Molecular insight of dissolved organic matter and chlorinated disinfection by-products in reclaimed water during chlorination with permanganate preoxidation.

Permanganate is a common preoxidant applied in water treatment to remove organic pollutants and to reduce the formation of disinfection by-products. However, the effect of permanganate preoxidation on the transformation of dissolved effluent organic matter (dEfOM) and on the formation of unknown chlorinated disinfection by-products (Cl-DBPs) during chlorination remains unknown at molecular level. In this work, the molecular changes of dEfOM during permanganate preoxidation and subsequent chlorination were characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Permanganate preoxidation was found to decrease the DBE (double bond equivalent) and AImod (modified aromaticity index) of the dEfOM. The identity and fate of over 400 unknown Cl-DBPs during KMnO4-chlorine treatment were investigated. Most Cl-DBPs and the precursors were found to be highly unsaturated aliphatic and phenolic compounds. The Cl-DBPs precursors with lower H/C and lower O/C were preferentially removed by permanganate preoxidation. Additionally, permanganate preoxidation decreased the number of unknown Cl-DBPs by 30% and intensity of unknown Cl-DBPs by 25%. One-chlorine-containing DBPs were the major Cl-DBPs and had more CH2 groups and higher DBEw than Cl-DBPs containing two and three chlorine atoms. 60% of the Cl-DBPs formation was attributed to substitution reactions (i.e., +Cl-H, +2Cl-2H, +3Cl-3H, +ClO-H, +Cl2O3-2H). This work provides detailed molecular level information on the efficacy of permanganate preoxidation on the control of overall Cl-DBPs formation during chlorination.

Reductive transformation of the insensitive munitions compound nitroguanidine by different iron-based reactive minerals.

Nitroguanidine (NQ) is an emerging contaminant being used by the military as a constituent of new insensitive munitions. NQ is also used in rocket propellants, smokeless pyrotechnics, and vehicle restraint systems. Its uncontrolled transformation in the environment can generate toxic and potentially mutagenic products, posing hazards that need to be remediated. NQ transformation has only been investigated to a limited extent. Thus, it is crucial to expand the narrow spectrum of NQ remediation strategies and understand its transformation pathways and end products. Iron-based reactive minerals should be investigated for NQ treatment because they are successfully used in existing technologies, such as permeable reactive barriers, for treating a wide range of organic pollutants. This study tested the ability of micron-sized zero-valent iron (m-ZVI), mackinawite, and commercial FeS, to transform NQ under anoxic conditions. NQ transformation followed pseudo-first-order kinetics. The reaction rate constants decreased as follows: commercial FeS > mackinawite > m-ZVI. For the assessed minerals, the NQ transformation started with the reduction of the nitro group forming nitrosoguanidine (NsoQ). Then, aminoguanidine (AQ) was accumulated during the reaction of NQ with m-ZVI, accounting for 86% of the nitrogen mass recovery. When NQ was reacted with commercial FeS, 45% and 20% of nitrogen were recovered as AQ and guanidine, respectively, after 24 h. Nonetheless, NsoQ persisted, contributing to the N-balance. When mackinawite was present, NsoQ disappeared, but AQ was not detected, and guanidine accounted for 11% of the nitrogen recovery. AQ was ultimately transformed into cyanamide, whose dimerization triggered the formation of cyanoguanidine. Alternatively, NsoQ was transformed into guanidine, which reacted with cyanamide to form biguanide. This is the first report systematically investigating the NQ transformation by different iron-based reactive minerals. The evidence indicates that these minerals are attractive alternatives for developing NQ remediation strategies.

Fate of bis-(4-tert-butyl phenyl)-iodonium under photolithography relevant irradiation and the environmental risk properties of the formed photoproducts.

