Challenging established norms: The unanticipated role of alcohols in UV/PDS radical quenching.

UV/peroxydisulfate (UV/PDS) process is known to be highly efficient for degrading micropollutants from water by generating sulfate (SO4•-) and hydroxyl radicals (HO•). Reliable analyses of short-lived SO4•- and HO• are therefore critical for understanding reaction mechanisms and optimizing operating conditions. Currently, alcohols are commonly used as quenchers to distinguish radicals based on the assumption that they exclusively react with target radicals without other influences. However, this study for the first time reveals a series of unexpected effects that challenge this conventional wisdom because: 1) adding alcohols altered the decomposition rates of PDS by replacing the reactions between SO4•- and HO• with PDS by the reactions between secondary reactive species and PDS; and 2) SO4•- preferably reacted with alcohols to generate nonnegligible level of hydrogen peroxide (H2O2) under oxygen-rich conditions, which subsequently led to indirect formation of HO•. Additionally, the formation of H2O2 was substantially impacted by the types of alcohols, dosages, dissolved oxygen, and solution pH. Using probe tests as tools, we found that the actual SO4•- levels after dosing alcohols were only slightly different from assumed/expected levels, whereas the actually HO• levels were 43.7, 3364.9, and 12.5 times higher than assumed/expected conditions for samples dosed with methanol, iso-propanol, and tert-butanol, respectively. These unanticipated effects thus suggest that cautions are needed when using alcohols to qualitative and quantitative determine HO• and SO4•- in UV/PDS process.

Inactivation of Heterosigma akashiwo under UV/peroxydisulfate advanced disinfection system in marine waters.

Heterosigma akashiwo (H. akashiwo) is recognized as a harmful algal bloom (HABs) species with a global distribution, capable of posing significant threats to marine ecosystems, particularly when spread through ship ballast water. This investigation focused on elucidating the inactivation kinetics and underlying mechanism of H. akashiwo through a combined ultraviolet irradiation and peroxydisulfate (UV/PDS) process. The results demonstrated a strong synergistic effect within the UV/PDS system, resulting in an inactivation of 0.78-ln and 2.67-ln within 40 min of UV and UV/PDS processes. The principal agents accountable for inactivation were identified as sulfate radicals (•SO4-) and hydroxyl radical (•OH), which exhibited a synergistic effect in the UV/PDS process. Furthermore, the study observed a negatively impact of seawater pH and salinity on the efficiency of inactivation. UV/PDS caused oxidative stress on algal cells, initially involving the participation of antioxidant enzymes in counteracting cellular damage, but this protective mechanism diminished as the reaction duration extended. The UV/PDS treatment not only inflicted damage upon H. akashiwo's photosynthetic system but also caused the extracellular release of DNA and algal organic matter (AOM) due to damaged cell membranes. Transcriptome analysis provided a molecular biology perspective on the cellular inactivation process. Upregulation of genes linked to photosynthesis and oxidative phosphorylation suggested a potential elevation in energy metabolism. In contrast, genes associated with cellular and metabolic processes, including glycolysis and the tricarboxylic acid cycle (TCA cycle), exhibited downregulation. Moreover, this treatment exerted an inhibitory influence on RNA polymerase and protein synthesis, resulting in the reduced expression of genetic information.

Inactivation of E. coli and Streptococcus agalactiae by UV/persulfate during marine aquaculture disinfection.

Sulfate radical (•SO4-)-based advanced oxidation processes have attracted a great deal of attention for use in water disinfection because of their strong oxidation ability toward electron-rich moieties on microorganism molecules. However, a few studies have focused on the effects of •SO4- on pathogenic microorganism inactivation in marine aquaculture water containing various inorganic anions. We employed the gram-negative bacteria E. coli and gram-positive bacteria S. agalactiae as representatives to evaluate the application of UV/persulfate (S2O82-, PDS), to the disinfection of marine aquaculture water in a comprehensive manner. Total inactivation of 4.13ˍlog of E. coli cells and 4.74ˍlog of S. agalactiae cells was reached within 120 s in the UV/PDS system. The inactivation of pathogenic bacteria in marine aquaculture water increased with the increasing PDS concentration and UV intensity. An acidic pH was beneficial for UV/PDS inactivation. Halogen-free radicals showed a strong influence on the inactivation. Anions in seawater, including Cl-, Br-, and HCO3- inhibited the disinfection. The inactivation rates of pathogenic bacteria followed the order seawater < marine aquaculture water < freshwater. Pathogenic bacteria could also be effectively inactivated in actual marine aquaculture water and reservoir water. The analysis of the inactivation mechanisms showed that S2O82- was activated by UV to produce •SO4-, which damaged the cell membranes. In addition, antioxidant enzymes, including SOD and CAT, were induced. The genomic DNA was also damaged. Inorganic disinfection byproducts such as chlorate and bromate were not formed during the disinfection of marine aquaculture water, which indicated that UV/PDS was a safe and efficient disinfection method.

