Natural Organic Matter Isolates Research Articles

Reactions of Monobromamine and Dibromamine with Phenolic Compounds and Organic Matter: Kinetics and Formation of Bromophenols and Bromoform.

Monobromamine (NH2Br) and dibromamine (NHBr2) produced from reactions of hypobromous acid (HOBr) with ammonia can react with phenolic structures of natural organic matter (NOM) to produce disinfection byproducts such as bromoform (CHBr3). The reactivity of NH2Br was controlled by the reaction of the bromoammonium ion (NH3Br+) with phenolate species, with specific rate constants ranging from 6.32 × 102 for 2,4,6-tribromophenol to 1.22 × 108 M-1 s-1 for phenol. Reactions of NHBr2 with phenol and bromophenols were negligible compared to its self-decomposition; rate constants could be determined only with resorcinol for pH > 7. At pH 8.1-8.2, no formation of CHBr3 was observed from the reaction of NH2Br with phenol while the reaction of NH2Br with resorcinol produced a significant concentration of CHBr3. In contrast to NH2Br, a significant amount of CHBr3 produced with an excess of NHBr2 over phenol was explained by the reactions of HOBr produced from NHBr2 decomposition. A comprehensive kinetic model including the formation and decomposition of bromamines and the reactivity of HOBr and NH2Br with phenolic compounds was developed at pH 8.0-8.3. Furthermore, the kinetic model was used to evaluate the significance of the NH2Br and NHBr2 reactions with the phenolic structures of two NOM isolates.

Reactivity of Dissolved Organic Matter with the Hydrated Electron: Implications for Treatment of Chemical Contaminants in Water with Advanced Reduction Processes.

Advanced reduction processes (ARP) have garnered increasing attention for the treatment of recalcitrant chemical contaminants, most notably per- and polyfluoroalkyl substances (PFAS). However, the impact of dissolved organic matter (DOM) on the availability of the hydrated electron (eaq-), the key reactive species formed in ARP, is not completely understood. Using electron pulse radiolysis and transient absorption spectroscopy, we measured bimolecular reaction rates constant for eaq- reaction with eight aquatic and terrestrial humic substance and natural organic matter isolates ( kDOM,eaq-), with the resulting values ranging from (0.51 ± 0.01) to (2.11 ± 0.04) × 108 MC-1 s-1. kDOM,eaq- measurements at varying temperature, pH, and ionic strength indicate that activation energies for diverse DOM isolates are ≈18 kJ mol-1 and that kDOM,eaq- could be expected to vary by less than a factor of 1.5 between pH 5 and 9 or from an ionic strength of 0.02 to 0.12 M. kDOM,eaq- exhibited a significant, positive correlation to % carbonyl carbon for the isolates studied, but relationships to other DOM physicochemical properties were surprisingly more scattered. A 24 h UV/sulfite experiment employing chloroacetate as an eaq- probe revealed that continued eaq- exposure abates DOM chromophores and eaq- scavenging capacity over a several hour time scale. Overall, these results indicate that DOM is an important eaq- scavenger that will reduce the rate of target contaminant degradation in ARP. These impacts are likely greater in waste streams like membrane concentrates, spent ion exchange resins, or regeneration brines that have elevated DOM concentrations.

Extraction and concentration of nanoplastic particles from aqueous suspensions using functionalized magnetic nanoparticles and a magnetic flow cell

Although a considerable knowledge base exists for environmental contamination from nanoscale and colloidal particles, significant knowledge gaps exist regarding the sources, transport, distribution, and effects of microplastic pollution (plastic particles < 5 mm) in the environment. Even less is known regarding nanoplastic pollution (generally considered to be plastic particles < 1 μm). Due to their small size, nanoplastics pose unique challenges and potential risks. We herein report a technique focused on the concentration and measurement of nanoplastics in aqueous systems. Hydrophobically functionalized magnetic nanoparticles (HDTMS-FeNPs) were used as part of a method to separate and concentrate nanoplastics from environmentally relevant matrices, here using metal-doped polystyrene nanoplastics (PAN-Pd@NPs) to enable low-level detection and validation of the separation technique. Using a magnetic separation flow cell, PAN-Pd@NPs were removed from suspensions and captured on regenerated cellulose membranes. Depending on the complexity of solution chemistry, variable extraction rates were possible. PAN-Pd@NPs were recovered from ultrapure water, synthetic freshwater, synthetic freshwater with a model natural organic matter isolate (NOM; Suwannee River Humic Acid), and from synthetic marine water, with recoveries for PAN-Pd@NPs of 84.9%, 78.9%, 70.4%, and 56.1%, respectively. During the initial method testing, it was found that the addition of NaCl was needed in the ultrapure water, synthetic freshwater and synthetic fresh water with NOM to induce particle aggregation and attachment. These results indicate that magnetic nanoparticles in combination with a flow-through system is a promising technique to extract nanoplastics from aqueous suspensions with various compositions.