Aryl-iodonium salts are utilized as photoacid generators (PAGs) in semiconductor photolithography and other photo-initiated manufacturing processes. Despite their utilization and suspected toxicity, the fate of these compounds within the perimeter of semiconductor fabrication plants is inadequately understood; the identification of photolithography products is still needed for a comprehensive environmental impact assessment. This study investigated the photolytic transformation of a representative iodonium PAG cation, bis-(4-tert-butyl phenyl)-iodonium, under conditions simulating industrial photolithography. Under 254-nm irradiation, bis-(4-tert-butyl phenyl)-iodonium reacted rapidly with a photolytic half-life of 39.2 s; different counter ions or solvents did not impact the degradation kinetics. At a semiconductor photolithography-relevant UV dosage of 25 mJ cm-2, 33% of bis-(4-tert-butyl phenyl)-iodonium was estimated to be transformed. Six aromatic/hydrophobic photoproducts were identified utilizing a combination of HPLC-DAD and GC-MS. Selected photoproducts such as tert-butyl benzene and tert-butyl iodobenzene had remarkably higher acute microbial toxicity toward bacterium Aliivibrio fischeri compared to bis-(4-tert-butyl phenyl)-iodonium. Octanol-water partition coefficients estimated using the Estimation Programs Interface Suite™ indicated that the photoproducts were substantially more hydrophobic than the parent compound. The results fill a critical data gap hindering the environmental impact assessment of iodonium PAGs and provide clues on potential management strategies for both iodonium compounds and their photoproducts.

Analysis of hydrophilic per- and polyfluorinated sulfonates including trifluoromethanesulfonate using solid phase extraction and mixed-mode liquid chromatography-tandem mass spectrometry.

Ultra-hydrophilic per- and polyfluorinated sulfonates (PFSA) are increasingly scrutinized in recent years due to their ubiquitous occurrence, persistence, and aqueous mobility in the environment, yet analysis remains a challenge. This study developed methods for the analysis of trifluoromethanesulfonate, perfluorobutanesulfonate, 10-camphorsulfonate, and a di-fluorinated sulfonate utilizing mixed-mode liquid chromatography, where all analytes were adequately retained and separated. Chromatography and electrospray ionization parameters were optimized; instrumental limits of quantification for the anionic target analytes were in the range of 4.3 - 16.1 ng L-1. Solid phase extraction (SPE) methods were developed using Oasis WAX cartridges; SPE recoveries for the analytes ranged from 86% to 125%. Salinity and total organic carbon both impaired the SPE performance to different extents, depending on the respective analyte. Utilizing widely accessible instrumentation and materials, this is a single method to simultaneously analyze conceivably the most hydrophilic PFAS chemical, i.e., trifluoromethanesulfonate, and moderately hydrophobic PFSAs.

The relationship of CCL4, BCL2A1, and NFKBIA genes with premature aging in women of Yin deficiency constitution.

BACKGROUND: Traditional Chinese Medicine (TCM) defined constitution as a health statue or physical fitness that determines individual susceptibility to diseases. Yin deficiency constitution (YinDC) is a type of constitution closely related to aging. Previous studies found that the characteristic genes of YinDC are part of the inflammatory aging signaling pathways (e.g., NF-kappa B). Therefore, the aim of the study was to further reveal the dysregulation of genes associated with inflammatory aging in YinDC women. METHODS: This study adopted the industrial standard of constitutional judgment, and screened YinDC (n = 30) and Balanced constitution (BC) (n = 30) from women between the ages of 35 to 49, a range categorized as the degenerating period by TCM. Five genes CCL4, BCL2A1, NFKBIA, TAK1, and IL-8 were analyzed by qRT-PCR. RESULTS: Logistical regression revealed the correlation between body constitution and the expression of the five genes: the expression of NFKBIA and CCL4 mRNA was significantly up-regulated, whereas the expression of BCL2A1 mRNA was significantly down-regulated in YinDC (P < 0.05). Age or weight, when included in the model, did not affected the correlations. CONCLUSION: Increased mRNA expression of CCL4 and NFKBIA and decreased mRNA expression of BCL2A1 may be the molecular basis of premature aging of YinDC women. These results provide a mechanistic basis for early conditioning of YinDC, anti-aging, and the prevention of aging-related diseases.

Bioconcentration potential and microbial toxicity of onium cations in photoacid generators.

