Effect Of Natural Organic Matter Research Articles

Molecular-weight dependent promotion and competition effects of natural organic matter on dissolved black carbon removal by coagulation

Dissolved black carbon (DBC) is the ubiquitous component of dissolved organic matter pools with the high reactivity for disinfection byproducts formation. However, it is unknown that the influence of molecular weight (MW) of natural organic matter (NOM) on the DBC removal from potable water sources. Therefore, it was studied that the DBC removal by coagulation in the presence of the NOM with various molecular weights. The DBC removal was promoted due to the presence of NOM and the promotion degree decreased with decreasing MW of NOM. Furthermore, the removal ratio of humic-like component increased as the MW of NOM decreased, suggesting that the competition between DBC and NOM increased with decreasing MW. The functional groups after coagulation were the same with that before coagulation as the MW of NOM varied, suggesting that the molecular structure was not the key factor of influencing the DBC removal. This study will give the deep insight into the prediction of the DBC removal ratio by coagulation based on the MW of NOM in water sources.

The inhibitory effect of natural organic matters and ions on 17ɑ-ethinylestradiol removal over new TiO2(B)/Bi5O7I and mesoporous carbon/TiO2(B)/BiOI composites: The role of mesoporous carbon

The natural organic matters (NOMs) and ions prevalent in water matrixes always inhibits photocatalytic degradation of pollutants by TiO2. Herein, we prepared TiO2(B)/Bi5O7I and mesoporous carbon/TiO2(B)/BiOI composites to investigate the inhibitory effect of NOMs and ions on photocatalytic degradation of 17ɑ-ethinylestradiol (EE2). The results show that Bi5O7I or BiOI is tightly anchored onto the large surface of TiO2(B) nanobelt to form heterojunction, and metallic Bi forms on the surface of TiO2(B) in MC/TiO2(B)/BiOI composite. This intimate contact is beneficial for the separation of hole-electron pairs and stability. More importantly, the introduction of mesoporous carbon (MC) not only improve the EE2 removal but also eliminate obvious inhibitory effect of NOMs and inorganic ions. The main cause is that MC component in MC/TiO2(B)/BiOI composite can preferentially adsorb EE2 molecules from water via π-π and hydrophobic interaction forces between EE2 and MC. Quenching experiments and electron paramagnetic resonance confirm that •O2- and h+ are main reactive species for EE2 degradation over both TiO2(B)/Bi5O7I and MC/TiO2(B)/BiOI composites. Besides, the degradation mechanism was investigated, and degradation pathways are proposed based on intermediates identification. The MCF-7 cell test shows that the estrogenic activity of the treated solution can be rapidly eliminated. More importantly, MC/TiO2(B)/BiOI has excellent anti-interference capacity for the EE2 removal in real complex water matrixes.

Scaling behavior in membrane distillation: Effect of Biopolymers and Antiscalants

Fouling and scaling are inherent characteristics of membrane-based separation. They lead to a reduced membrane throughput. In the case of membrane distillation (MD), they can possibly result in pore wetting and irreversible failure to sustain the mass transfer interface. Most prior research on understanding fouling and scaling uses indirect measurements (flux) or ex-situ analyses methods (such as SEM and EDX), which limit the outcomes to indirect qualitative conclusions. Particularly, studying scaling tends to be more challenging due to the complexity of the experiments and the method of investigation; it is imperative to distinguish the contributions from the bulk phase and heterogeneous nucleation. In this work, we established a non-invasive, in-situ, real-time imaging experimental apparatus to study the scaling mechanism. Our experimental setup assisted us in distinguishing distinct phases of scaling during the filtration tests. We studied the scaling mechanism of various single-component systems (sodium chloride, strontium sulfate, calcium sulfate, and calcium carbonate) in vacuum MD filtration. The effect of natural organic matter and antiscalants on gypsum scaling were systematically investigated. Overall, organic fouling on the membrane surface expedited heterogeneous crystallization while decelerating crystal growth in the bulk phase. For instance, deposited humic acid (HA) on the membrane surface promoted gypsum heterogeneous nucleation on the membrane surface due to the interactions between HA carboxylic functional groups and calcium ions. The adsorption of HA on the salt crystal also decelerated crystal growth in the bulk phase. Antiscalants delayed and decelerated both crystal nucleation and crystal growth. PAA, a polycarboxylate antiscalant at 5 ppm, was found to effectively delay the onset of nucleation and crystal growth in the bulk phase, while phosphorous antiscalants at 5 ppm only delayed the onset of nucleation in the bulk phase with a negligible influence on crystal growth. Real-time, in-situ, and non-invasive monitoring shed light on the scaling mechanism and can further be used to identify mitigation strategies.

