater degradation. The degradation was maximized by combining tylosin tartrate with an experimentally determined optimal concentration of humic acid (15 mg/L), which readily produced singlet oxygen and increased the overall degradation (k = 1.31 ± 0.05) × 10-3 s-1) by means of indirect photolysis. Absolute pseudo-first-order bimolecular reaction rate constants for tylosin tartrate were measured with singlet oxygen [(4.7936 ± 0.0001) × 105 M-1 s-1] and hydroxyl radical [(5.2693 ± 0.0002) × 109 M-1 s-1] using competition kinetics, and when combined with data on concentration of the reactive oxygen species, showed that the hydroxyl radical makes a contribution to the degradation that is approximately eleven orders of magnitude greater than singlet oxygen.

Exploring high-performance photocatalysts still remains a big challenge due to poor charge separation efficiency. Herein, we prepare a novel anatase/rutile TiO2-Ag3PO4 hollow photocatalyst (A/R-TiO2-Ag3PO4) for addressing this challenge. Microstructural characterization and photoelectric measurements confirm that the synergy of hollow structure and dual-heterojunction can provide abundant active sites and boost efficient charge separation through dual-pathway charge transfer mechanism. The A/R-TiO2-Ag3PO4 photocatalyst exhibits the highest photocurrent density (15.25 µA cm-2), which is 8.4 and 5.2 times than that of A-TiO2-Ag3PO4 (1.82 µA cm-2) and P25-Ag3PO4 (2.93 µA cm-2), respectively. Photo-degradation experiment shows that A/R-TiO2-Ag3PO4 presents a high degradation percentage (98.7 %) of thiamethoxam (THX) within 30 min, which is 1.45 and 1.23 times than that of A-TiO2-Ag3PO4 (68.1 %) and P25-Ag3PO4 (80.7 %), respectively. Furthermore, the degradation percentage of THX by A/R-TiO2-Ag3PO4 is as high as 96.4 % after seven successive cycles, indicating excellent cycling stability. Therefore, this work provides a new insight into exploring other high-performance photocatalysts by combining hollow structure and dual-heterojunction.

This research addresses the scalable and inexpensive synthesis of α-Fe2O3via hydrothermal method without any precipitating agent as well as the enhancement of solar driven photocatalytic and H2 production through doping different chromium proportions. Competency of α-Fe2O3, both pure and doped with chromium, to function as photocatalyst was evaluated by its interaction with multiple dyes, which was real-time monitored utilizing (Internet of Things) IoT technique. By adding chromium, the rate of deterioration increased substantially from 15 to 94% for TB under sunlight in a remarkably brief 20 min by employing a very small amount of Cr0.8Fe1.2O3 (0.3 g/L), as evidenced by high degree of mineralization i.e. 85% and LC-HRMS. Also, the rapid breakdown of Trypan Blue (TB) was indicated by BOD5/COD ratio. Moreover, Cr-doped α-Fe2O3 displays excellent H2 production (~ 132 μmol h-1 g-1) as compared to α-Fe2O3. This work highlights the potential utilization of Cr-doped α-Fe2O3 for the purification of industrial waste water and green energy harvesting.

In this work, polyvinylidene fluoride (PVDF) intercalated CuFe layered double hydroxides (LDH) membranes were fabricated and investigated for UV-LED/persulfate degradation of methylene blue (MB), crystal violet (CV), methyl orange (MO), and Eriochrome black T (EBT) dyes from water. The PVDF-CuFe membrane exhibited improved heterogeneity, surface functionality (CuO, Fe-O, Cu-O-Fe), surface roughness, and hydrophilicity. The process parameters were optimized by response surface methodology, and maximum MB removal (100%) was achieved within 45.22-178.5 min at MB concentration (29.45-101.93 mg/L), PP concentration (0.5-2.41 g/L) and catalyst dosage (1.84-1.95 g/L). The degradation kinetics was well described by a pseudo-first-order model (R2 = 0.982) and fast reaction rate (0.029-0.089/min). The MB dye degradation mechanism is associated with HO·/SO4•- reactive species generated by Fe3+/Fe2+ or Cu2+/Cu+ in PVDF-CuFe membrane and PP dissociation. The PVDF-CuFe membrane demonstrated excellent recyclability performance with a 12% reduction after five consecutive cycles. The catalytic membrane showed excellent photocatalytic degradation of crystal violet (100%), methyl orange (79%), and Eriochrome black T (60%). The results showed that UV-LED/persulfate-assisted PVDF-CuFe membranes can be used as a recyclable catalyst for the effective degradation of dye-contaminated water streams.