Despite the widespread utilization of onium salts as photoacid generators (PAGs) in semiconductor photolithography, their environmental, health, and safety (EHS) properties remain poorly understood. The present work reports the bioconcentration potential of five representative onium species (four sulfonium and one iodonium compound) by determining the octanol-water partition coefficient (POW) and lipid membrane affinity coefficient (KMA); microbial toxicity was evaluated using the bioluminescent bacterium Aliivibrio fischeri (Microtox bioassay). Four of the oniums exhibited varying degrees of hydrophobic (lipophilic) partitioning (log POW: 0.08-4.12; KMA: 1.70-5.62). A strong positive linear correlation was observed between log POW and KMA (KMA = log POW + 1.76, R2 = 0.99). The bioconcentration factors (log BCF) estimated from POW and KMA for the four oniums ranged from 0.13 to 3.67 L kg-1. Bis-(4-tert-butyl phenyl)-iodonium and triphenylsulfonium had 50% inhibitory concentrations (IC50) of 4.8 and 84.6 µM, whereas the IC50 values of the other three oniums were not determined because these values were higher than their aqueous solubility. Given the increased regulatory scrutiny regarding the use and potential health impacts from onium PAGs, this study fulfills critical knowledge gaps concerning the EHS properties of PAG oniums, enabling more comprehensive evaluation of their environmental impacts and potential risk management strategies.

Sunlight-induced phototransformation of transphilic and hydrophobic fractions of Suwannee River dissolved organic matter.

Sunlight-induced chemical changes of both transphilic (SWR-TPH) and hydrophobic (SWR-HPO) fractions of Suwannee River dissolved organic matter (DOM) were followed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Irradiated SWR-TPH exhibited increase of chemodiversity, loss of some aromatic compounds, and almost no change in terms of average values of m/z, O/C and double bond equivalents (DBE). Irradiated SWR-HPO showed decrease of chemodiversity, average values of m/z, O/C and DBE. Irradiation of SWR-HPO produced oxygenated (O/C > 0.7) and aliphatic new compounds and removed some aromatics and carboxyl-rich alicyclic molecules (CRAM). Comparatively, CHO-compounds of SWR-TPH were relatively stable with a minor class of aromatic compounds disappeared under sunlight irradiation. Photochemical processing of SWR-HPO generated highly oxygenated new compounds that were readily present in SWR-TPH, implying that sunlight changes the hydrophobicity of DOM and that SWR-HPO is a photochemical precursor for SWR-TPH. This study contributed to the developing knowledge on organic matter phototransformation, particularly the transformation pattern of SWR-TPH that was never described previously; it also demonstrated the role of sunlight in producing SWR-TPH compounds from SWR-HPO and consequently driving the transformation of organic matter.

Photochemical production of hydroxyl radical from algal organic matter.

Photochemical production of hydroxyl radical (·OH) from algal organic matter (AOM) collected from Lake Torrens in South Australia was examined using a sunlight simulator. The two AOM isolates featured lower molecular weight, lower chromophoric content, and lower SUVA254 (0.7 and 0.9, L mgC-1 m-1) than the reference Suwannee River hydrophobic acid (SR-HPO), they had considerably higher apparent quantum yields (ϕNOMOH, 3.03 × 10-5 and 2.18 × 10-5) than SR-HPO (0.84 × 10-5). Fluorescence excitation-emission matrix (FEEM) showed that the major components in the AOM were aromatic protein-like and soluble microbial substances. Unique formulas of the two AOM isolates as compared to SR-HPO were revealed using FTICR-MS and classified into four areas, namely protein-like molecules with low O/C (H/C > 1.5, O/C: 0.2-0.4), lignin-derived moieties with low O/C (H/C:1.0-1.5, O/C: 0.1-0.3), protein-like molecules with high O/C (H/C > 1.5, O/C: 0.5-0.7), and carbohydrate derivatives (H/C > 1.5, O/C > 0.7). These unique AOM moieties characterised utilizing FEEM and FTICR-MS were tentatively postulated to contribute to the high ϕNOMOH. To the best of our knowledge, this is the first study performed to both evaluate natural AOM as an efficient photosensitiser of ·OH and propose AOM moieties responsible for the high ϕNOMOH.