Evaluation of Carbonized Corncobs for Removal of Microcystins and Nodularin-R from Water

Microcystins (MCs) and nodularins (NODs) are cyanotoxins that can be found in water bodies during cyanobacterial harmful algal blooms (cyanoHABs). Consumption of water contaminated with cyanotoxins leads to health risks for humans and animals. Herein, corncob-based biochar and activated carbon (AC) were initially investigated for the sorption of six common MC congeners (MC-RR, MC-YR, MC-LR, MC-LA, MC-LW, and MC-LF) and nodularin-R (NOD-R) from spiked water. Biochar was prepared by refluxing commercial corncob with HCl and heating it to 250, 300, or 350 °C. AC was prepared by chemical activation of corncob with H3PO4 at 500 °C under a nitrogen atmosphere. Low-temperature nitrogen adsorption measurements confirmed that H3PO4-AC has a higher specific surface area (≈1100 m2/g) and total pore volume (≈0.75 cm3/g) than biochar and commercial AC. H3PO4-AC showed the maximum efficacy, among all corncob-based sorbents, to remove MCs and NOD-R from water as confirmed by experiments that involved sample analyses by ultrahigh-pressure liquid chromatography-mass spectrometry (UHPLC-MS). The effect of natural organic matter (NOM) on the adsorption of MCs was checked by incubating sorbents with Lake Erie water collected during cyanoHABs from 2020 to 2022. The total concentration (extracellular and intracellular) of studied MC congeners ranged from 1.37 µg/L to 438.51 µg/L and 50 mg of H3PO4-AC completely removed them from 3 mL of lake water. The effect of water pH on cyanotoxin adsorption was studied at pH values of 5.5, 7.0, and 8.5 at both a lower (10 μg/L each) and a higher (50 μg/L each) toxin concentration. Removal was influenced by solution pH at both concentrations when using biochar, while only at higher toxin concentration when using H3PO4-AC. At higher MC and NOD-R concentrations, competitive adsorption was prominent, and overall, the adsorption increased at acidic pH (5.5). The study results suggest that processed corncobs can remove a significant amount of MCs and NOD-R from water, and the measured sorption capacity of H3PO4-AC was ~20 mg of MC-LR and NOD-R per g of this sorbent.

Elucidating the inhibitory effects of natural organic matter on the photodegradation of organic micropollutants: Atrazine as a probe compound

Natural organic matter (NOM) is a complex mixture of heterogeneous compounds with varying functional groups and molecular sizes. Understanding the impact of NOM on the generation of photochemically produced reactive intermediates (PPRIs) and their potential inhibitory effects on photolysis has remained challenging due to the variations in the reactivities and concentrations of these functional groups. To address this gap, tannic acid (TA), gallic acid (GA), catechin (CAT), and tryptophan (Trp), were chosen as potential substitutes for NOM. Their effects on the photochemical transformation process were evaluated and compared with the widely used Suwannee River NOM (SRNOM). Atrazine (ATZ) was selected as a probe organic micropollutant (OMP). In this investigation, a significantly higher concentration of HO• was observed compared to O21, and the triplet excited state ( NOM*3). The findings suggest that the substituted phenols, particularly those with carboxylate-substitutions, played a substantial role in HO• formation, while electron-rich moieties acted as antioxidants, consuming NOM*3. Hydroxyl, carboxylic, and amino acid were the active groups for O21 formation. However, the inhibitory effects induced by the NOM surrogates were significant and mainly attributed to the direct photolysis inhibition caused by the inner filter effect. The scope of this work was further extended to include SRNOM, where similar trends with less pronounced formation of PPRIs and inner filter effects were observed. Therefore, this study sheds some light on the role of the functional groups in NOM during photochemical transformations of OMPs, thereby deepening our understanding of their fate in aqueous systems.