Study on influence factors of treating landfill leachate by ultraviolet-activated persulfate system.

In recent years, there have been many studies on treating pollutants with ultraviolet-activated persulfate (UV/PDS) system. In this paper, the biochemical treatment effluent of landfill leachate from garbage incineration power plant was treated. The effect of treating landfill leachate with UV/PDS system in the low-pressure external device and medium-pressure built-in device was compared; it was concluded that in the latter device, the photon quantity increased, the energy loss decreased, and the probability of generating free radicals in the reaction between photons and S2O82- increased, which result the treatment efficiency of this system was higher. In addition, the leachate was treated by combining the activation method of spinel composite (CuO-MgAl2O4) with UV activation method, called CuO-MgAl2O4/UV/PDS. The experimental data showed that the processing effect of segmented dosing PDS process was higher than that of one-time addition process. Under the same conditions, the removal rates of CODcr were 83.10% and 19.76%, respectively. One of the reasons for this result may be that excessive PDS in CuO-MgAl2O4/PDS system of the latter process inhibited the treatment effect. This paper analyzes the efficiency of UV/PDS system, as well as CuO-MgAl2O4/UV/PDS combination process which were used to treat landfill leachate under different conditions; the results showed that the medium-pressure built-in device and segmented-dosing process could get better treatment effect.

Giant UV Photoresponse of GaN-Based Photodetectors by Surface Modification Using Phenol-Functionalized Porphyrin Organic Molecules.

Organic molecular monolayers (MoLs) have been used for improving the performance of various electronic device structures. In this work, the concept of organic molecular surface modification is applied for improving the performance of GaN-based metal-semiconductor-metal (MSM) ultraviolet (UV) photodetectors (PDs). Organic molecules of phenol-functionalized metallated porphyrin (hydroxyl-phenyl-zinc-tetra-phenyl-porphyrin (Zn-TPPOH)) were adsorbed on GaN, and Ni/Zn-TPPOH/GaN/Zn-TPPOH/Ni PD structures were fabricated. This process was beneficial in two ways: first, the reverse-bias dark current was reduced by 1000 times, and second, the photocurrent was enhanced by ∼100 times, in comparison to the dark and photocurrent values obtained for Ni/GaN/Ni MSM PDs, at high voltages of ±10 V. The responsivity of the devices was increased from 0.22 to 4.14 kA/W at 5 µW/cm2 optical power density at -10 V bias and at other voltages also. In addition to this, other PD parameters such as photo-to-dark current ratio and UV-to-visible rejection ratio were also enhanced. The spectral selectivity of the PDs was improved, which means that the molecularly modified devices became more responsive to UV spectral region and less responsive to visible spectral region, in comparison to bare GaN-based devices. Photoluminescence measurements, power-dependent photocurrent characteristics, and time-resolved photocurrent measurements revealed that the MoL was passivating the defect-related states on GaN. In addition, Kelvin probe force microscopy showed that the MoL was also playing with the surface charge (due to surface states) on GaN, leading to increased Schottky barrier height in dark conditions. Resultant to both these phenomena, the reverse-bias dark current was reduced for metal/MoL/GaN/MoL/metal PD structures. Further, the unusual photoconductive gain in the molecularly modified devices has been attributed to Schottky barrier lowering for UV-illuminated conditions, leading to enhanced photocurrent.

Comparison of UV/hydrogen peroxide and UV/peroxydisulfate processes for the degradation of humic acid in the presence of halide ions.

This study compared the behaviors of two classic advanced oxidation processes (AOPs), hydroxyl radical-based AOPs ((•)OH-based AOPs) and sulfate radical-based AOPs (SO4 (•-)-based AOPs), represented by UV/ hydrogen peroxide (H2O2) and UV/peroxydisulfate (PDS) systems, respectively, to degrade humic acid (HA) in the presence of halide ions (Cl(-) and Br(-)). The effects of different operational parameters, such as oxidant dosages, halide ions concentration, and pH on HA degradation were investigated in UV/H2O2/Cl(-), UV/PDS/Cl(-), UV/H2O2/Br(-), and UV/PDS/Br(-) processes. It was found that the oxidation capacity of H2O2 and PDS to HA degradation in the presence of halides was nearly in the same order. High dosage of peroxides would lead to an increase in HA removal while excess dosage would slightly inhibit the efficiency. Both Cl(-) and Br(-) would have depressing impact on the two AOPs, but the inhibiting effect of Br(-) was more obvious than that of Cl(-), even the concentration of Cl(-) was far above that of Br(-). The increasing pH would have an adverse effect on HA decomposition in UV/H2O2 system, whereas there was no significant impact of pH in UV/PDS process. Furthermore, infrared spectrometer was used to provide the information of degraded HA in UV/H2O2/Cl(-), UV/PDS/Cl(-), UV/H2O2/Br(-), and UV/PDS/Br(-) processes, and halogenated byproducts were identified in using GC-MS analysis in the four processes. The present research might have significant technical implications on water treatment using advanced oxidation technologies.