The characteristics of organic matter influence its interfacial interactions with MnO2 and catalytic oxidation processes.

The influence of dissolved organic matter (DOM) properties on its interfacial interactions with MnO2 and on catalytic oxidation processes was studied by Time-Resolved Dynamic Light Scattering (TR-DLS) and Atomic Force Microscopy (AFM) under varied solution conditions. Four DOM fractions of different characteristics (e.g., SUVA, hydrophobic character, structural properties) were selected. Bared-MnO2 nanoparticles readily aggregated in NaCl and CaCl2 solutions. Classic DLVO Theory successfully described critical coagulation concentrations and aggregation behaviors. In NaCl solution, DOM adsorbed on MnO2 nanoparticles and provided electrosteric stabilization. The two DOM fractions of higher hydrophobic (HPO) character were more efficient in decreasing the aggregation rates. Enhanced MnO2 aggregation was observed at high Ca2+ concentrations due to charge screening and cation bridging between carboxyl groups in DOM structures. The addition of oxidant (H2O2) induced a high aggregation of bared-MnO2 nanoparticles, possibly due to the release of Mn2+ (i.e., complexation mechanisms) and generation of reactive species (O2-, HO2-, and H). Contrasted with their hydrophilic (HPI) counterparts, HPO isolates adsorbed on MnO2 significantly decreased the catalytic oxidation processes between H2O2/MnO2; suggesting a more efficient and stronger DOM coating. Interfacial forces measured by AFM, showed weaker interactions between HPI isolates and MnO2; suggesting unfavorable polar interactions. Conversely, the high adhesion forces between MnO2/HPO isolate would indicate stronger bonds and hydrophobic interactions. This study provided a nanoscale understanding of the impact of DOM characteristics on: a) performance of the MnO2 coated ceramic membranes in water treatment, and b) biogeochemical cycle of Mn-oxides in the environmental.

Excited Triplet State Interactions of Fluoroquinolone Norfloxacin with Natural Organic Matter: A Laser Spectroscopy Study.

In sunlit waters, the fate of fluoroquinolone antibiotics is significantly impacted by photodegradation. The mechanism of how natural organic matter (NOM) participates in the reaction has been frequently studied but still remains unclear. In this work, the interactions between the excited triplet state of the fluoroquinolone antibiotic norfloxacin (3NOR*) and a variety of NOM extracts were investigated using time-resolved laser spectroscopy. The observed transient absorption spectrum of 3NOR* showed a maximum at ca. 600 nm, and global fitting gave a lifetime of 1.0 µs for 3NOR* in phosphate buffer at pH = 7.5. Quenching of 3NOR* by Suwannee River hydrophobic acids (HPO), Beaufort River HPO, and Gartempe River HPO yielded rate constants of 1.8, 2.6, and 4.5 (×107 molC-1 s-1) respectively, whereas HPO from South Platte River unexpectedly increased the lifetime of 3NOR* with an as yet unknown mechanism. Concurrent photodegradation experiments of NOR (5 µM) in the presence of these NOM were also performed using a sunlight simulator. In general, the effects of NOM on the photodegradation rate of NOR were in agreement with observations from transient absorption studies. We suggest that adsorption of NOR to NOM is one of the major factors contributing to the observed quenching. These results yield a new insight into the likely role of NOM in sunlight-induced degradation of micropollutants.

Characterisation of dissolved organic matter using Fourier-transform ion cyclotron resonance mass spectrometry: Type-specific unique signatures and implications for reactivity.