Effect of natural organic matter (NOM) on the removal efficiency of Hg(ii) by MoS2: dependence on the Hg/MoS2 ratio and NOM properties

In groundwater, the efficiency of MoS2 nanosheets for Hg(ii) removal is significantly hindered by natural organic matter (NOM) at high molar ratios of Hg/MoS2, whereas at low ratios, NOM has minimal impact on Hg(ii) removal.

Degradation of 2,4-dichlorophenol by carboxymethylcellulose stabilized Fe/Ni activating persulfate system: The DFT calculation and mechanistic insights

2,4-dichlorophenol (2,4-DCP) was degraded by synthesizing a novel carboxymethyl cellulose (CMC) stabilized Fe/Ni nanocomposite and activating persulfate (PS), meaning Fe/Ni-CMC-PS system. The feasibility of the degradation of 2,4-DCP in Fe/Ni-CMC system was determined by the comparison of blank, PS, nZVI, nZVI-PS, Fe/Ni-CMC and Fe/Ni-CMC-PS systems, respectively. The consequences of different influencing factors showed that the degradation efficiency reached the optimum value of 95.62% when pH was 5.5, Fe/Ni-CMC dose was 0.8 g/L, Fe/Ni ratio was 0.10 (Wt (Fe):Wt (Ni) = 9:1) and PS concentration was 2 mM. At the same time, the inhibition effect of natural organic matter (humic acid) and inorganic anions on the activity of iron-based materials was studied. The quenching experiments showed that SO4.- radical and .OH radical were mainly produced in the reaction system of Fe/Ni-CMC-PS, and SO4.- radical was the primary free radical to degrade 2,4-DCP. Based on the consequences of DFT calculation and experimental analysis, the possible mechanisms of degrading 2,4-DCP by Fe/Ni-CMC-PS was proposed, which provided a novel idea for the actual practice of iron-based materials in the treatment of environmental water pollution.

Combined toxicity of fluorescent silica nanoparticles with cadmium in Ceriodaphnia dubia: Interactive effects of natural organic matter and green algae feeding

The environmental risks of silica nanoparticles (SiNP) reported in the literature are contradictory and bring into question its safety for use in consumer applications. Organisms are never exposed to NPs alone in the real environment, while studies of the combined toxicity of SiNP are limited. To address this, we compared the acute toxicity of fluorescent core-shell SiNPs alone and in mixtures with Cd2+ to Ceriodaphnia dubia in the absence and presence of NOM. We identified biodistribution and feeding behaviour in addition to the traditional endpoints. NOM increased the colloidal stability of SiNPs in reconstituted water. In immobility tests, no significant effects were observed from Cd2+ exposure with NOM and varying concentrations of SiNPs. A similar pattern of curve dose-response was observed for varying concentrations of SiNPs and increasing Cd2+ concentration and constant NOM. Fluorescence microscopy verified a dose-dependent bioaccumulation of SiNPs in C. dubia. Co-exposure to 10 mg L−1 SiNP with NOM and Cd2+ resulted in a stimulated stress feeding response at the lower Cd2+ concentrations which declined at the higher dose due to a functional impairment of the digestive tract. Alterations in feeding behaviour and the increasing bioaccumulation of SiNP indicate a potential ecological risk for Ceriodaphnia dubia from the mixture exposure.

The effect of natural organic matter (NOM) on the distribution and resources of mobile phosphorus in the bottom sediments of small retention reservoirs

The purpose of the work detailed here was to determine the impact of the distribution of natural organic matter and grain size on the resources and distribution of mobile phosphorus in the bottom sediments of small reservoirs located in catchments subject to different levels of anthropopressure. The research objects were five small reservoirs located in southeast Poland. In small retention reservoirs, it is the anthropogenic impact of the catchment and its geological structure, and to a lesser extent sediment granulation, that determine the distribution of phosphorus fractions (especially in inorganic compounds) and the share of total P they account for. In general, a higher level of contamination of sediments with organic matter (OSION increase) is shown to be associated with a higher content of the organic fraction of phosphorus and easily decomposable organic matter. Within small retention reservoirs under significant anthropogenic influence from the catchment, sandy sediments compared with silty sediments were significantly less loaded with potentially mobile phosphorus as well as with organic forms of phosphorus and (sometimes) nitrogen. The occurrence of humic-metal-phosphate complexes is determined by there being sufficient organic matter, especially humic fractions. Fractions of inorganic phosphorus compounds and organic matter have the terrigenous source of these pollutants in common. The organic sediment index can serve as an adjunctive indicator with which to assess the potential ability of the sediments in small retention reservoirs to internal supply of the water column in nutrients.

