How I- alters UV and UV/VUV processes' redox capacities: Evidences from iodine species evolution, hydrogen peroxide formation, and oxyhalides degradation?

Although UV and/or VUV tandem I- are often proposed as advanced reduction processes (ARPs) to eliminate micropollutants by generating eaq-, the fate of I- and its byproducts formation remain to be explored. Therefore, this study investigated the iodine species evolution during UV/I- and UV/VUV/I- processes under different influencing factors. Results show that UV/VUV oxidized most of I- to IO3- whereas UV only oxidized a portion of I- to intermediate reactive iodine species (RISs, including I2, HOI, and I3-); meanwhile, substantial H2O2 was generated only in UV/VUV/I- process but not in UV/I- process, proving that UV/VUV owns stronger oxidation ability than UV alone. Spiking I- into water exerted triple-sided effects by consuming •OH, generating eaq-, and shielding light, thus complicating the systems. Holistically, increasing pH or decreasing dissolved oxygen converted oxidizing environment into reducing condition and caused less RISs formation, especially for UV/VUV/I-. For oxyhalides, neither UV/I- nor UV/VUV/I- degraded ClO4-. While UV/I- cannot remove ClO3-, UV/VUV/I- reduced ClO3- to Cl-. Expectedly, both UV/I- and UV/VUV/I- reduced BrO3- to Br- more efficiently than UV and UV/VUV, confirming that I- can enhance the reduction capacities of UV/VUV and UV technologies.

A review of factors affecting the formation and roles of primary and secondary reactive species in UV254-based advanced treatment processes.

The presence of organic micropollutants (OMPs) in water has been threatening human health and aquatic ecosystems worldwide. Ultraviolet-based advanced treatment processes (UV-ATPs) are one of the most effective and promising technologies to transform OMPs in water; therefore, an increasing number of emerging UV-ATPs are proposed. However, appropriate selection of UV-ATPs for practical applications is challenging because each UV-ATP generates different types and concentrations of reactive species (RSs) that may not be sufficient to degrade specific types of OMPs. Furthermore, the concentrations and types of RSs are highly influenced by anions and dissolved organic matter (DOM) coexisting in real waters, making systematic understandings of their interfering mechanisms difficult. To identify and address the knowledge gaps, this review provides a comparison of the generations and variations of various types of RSs in different UV-ATPs. These analyses not only prove the importance of water matrices on formation and consumption of primary and secondary RSs under different conditions, but also highlight the non-negligible roles of optical properties and reactivities of DOM and anions. For example, different UV-ATPs may be applicable to different target OMPs under different conditions; and the concentrations and roles of secondary RSs may outperform those of primary RSs in OMP degradation for real applications. With continuous progress and outstanding achievements in the UV-ATPs, it is hoped that the findings and conclusions of this review could facilitate further research and application of UV-ATPs.

Iodine revisited: If and how inorganic iodine species can be measured reliably and what cause their conversions in water?

This study revisited a list of inorganic iodine species on their detections and conversions under different water conditions. Several surprising results were found, e.g., UV-vis spectrophotometry is the only reliable method for I3- and I2 determinations with coexisting I-/IO3-/IO4-, while alkaline eluent of IC and LC columns can convert them into I- completely; IO4- can be converted into IO3- completely in IC columns and partly in LC columns; a small portion of IO3- was reduced to I- in LC columns. To avoid errors, a method for detecting multiple coexisting iodine species is suggested as follows: firstly, detecting I3- and I2 via UV-vis spectrophotometry; then, analyzing IO4- (> 0.2 mg/L) through LC; and lastly, obtaining I- and IO3- concentrations by deducting I- and IO3- measured by IC from the signals derived from I3-/I2/IO4-. As for stability, I- or IO3- alone is stable, but mixing them up generates I2 or H2OI+ under acidic conditions. Although IO4- is stable within pH 4.0-8.0, it becomes H5IO6/H3IO62- in strongly acidic/alkaline solutions. Increasing pH accelerates the conversions of I3- and I2 into I- under basic conditions, whereas dissolved oxygen and dosage exert little effect. Additionally, spiking ICl into water produces I2 and IO3- rather than HIO.