This study investigated the chemodiversity and unique signatures for dissolved organic matter (DOM) from different types of water using high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Eight freshwater hydrophobic DOM (HPO) share 10-17% formulas that were mainly lignin-like compounds. Unique signatures were synthesized: unique to the high-humic HPO (Suwannee River and Blavet River) were condensed aromatic and some aliphatic compounds with H/C > 1.5 and O/C < 0.2, which is considered as decisive of these black river water. Medium-humic isolates (Loire River, Seine River, South Platte River, and Ribou Dam) did not show explicit unique signatures. Nonetheless, enhanced chemodiversity was observed for medium-humic isolates extracted from a variety of indigenous environmental conditions. As an example, South Platte River HPO isolated in winter showed signatures similar to low-humic HPO (Colorado River), i.e., predominantly aliphatic CHO (H/C > 1.0). Effluent HPO was mainly aliphatic molecules with 0.2 < O/C < 0.5 and enriched in S-bearing molecules, and molecules unique to glacial DOM (Pony Lake) incorporated N-bearing compounds that were inferiorly oxidized and were considered as microbial-derived. The weight-averaged double bond equivalent and elemental ratio derived from FTICR-MS were compared with SUVA254 and the results from elemental analysis. This acts as the first study to synthesize unique chemical compositions that distinguish different types of DOM and determine certain reactivity. It is also a significant reference for future studies using similar types of DOM.

Survival of antibiotic resistant bacteria following artificial solar radiation of secondary wastewater effluent.

Urban wastewater treatment plant effluents represent one of the major emission sources of antibiotic-resistant bacteria (ARB) in natural aquatic environments. In this study, the effect of artificial solar radiation on total culturable heterotrophic bacteria and ARB (including amoxicillin-resistant, ciprofloxacin-resistant, rifampicin-resistant, sulfamethoxazole-resistant, and tetracycline-resistant bacteria) present in secondary effluent was investigated. Artificial solar radiation was effective in inactivating the majority of environmental bacteria, however, the proportion of strains with ciprofloxacin-resistance and rifampicin-resistance increased in the surviving populations. Isolates of Pseudomonas putida, Serratia marcescens, and Stenotrophomonas maltophilia nosocomial pathogens were identified as resistant to solar radiation and to at least three antibiotics. Draft genome sequencing and typing revealed isolates carrying multiple resistance genes; where S. maltophilia (resistant to all studied antibiotics) sequence type was similar to strains isolated in blood infections. Results from this study confirm that solar radiation reduces total bacterial load in secondary effluent, but may indirectly increase the relative abundance of ARB.

Syntrophic effect of indigenous and inoculated microorganisms in the leaching of rare earth elements from Western Australian monazite.

The unique physiochemical properties exhibited by rare earth elements (REEs) and their increasing application in high-tech industries has created a demand for secure supply lines with established recovery procedures that create minimal environmental damage. Bioleaching experiments conducted on a non-sterile monazite concentrate with a known phosphate solubilising microorganism (PSM) resulted in greater mobilisation of REEs into solution in comparison to experiments conducted on sterile monazite. By combining the native consortia with an introduced PSM, a syntrophic effect between the populations effectively leached a greater amount of REEs than either a single PSM or the indigenous population alone. With sterile monazite, Penicillium sp.CF1 inoculated experiments released a total REE concentration of 12.32 mg L-1 after incubation for 8 days, whereas on non-sterile ore, double the soluble REE concentration was recorded (23.7 mg L-1). Comparable effects were recorded with Enterobacter aerogenes, Pantoea agglomerans and Pseudomonas putida. Alterations in the microbial populations during bioleaching of the monazite ore were determined by diversity profiling and demonstrated noticeable changes in community inhabitants over 14 days. The presence of native Firmicutes on the monazite appears to greatly contribute to the increased leaching recorded when using non-sterile monazite for REE recovery.

Photodegradation of sulfathiazole under simulated sunlight: Kinetics, photo-induced structural rearrangement, and antimicrobial activities of photoproducts.