Nematodes Degrade Extracellular Antibiotic Resistance Genes by Secreting DNase II Encoded by the nuc-1 Gene.

This study investigated the degradation performance and mechanism of extracellular antibiotic resistance genes (eARGs) by nematodes using batch degradation experiments, mutant strain validation, and phylogenetic tree construction. Caenorhabditis elegans, a representative nematode, effectively degraded approximately 99.999% of eARGs (tetM and kan) in 84 h and completely deactivated them within a few hours. Deoxyribonuclease (DNase) II encoded by nuc-1 in the excretory and secretory products of nematodes was the primary mechanism. A neighbor-joining phylogenetic tree indicated the widespread presence of homologs of the NUC-1 protein in other nematodes, such as Caenorhabditis remanei and Caenorhabditis brenneri, whose capabilities of degrading eARGs were then experimentally confirmed. C. elegans remained effective in degrading eARGs under the effects of natural organic matter (5, 10, and 20 mg/L, 5.26-6.22 log degradation), cation (2.0 mM Mg2+ and 2.5 mM Ca2+, 5.02-5.04 log degradation), temperature conditions (1, 20, and 30 °C, 1.21-5.26 log degradation), and in surface water and wastewater samples (4.78 and 3.23 log degradation, respectively). These findings highlight the pervasive but neglected role of nematodes in the natural decay of eARGs and provide novel approaches for antimicrobial resistance mitigation biotechnology by introducing nematodes to wastewater, sludge, and biosolids.

Componential and molecular-weight-dependent effects of natural organic matter on the colloidal behavior, transformation, and toxicity of MoS2 nanoflakes

The potential widespread applications in water processing have rendered the necessity for investigations of the fate and hazard of molybdenum disulfide (MoS2) nanosheets. Herein, it was found that humic acid (HA) had better performances toward stabilizing pure 2H phase MoS2 and chemical-exfoliated MoS2 (ce-MoS2) in electrolyte solutions than fulvic acid (FA), and molecular weight (MW)-dependent manners were disclosed due to steric repulsions. Compared with darkness, the extent to which the aggregation and sedimentation of ce-MoS2 facilitated by visible light irradiation was greater in the presence of HA and FA fractions, likely due to the introduction of stronger plasmonic dipole-dipole interaction and Van der Waals attraction forces. HA-triggered structural disintegration of nanosheets was performed after irradiation and it was observed to be more significant with the increase in MWs, whereas the MW-dependent dissolution of MoS2 caused by FA was much quicker than that by HA owing to the higher generation of singlet oxygen. Moreover, FA lowered the bioavailability of MoS2 and relieved its toxicity to zebrafish more effectively than HA. Our findings boost the insights into the effects of organic molecules on the fates and hazards of MoS2, providing guidance for the MoS2-based nanotechnological development on environment.

The comparative study on inhibitory effect of natural organic matters on the TiO2 and activated carbon/TiO2 composites for the removal of 17α-ethinylestradiol

To reduce or eliminate the inhibition effect of natural organic matters (NOMs) in water on TiO2 photocatalysis for removal of emerging contaminants, four activated carbon/titanium dioxide (AC/TiO2) composites with different pore structure were prepared by hydrothermal method. The results showed that anatase TiO2 particles were uniformly distributed in the pores or onto the surface of activated carbons. The total removal rate of 6 mg L−1 17α-ethinylestradiol (EE2) on the four AC/TiO2 composites reached above 90%, 30% higher than that of EE2 on TiO2. The degradation rate constants of EE2 on four kinds of AC/TiO2 were much higher than that on TiO2. Further study indicated that the adsorption removal ratio of EE2 on the composites was slightly reduced mainly because competitive adsorption between hydrophilic NOMs (HA and FA) and EE2 molecules when HA and FA coexisted with EE2 in water. But importantly, the obvious inhibitory effect of FA for TiO2 photocatalysis was eliminated on four composites because the introduction of AC with excellent adsorption capacity can preferentially transfer hydrophobic EE2 molecules onto adsorption sites of TiO2/AC composites.