Applications of two-dimensional ion chromatography for analytes determination in environmental matrix: A review.

Ion chromatography (IC) has grown in usage rapidly since its first introduction in 1975. However, IC is still sometimes unable to separate target analytes from coexisting components well with identical elution time, due to the limited resolution and column capacity, especially in the presence of high-level salt matrix. These limitations hence drive IC to develop two-dimensional IC (2D-IC). In this review, we capture the 2D-IC applications in environmental samples via the perspective of coupling different IC columns, which aim to summarize where these 2D-IC methods fit in. In sequence, we firstly review the principles of 2D-IC and emphasize one-pump column-switching IC (OPCS IC) because it is a simplified 2D-IC that only uses one set of IC system. We then compare typical 2D-IC and OPCS IC performances in terms of application scope, method detection limit, drawbacks, and expectations. Finally, we propose some challenges of current methods and opportunities for future research. For instance, it is challenging to couple anion exchange column and capillary column in OPCS IC due to the incompatibility between flow path dimensions and suppressor; coupling ion exclusion column and mixed-bed column may be promising to simultaneously determine anions and cations in weak acids or salts. The details of this study may help practitioners to better understand and implement 2D-IC methods and meanwhile motivate researchers to fill in the knowledge gap in the future.

Total organic fluorine (TOF) analysis by completely converting TOF into fluoride with vacuum ultraviolet.

Quantifying total organic fluorine (TOF) in water is vital in monitoring the occurrence and persistence of all fluorine-containing organic compounds in the environment, while currently most studies focus on analyzing individual fluorine-containing organic compounds. To fill the technology gap, we herein proposed to convert TOF completely into fluoride with vacuum ultraviolet (VUV) photolysis, followed by analysis of fluoride with ion chromatography. Results showed that the tailored VUV photoreactor achieved satisfying recoveries of fluorine from ten model TOF compounds not only in ultrapure water (83.9 ± 2.0% to 109.4 ± 0.8%) but also in real water samples (92.1 ± 1.0%-106.2 ± 15.7%). Unlike other ultraviolet-based processes that favor alkaline conditions, this VUV process preferred either neutral or acidic conditions to defluorinate selected compounds. While the mechanisms remain to be explored in the future, it has been evidenced that the photo-degradation and photo-defluorination rates of these TOF compounds varied significantly among compounds and operation conditions. The method obtained a method detection limit (MDL) of 0.15 µg-F/L, which is lower than the MDLs of many other TOF analytical methods, along with excellent calibration curves for concentrations ranging from 0.01 to 10.0 mg-F/L. Notably, minimizing fluoride in sample prior to photoconversion was necessary to avoid subtraction-induced errors for TOF measurement, especially when the fluoride/TOF ratio was high. The robust VUV is also green for sample pretreatment due to its unreliance of chemicals or additives.

Coexisting oxidation and reduction of chloroacetaldehydes in water by UV/VUV irradiation.