Photolysis is a core natural process impacting the fate of some sulfonamide antibiotics in sunlit waters. In this study, sunlight-induced phototransformation of sulfathiazole was investigated. A photolytic quantum yield of 0.079 was obtained in buffered water (pH = 8.0). Different natural organic matter isolates inhibited the photolysis of sulfathiazole by light screening effect. A kinetic model was developed to predict the photodegradation rate of sulfathiazole using the light screening correction factor of the water matrix in the wavelength range of 300-350 nm. An isomeric photoproduct of sulfathiazole with a longer retention time was observed on liquid chromatography. Based on its MS/MS spectra and absorption characteristics, the isomer was postulated as 2-imino-3-(p-aminobenzenesulfinyl-oxy)-thiazole. A reaction mechanism for the photo-cleavage and photo-induced structural rearrangement was proposed. The formation mechanism of the isomer was supported by photochemical experiments spiking synthetic 2-aminothiazole; while the formation kinetics were treated with a partly-diffusion-controlled model. The three identified products showed significantly enhanced photo-stability. Antimicrobial assay of irradiated sulfathiazole solutions with Escherichia coli indicated little antimicrobial potency ascribed to photoproducts. This study demonstrates the efficacy of sunlight in rapidly degrading sulfathiazole at a predictable rate, leading to photoproducts of low antimicrobial potency. The mass spectrometry and mechanistic work described here are new insights into the photochemistry of sulfonamides.

Interactions of phosphate solubilising microorganisms with natural rare-earth phosphate minerals: a study utilizing Western Australian monazite.

Many microbial species are capable of solubilising insoluble forms of phosphate and are used in agriculture to improve plant growth. In this study, we apply the use of known phosphate solubilising microbes (PSM) to the release of rare-earth elements (REE) from the rare-earth phosphate mineral, monazite. Two sources of monazite were used, a weathered monazite and mineral sand monazite, both from Western Australia. When incubated with PSM, the REE were preferentially released into the leachate. Penicillum sp. released a total concentration of 12.32 mg L-1 rare-earth elements (Ce, La, Nd, and Pr) from the weathered monazite after 192 h with little release of thorium and iron into solution. However, cultivation on the mineral sands monazite resulted in the preferential release of Fe and Th. Analysis of the leachate detected the production of numerous low-molecular weight organic acids. Gluconic acid was produced by all microorganisms; however, other organic acids produced differed between microbes and the monazite source provided. Abiotic leaching with equivalent combinations of organic acids resulted in the lower release of REE implying that other microbial processes are playing a role in solubilisation of the monazite ore. This study demonstrates that microbial solubilisation of monazite is promising; however, the extent of the reaction is highly dependent on the monazite matrix structure and elemental composition.

Roles of singlet oxygen and dissolved organic matter in self-sensitized photo-oxidation of antibiotic norfloxacin under sunlight irradiation.

Many fluoroquinolone (FLQ) antibiotics undergo rapid photodegradation in sunlit waters and form multifaceted photo-products. The high photodegradation rate is primarily ascribed to their photosensitizing properties. Though widely studied, the photo-reaction pathways are not completely revealed; photo-products mediated by different reactive oxygen species are not identified. In our study, photo-degradation of fluoroquinolone norfloxacin was investigated. A rapid degradation in buffered water was observed with a first-order rate constant of 2.45/hr and a quantum yield of 0.039. After light screening correction, selected DOMs (5 mg C/L) slightly enhanced the photodegradation rate with the exception of Suwannee river hydrophobic organic matter (SR-HPO). Three major photo-products were identified using high resolution mass spectrometry (HRMS). With 1O2 dark formation and competitor experiments, norfloxacin self-sensitized 1O2 was found to oxidize norfloxacin by inducing its piperazine chain cleavage. DOMs exhibited a dual role by inhibiting the 1O2-mediated reaction while enhancing the heterolytic defluorination pathway. DOMs were proposed to enhance heterolytic defluorination by donating electron to triplet state FLQ, this proposal was supported with specific UV absorbance (SUVA) as an indicator for the abundance of π bonds. Fluoride formation indicated a 79% elimination ratio of fluorine, an important functional group for antimicrobial activity. This work provides important new insights into the photochemical fate of fluoroquinolone antibiotics in natural water.

Photobleaching-induced changes in photosensitizing properties of dissolved organic matter.