Reciprocal effects of NOM and solution electrolyte ions on aggregation of ferrihydrite nanoparticles

The effects of natural organic matter (NOM) types and electrolyte ions are crucial to the aggregation of ferrihydrite nanoparticles (Fh NPs) in the environment. Dynamic light scattering (DLS) was employed for the aggregation kinetics of Fh NPs (10 mg/L as Fe) in the present study. The critical coagulation concentration (CCC) values of Fh NPs aggregation in NaCl were obtained in the presence of 15 mg C/L NOM as SRHA (857.4 mM) > PPHA (752.3 mM) > SRFA > (420.1 mM) > ESHA (141.0 mM) > NOM-free (125.3 mM), indicating Fh NPs aggregation was inhibited as the above order. Comparatively in CaCl2, the CCC values were measured in ESHA (0.9 mM), PPHA (2.7 mM), SRFA (3.6 mM), SRHA (5.9 mM), NOM-free (76.6 mM), implying NPs aggregation was enhanced following the order of ESHA > PPHA > SRFA > SRHA. To investigate the dominant mechanisms, the aggregation of Fh NPs was comprehensively studied under the effects of NOM types, concentrations (0–15 mg C/L) and electrolyte ions (NaCl/CaCl2 beyond CCC). In NaCl/CaCl2, the low concentration of NOM (<7.5 mg C/L) could accelerate NPs aggregation mainly due to patch-charge attraction. When NOM concentration was high (> 7.5 mg C/L), the inhibition effect on NPs aggregation occurred in NaCl due to steric repulsion, whereas the enhancement effect in CaCl2 of aggregation was dominated by the bridging effect. The results indicated that the effects of NOM types, concentration and electrolyte ions should be carefully considered for the environmental behavior of NPs.

Applicability of Electron Beam Technology for the Degradation of Microcystin-LR in Surface Waters.

Studies were performed to investigate the effects of surface water quality parameters on the degradation of microcystin-LR (MC-LR) using high-energy electron beam (eBeam) technology. Surface water samples were collected across different geographic locations in the United States. Water quality parameters including pH, alkalinity, TDS, and dissolved oxygen were measured in all samples. Degradation of MC-LR in all samples, regardless of parameter concentrations, was above 99%. The effect of natural organic matter (NOM) on MC-LR degradation was also investigated in the presence of fulvic acid. Similarly, the degradation efficiency of MC-LR exceeded 99% for all concentrations of fulvic acid at 5 kGy. This study suggests that surface water quality has a negligible effect on the degradation of MC-LR via eBeam treatment. The results indicate that eBeam technology is a promising technique for the treatment of water contaminated with microcystins.

PPCP degradation by ammonia/chlorine: Efficiency, radical species, and byproducts formation

Pharmaceutical and personal care products (PPCPs) are frequently detected in water bodies and have potential risks to human health and the ecosystem. The degradation of eight structurally diverse PPCPs by ammonia/chlorine was systematically investigated in this study. Compared with chlorination, ammonia/chlorine markedly enhanced PPCP degradation, and the degradation efficiencies of most PPCPs were greater than 70%. Tert-butanol strongly suppressed PPCP degradation, while bicarbonate suppressed it moderately, suggesting the importance of ClO⋅and ⋅CO3− in PPCP degradation. In neutral conditions, PPCP degradation was mainly attributed to ⋅OH, with its contribution ranging from 74% to 100% at a Cl2/N molar ratio of 1.6. Regarding the effect of natural organic matter, atrazine and primidone were inhibited the most, while carbamazepine (CBZ), metoprolol (MTP), and atenolol (ATN) were affected the least. PPCP degradation was suppressed in reclaimed water; the degradation of CBZ, MTP, and ATN was suppressed the least, with degradation efficiencies of 77.1%–85.4%, 75.1%–77.1%, and 64.6%–68.8%, respectively. Furthermore, compared with chlorination, fewer volatile halogenated byproducts were formed in reclaimed water when using the ammonia/chlorine process, and the concentration of each byproduct formed by ammonia/chlorine was less than 10 µg/L. This study suggests the feasibility of using ammonia/chlorine oxidation to degrade PPCPs in reclaimed water.