Haloacetaldehydes (HALs) are the third largest disinfection by-product (DBP) ubiquitously detected in finished drinking water and have relatively higher toxicity than currently regulated DBPs. To efficiently alleviate them, this study investigated a green, chemical-free technology by using ultraviolet/vacuum ultraviolet (UV/VUV) on degrading three refractory chlorinated HALs (Cl-HALs). The results indicate that the rates of Cl-HALs decomposition in tap water irradiated by UV/VUV were 23-70 times higher than those irradiated by UV, proving that VUV instead of UV played the key role in degrading Cl-HALs. Increasing Cl-HALs dosage, pH, and dissolved oxygen (DO) all decreased the Cl-HALs degradations significantly, and the rates in tap water were apparently lower than those in ultrapure water. Unlike previous studies, this study proved that both oxidation and reduction were present during the VUV process. Photooxidation via oxidative radicals like •OH mineralized Cl-HALs, leading to substantial drops of total organic carbon; photoreduction via reductive radicals like •H dehalogenated Cl-HALs, resulting in formation of considerable intermediate organics (e.g., formic acid and acetic acid). No matter what pathway, the mass balances of chlorine were always maintained, meaning that dehalogenation occurred instantaneously rather than sequentially. Although the overall photodegradation rates dropped with rising pH and DO, photoreduction was increased with rising pH while photooxidation was elevated with rising DO. The results hence provide insights to better understand the VUV technology in controlling micropollutants in water.

Extracellular galectin-3 facilitates colon cancer cell migration and is related to the epidermal growth factor receptor.

We previously found that galectin-3 enhanced DLD-1 cell migration through the K-Ras-Raf-Erk1/2 pathway, but the effect of extracellular galectin-3 on cancer cell migration and its interaction with the epidermal growth factor receptor (EGFR) remained unknown. We aimed to determine the effect of extracellular galectin-3 on colon cancer cell migration and its correlation with the EGFR expression. Western blotting was performed to analyze galectin-3 secretion, shRNA was used to stably knock down galectin-3 expression and a migration assay was performed to evaluate colon cancer cell migration. Tissues from eighty patients with four different stages of colon cancer were obtained and compared to normal colon tissue. The galectin-3 knockdown colon cancer cells exhibited decreased migration, which was restored by recombinant galectin-3. An EGFR blocking antibody decreased colon cancer cell migration. The addition of recombinant galectin-3 increased phosphorylated EGFR expression within minutes and enhanced the internalization of the EGFR from the cell membrane to the cytoplasm, particularly upon EGF stimulation. Extracellular galectin-3 increased colon cancer cell migration, which correlated with the EGFR. Targeting galectin-3 may have a synergistic effect on EGFR-targeted therapy.

[Spatial Distribution Study and Pollution Assessment of Pb in Soils in the Xijiang River Drainage of Guangxi].

To obtain data for the accumulation of Pb and its risk in soils in the Xijiang River drainage of Guangxi, 2594 samples were collected from nonferrous metal mining soils, farmland soils (paddy soils and dryland soils), and the background soils in the drainage area. Geostatistical analysis combined with GIS was used to study the soil spatial distribution characteristics and pollution distribution of the soil Pb content. The results showed that the Pb background value of the soil was 51.84 mg ·kg-1 in the Xijiang River Basin, and the results of the single sample T test showed that the soil background value was significantly higher than that of a previous study (22.08 mg ·kg-1) and the soil background value (20.50 mg ·kg-1) in Guangxi province. The geometric mean concentration of Pb in the mining soils, dryland soils, and paddy soils were 655.9, 116.7, and 40.63mg ·kg-1, respectively, significantly higher than that in other soils. Using GB 15618-1995 and the baseline as the limiting value, the corresponding exceedance rate of the mining soils, dryland soils, and paddy soils were 57.69%, 16.40%, and 8.92% and 54.95%, 8.09%, and 2.03%. The mining soils and farmland soils had an obvious lead accumulation trend. There was an obvious spatial autocorrelation of Pb in the soil, and the structural variation was dominant. The content of Pb in the upper reaches of the Xijiang River reached the middle and lower reaches of the Xijiang River, and the soil Pb was characterized by an obvious decrease. The accumulation of high Pb content in the upper reaches of Diaojiang River is much larger than that in the lower reaches of Diaojiang River. The content of Pb in soil samples in the Xijiang River Basin was mainly rated between mild pollution and moderate pollution, and the pollution was concentrated in the municipal administrative area and the mining activity area. The pollution of the soil in Jinchengjiang and Nandan counties was closely related to the frequent local mining activities.