Photosensitizing properties of different dissolved organic matter (DOM) were investigated according to their performance in singlet oxygen ((1)O2), triplet state of DOM ((3)DOM*), and hydroxyl radical (·OH) productions. The photobleaching of DOM solutions after irradiation was characterized by fluorescence excitation-emission matrix and UV-Vis spectroscopy. The photosensitizing properties of pre-irradiated DOM solutions were changed in a sunlight simulator. The performance of DOMs in photosensitized degradation of several contaminants was investigated. For a 20 h exposure, the observed degradation rate constant (kobs) of some contaminants decreased as a function of exposure time, and highly depended on the properties of both DOM and contaminant. Degradation of contaminants with lower kobs was more susceptible to DOM photobleaching-induced decrease in kobs. Under the current experimental conditions, the photobleaching-induced decrease of DOM photo-reactivity in contaminant degradation was mainly attributed to indirect phototransformation of DOM caused by the interactions between photo-inductive DOM moieties and photochemically-produced reactive species. Reactive contaminants can inhibit DOM indirect photobleaching by scavenging reactive species, photosensitized degradation of these contaminants exhibited a stable kobs as a result. This is the first study to report DOM photobleaching-induced changes in the simultaneous DOM photosensitized degradation of contaminants and the inhibitory effect of reactive contaminants on DOM photobleaching.

Sunlight-induced inactivation of human Wa and porcine OSU rotaviruses in the presence of exogenous photosensitizers.

Human rotavirus Wa and porcine rotavirus OSU solutions were irradiated with simulated solar UV and visible light in the presence of different photosensitizers dissolved in buffered solutions. For human rotavirus, the exogenous effects were greater than the endogenous effects under irradiation with full spectrum and UVA and visible light at 25 °C. For porcine rotavirus, the exogenous effects with UVA and visible light irradiation were only observed at high temperatures, >40 °C. The results from dark experiments conducted at different temperatures suggest that porcine rotavirus has higher thermostability than human rotavirus. Concentrations of 3'-MAP excited triplet states of 1.8 fM and above resulted in significant human rotavirus inactivation. The measured excited triplet state concentrations of ≤0.45 fM produced by UVA and visible light irradiation of natural dissolved organic matter solutions were likely not directly responsible for rotavirus inactivation. Instead, the linear correlation for human rotavirus inactivation rate constant (kobs) with the phenol degradation rate constant (kexp) found in both 1 mM NaHCO3 and 1 mM phosphate-buffered solutions suggested that OH radical was a major reactive species for the exogenous inactivation of rotaviruses. Linear correlations between rotavirus kobs and specific UV254 nm absorbance of two river-dissolved organic matter and two effluent organic matter isolates indicated that organic matter aromaticity may help predict formation of radicals responsible for rotavirus inactivation. The results from this study also suggested that the differences in rotavirus strains should be considered when predicting solar inactivation of rotavirus in sunlit surface waters.

Roles of singlet oxygen and triplet excited state of dissolved organic matter formed by different organic matters in bacteriophage MS2 inactivation.

Inactivation of bacteriophage MS2 by reactive oxygen species (ROS) and triplet excited state of dissolved organic matter ((3)DOM*) produced by irradiation of natural and synthetic sensitizers with simulated sunlight of wavelengths greater than 320 nm was investigated. Natural sensitizers included purified DOM isolates obtained from wastewater and river waters, and water samples collected from Singapore River, Stamford Canal, and Marina Bay Reservoir in Singapore. Linear correlations were found between MS2 inactivation rate constants (kobs) and the photo-induced reaction rate constants of 2,4,6-trimethylphenol (TMP), a probe compound shown to react mainly with (3)DOM*. Linear correlations between MS2 kobs and singlet oxygen ((1)O2) concentrations were also found for both purified DOM isolates and natural water samples. These correlations, along with data from quenching experiments and experiments with synthetic sensitizers, Rose Bengal (RB), 3'-methoxyacetophenone (3'-MAP), and nitrite [Formula: see text] , suggest that (1)O2, (3)DOM*, and hydroxyl radicals ((•)OH) could inactivate bacteriophage MS2. Linear correlations between MS2 kobs and Specific Ultraviolet Absorption determined at 254 nm (SUVA254) were also found for both purified DOM isolates and natural samples. These results suggest the potential use of TMP as a chemical probe and SUVA254 as an indicator for virus inactivation in natural and purified DOM water samples.