Insight into the effect of natural organic matter on the photooxidation of arsenite induced by colloidal ferric hydroxides in water

Surface complexation of arsenite (As(III)) on colloidal ferric hydroxide (CFH) plays an important role not only in the adsorptive immobilization of As(III) but also in the subsequent oxidation of As(III) to arsenate (As(V)) through light-induced ligand-to-metal charge transfer (LMCT) in water at near-neutral pH. However, the effects of natural organic matter (NOM), especially humic substances (HSs) and low molecular weight carboxylic acids (CAs), on the photochemistry of the CFH-As(III) system have not been sufficiently understood. In this work, the inhibition of photooxidation of As(III) in terms of the observed apparent rate constant (kobs) by six HSs (below 16 mg L−1) and seven CAs (below 2.5 mM) has been observed in water containing 66 μM Fe(III) and 5 μM As(III) at pH 7 under simulated solar irradiation consisting of UVA (λmax 365 nm) and UVB (λmax 313 nm) lights. Total inhibition factors (T) have been determined from the combined effect of light-screening factor (S) and competitive complexation factor (C), wherein both S and C varied with NOM concentration. S was obtained by determining the absorbance of NOM, and C was obtained by fitting modified Langmuir or Freundlich models to the amount of As(III) desorbed from CFH upon the addition of NOM. Statistical analysis between the experimental Texp and the calculated one according to Tcal = S × C showed that the Freundlich model (RMSE for HS 0.1609 and for CA 0.1771) was better than the Langmuir model and was statistically robust (QLOO2= 0.691 > 0.5). This work provided an estimation method for the effects of NOM on As(III) photooxidation in the presence of CFH as well as a deeper understanding of the transformation of arsenic species in sunlit water.

Natural organic matter flocculation behavior controls lead phosphate particle aggregation by mono- and divalent cations

Phosphate addition is commonly applied to remediate lead contaminated sites via the formation of lead phosphate particles with low solubility. However, the effects of natural organic matter (NOM) with different properties, as well as the contributions of specific interactions (particle-particle, particle-NOM, and NOM-NOM) in enhanced stabilization or flocculation of the particles, are not currently well understood. This study investigates the influence of two aquatic NOM and two soil or coal humic acid (HA) extracts on the aggregation behavior of lead phosphate particles and explores the controlling mechanisms. All types of NOM induced disaggregation and steric stabilization of the particles in the presence of Na+ (100 mM) or low (1 mM) Ca2+ concentrations, as well as at low NOM concentrations (1 mgC/L). However, for the soil and coal HA, a threshold at NOM concentrations of 10 mgC/L and high (3 mM) Ca2+ concentrations was observed where bridging flocculation (rather than steric stabilization) occurred. In situ attenuated total reflectance – Fourier transform infrared characterization confirmed adsorption of the soil and coal humic acid extracts (10 mgC/L) onto the surface of the lead phosphate particles in 3 mM Ca2+, whereas dynamic and static light scattering demonstrated extensive HA flocculation that dominated the overall scattered light intensities. These results imply that the accelerated aggregation was induced by a combination of HA adsorption and bridging flocculation by Ca2+. Overall, this research demonstrates that the type of NOM is critical to predict the colloidal stability of lead phosphate particles. Aquatic NOM stabilized the particles under all conditions evaluated, but soil or coal HA with higher molecular weight and aromaticity showed highly variable stabilization or flocculation behavior depending on the HA and Ca2+ concentrations available to adsorb to the particles and participate in bridging. These results provide new mechanistic insights on particle stabilization or destabilization by NOM.