Parabens are classified as emerging contaminants in global waters, and the ubiquitous emergence of their high-risk chlorinated products generated from chlorine-based wastewater disinfection has attracted increasing attention. However, rather limited information is available on their photofate after discharging into surface waters, and their degradation behavior after solar-based engineering water treatment is unclear. Herein, the reactivity of four chlorinated parabens with different photochemically produced reactive intermediates was measured. Quantitative contribution analysis in abating such compounds showed the dominance of direct photolysis in sunlit natural freshwaters. Introducing a technical solar/peroxymonosulfate (PMS) system could greatly improve the removal of chlorinated parabens. The economic analysis suggested that chlorinated parabens exhibited a minimum value of economic input as 93.41-158.04 kWh m-3 order-1 at 0.543-0.950 mM PMS. The high-resolution mass spectrometry analysis of the degradation products suggested that dechlorination, hydroxylation, and ester chain cleavage were the dominant transformation pathways during photolysis and solar/PMS treatment. Furthermore, the in silico prediction indicated severe aquatic toxicity of certain products but enhanced biodegradability. Overall, this investigation filled a knowledge gap on the reactivity of chlorinated parabens with diverse reactive transients and their quantitative contributions to the photolysis and solar/PMS treatment of emerging micropollutants in water.

Methylisothiazolinone (MIT) and Benzisothiazolinone (BIT) are two widely used non-oxidizing biocides of isothiazolinones. Their production and usage volume have sharply increased since the pandemic of COVID-19, inevitably leading to more release into water environment. However, their photochemical behaviors in water environment are still unclear. Therefore, this study investigated photodegradation properties of MIT and BIT in natural water under simulated sunlight. The results demonstrated that direct photolysis was mainly responsible for their photodegradation which occurred through their excited singlet states rather than triplet states. The quantum yields of MIT and BIT photodegradation were 11 - 13.6 × 10-4 and 2.43 - 5.79 × 10-4, respectively. pH had almost no effect on the photodegradation of MIT, while the photodegradation of BIT was significantly promoted under alkaline condition due to abundance of BIT in its deprotonated form (BIT-N-). Cl-, NO3- and dissolved organic matter (DOM) in natural water inhibited the photodegradation of both MIT and BIT, with the light screening effect of DOM being the most significantly inhibitory factor. The addition of other isothiazolinones, which possibly coexisted with MIT and BIT in actual condition, slightly inhibited the photodegradation of MIT and BIT. The estimated half-life under natural sunlight at a 30°N latitude was estimated to be approximately 1.1 days. The photodegradation pathways of MIT and BIT are similar, primarily initiated from the ring-opening at the N-S bond, with Frontier electron densities (FED) calculations suggesting the likelihood of oxidation and ·OH addition reactions at the O, N, and S sites. While the photodegradation products exhibited significantly reduced acute toxicity compared to their parent compounds, they nonetheless posed substantial chronic toxicity. These insights are vital for assessing the ecological impacts of MIT and BIT in aquatic environments.

BACKGROUND: Stilbenoid extracts, such as those originating from grapevine by-products (e.g. canes), are of interest for use as biopesticides in vineyard owing to their antimicrobial activities. However, stilbenoids are unstable in the environment, especially under light. This study aimed to chemically characterize the effect of UV light on stilbenoids present in a grapevine cane extract (CE), and to evaluate the antimicrobial activities against two major grapevine pathogens (Plasmopara viticola and Botrytis cinerea) of grapevine extracts exposed to UV.
RESULTS: Treatment with UV (365 nm) on a grapevine CE led to degradation of stilbenoids (up to 71% after 1 h). The stilbenoid stability depended on their chemical structure: only those possessing CC, as trans-resveratrol and trans-ε-viniferin, were affected with first their isomerization and secondly their oxidation/cyclization. As a consequence, UV-exposed extracts (UV-CEs) showed reduced antimicrobial activities against the two pathogens (mycelium and spores). For instance, regarding P. viticola, an UV-CE exposed during 4 h showed an almost total loss of its activity on oomycete development and a 2.4-fold inhibition of zoospore mobility in comparison to CE. For B. cinerea, the inhibition capacity of the same UV-CE was reduced by only 1.1-fold on mycelial development and by 3.2-fold on conidial germination compared to CE.
CONCLUSIONS: UV light triggered modifications on the structure of bioactive stilbenoids, resulting in losses of their antimicrobial activities. Photoprotection of stilbenoids has to be considered in the perspective of using them in vineyards as biopesticides. © 2024 The Author(s). Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.