Comparison of ribavirin degradation in the UV/H2O2 and UV/PDS systems: Reaction mechanism, operational parameter and toxicity evaluation

Residues in surface water of ribavirin, which used extensively during the COVID-19 pandemic, have become an emerging issue due to its adverse impact on the environment and human health. UV/H2O2 and UV/peroxydisulfate (PDS) have different degradation effects on ribavirin, and the same operational parameter have different effects on the two processes. In this study, the reaction mechanism and degradation efficiency for ribavirin were studied to compare the differences under UV/H2O2 and UV/PDS processes. We calculated the total rate constants of ribavirin with HO• and SO4•- in the liquid phase as 2.73 × 108 and 9.39 × 105 M−1s−1. The density functional theory (DFT) calculation results showed that HO• and SO4•- react more readily with ribavirin via H-abstraction (HAA). The nitrogen-containing heterocyclic ring is difficult to undergo ring-opening degradation. The UV/PDS process was more stable and performed better than the UV/H2O2 for the ribavirin degradation when the same molar oxidant dosage was applied. HO• plays an extremely important role in the degradation of ribavirin by UV/PDS. The reason for this phenomenon is the combination of the higher yield of HO• produced in the UV/PDS process and the faster reaction rate of ribavirin with HO•. The UV/H2O2 process is more sensitive to pH than UV/PDS. Alkaline condition can significantly inhibit the ribavirin degradation. The effects of natural organic matter (NOM) and ribavirin concentration were also compared. Eventually, the toxicity prediction of the product showed that the opening-ring products were more toxic than the parent compound.

Influence of water matrix components on the UV/chlorine process and its reactions mechanism

The UV/chlorine system has become an attractive alternative Advanced Oxidation Process (AOP) for the removal of recalcitrant pollutants in the last decade due to the simultaneous formation of chlorine and hydroxyl radicals. However, there is no consensus regarding the results and trends obtained in previous micropollutant removal studies by AOPs, highlighting the complexity of the UV/chlorine process and the need for further research. This study investigates the degradation of acetaminophen (ACTP) by UV/chlorine and the effects of the water matrix in the reaction kinetics. In particular, the effects of natural organic matter (NOM), alkalinity and mineral salts on the kinetics and reactive species were elucidated. The complexity of the system was revealed by the analysis of the radical generation and transformation in different water matrices, applying the kinetic modelling approach to complement the scavenger tests.The higher kinetic rates of ACTP at alkaline pH provided new insights into the chlorine reactions under UV radiation, where secondary and tertiary reactive oxygen species including ozone were proven to play the major role in degradation. On the contrary, at acidic pH, reaction kinetic modelling demonstrated that ClO• radical occurs at high concentrations in the order of 10−10 M, being therefore the main oxidant, followed by other chlorine radicals. It is noteworthy that at alkaline pH the presence of typical inorganic ions such as carbonate had little impact on ACTP degradation, contrary to the observed reduction of degradation rates at acidic pH. The expected detrimental effect of the NOM in AOPs was also evidenced, although the use of chlorine as radical source reduces the relevance of the inner filter effect in comparison to UV/H2O2.

Factors Affecting the Interpretation of Online Phycocyanin Fluorescence to Manage Cyanobacteria in Drinking Water Sources

Recently, in situ YSI EXO2 phycocyanin fluorescence probes have been widely deployed as a means to determine cyanobacterial abundance in drinking water sources, yet few studies have evaluated the effects of natural organic matter (NOM) and the ambient water temperature on the probe readings. In this study, Suwannee River NOM was added to laboratory cultivated cyanobacterial species to test the performance of the phycocyanin probe. The impact of temperature on phycocyanin fluorescence was evaluated by monitoring the laboratory cultivated cyanobacterial species and extracted phycocyanin pigment. Additionally, in situ phycocyanin fluorescence of the field samples from the water intake of a drinking water treatment plant (DWTP) in 2018 were compared with grab sample laboratory taxonomic analyses. We found: (1) the presence of Suwannee River NOM leads to the decrease in cell-bound cyanobacterial phycocyanin readings; (2) increasing ambient water temperature reduces dissolved and cell-bound cyanobacterial phycocyanin readings; (3) field study phycocyanin probe readings significantly correlated with the total cyanobacterial biovolume (R = 0.73, p &lt; 0.1), and the relationship depends on the biovolume of dominant cyanobacterial species; (4) phycocyanin probe readings have a strong positive correlation with the natural light intensities; and (5) probe users should be fully aware of the sources of interferences when interpreting the results and apply the other physical-chemical parameters data simultaneously generated by the fluorometry to improve the probe’s measurements.