Trichloramine and Hydroxyl Radical Contributions to Dichloroacetonitrile Formation Following Breakpoint Chlorination.

Breakpoint chlorination is applied to remove ammonia in water treatment. Trichloramine (NCl3) and transient reactive species can be present, but how they affect the formation of nitrogenous disinfection byproducts is unknown. In this study, the dichloroacetonitrile (DCAN) formation mechanisms and pathways involved during breakpoint chlorination (i.e., free chlorine to ammonia molar ratio ≥2.0) were investigated. DCAN formation during breakpoint chlorination of natural organic matter (NOM) isolates was 14.3-20.3 μg/L, which was 2-10 times that in chlorination without ammonia at similar free chlorine residual conditions (2.1-2.9 mg/L as Cl2). The probe tests and electron paramagnetic resonance spectra supported the presence of •OH, •NO, and NCl3 besides free chlorine in breakpoint chlorination. 15N-labeled ammonium-N tests indicated the incorporation of ammonium-N in DCAN formation though ammonia was eliminated during breakpoint chlorination. Aromatic non-nitrogenous moieties, such as phenols (i.e., none DCAN precursors in the free-chlorine-only system), became DCAN precursors during breakpoint chlorination. The reactions involved in reactive nitrogen species, such as •NO/•NO2 and NCl3, led to additional nitrogen sources in DCAN formation, accounting for 36-84% of total nitrogen sources in DCAN formation from NOM isolates and real water samples. Scavenging •OH by tert-butanol reduced DCAN formation by 40-56%, indicating an important role of •OH in transforming DCAN precursors. This study improves the understanding of breakpoint chlorination chemistry.

Influence of Organic Ligands on the Redox Properties of Fe(II) as Determined by Mediated Electrochemical Oxidation.

Fe(II) has been extensively studied due to its importance as a reductant in biogeochemical processes and contaminant attenuation. Previous studies have shown that ligands can alter aqueous Fe(II) redox reactivity but their data interpretation is constrained by the use of probe compounds. Here, we employed mediated electrochemical oxidation (MEO) as an approach to directly quantify the extent of Fe(II) oxidation in the absence and presence of three model organic ligands (citrate, nitrilotriacetic acid, and ferrozine) across a range of potentials (EH) and pH, thereby manipulating oxidation over a broad range of fixed thermodynamic conditions. Fe(III)-stabilizing ligands enhanced Fe(II) reactivity in thermodynamically unfavorable regions (i.e., low pH and EH) while an Fe(II) stabilizing ligand (ferrozine) prevented oxidation across all thermodynamic regions. We experimentally derived apparent standard redox potentials, EHϕ, for these and other (oxalate, oxalate2, NTA2, EDTA, and OH2) Fe-ligand redox couples via oxidative current integration. Preferential stabilization of Fe(III) over Fe(II) decreased EHϕ values, and a Nernstian correlation between EHϕ and log(KFe(III)/KFe(II)) exists across a wide range of potentials and stability constants. We used this correlation to estimate log(KFe(III)/KFe(II)) for a natural organic matter isolate, demonstrating that MEO can be used to measure iron stability constant ratios for unknown ligands.

Preferential Halogenation of Algal Organic Matter by Iodine over Chlorine and Bromine: Formation of Disinfection Byproducts and Correlation with Toxicity of Disinfected Waters.

The increasing occurrence of harmful algal blooms (HABs) in surface waters may increase the input of algal organic matter (AOM) in drinking water. The formation of halogenated disinfection byproducts (DBPs) during combined chlorination and chloramination of AOM and natural organic matter (NOM) in the presence of bromide and iodide and haloform formation during halogenation of model compounds were studied. Results indicated that haloform/halogen consumption ratios of halogens reacting with amino acids (representing proteins present in AOM) follow the order iodine > bromine > chlorine, with ratios for iodine generally 1-2 orders of magnitude greater than those for chlorine (0.19-2.83 vs 0.01-0.16%). This indicates that iodine is a better halogenating agent than chlorine and bromine. In contrast, chlorine or bromine shows higher ratios for phenols (representing the phenolic structure of humic substances present in NOM). Consistent with these observations, chloramination of AOM extracted from Microcystis aeruginosa in the presence of iodide produced 3 times greater iodinated trihalomethanes than those from Suwannee River NOM isolate. Cytotoxicity and genotoxicity of disinfected algal-impacted waters evaluated by Chinese hamster ovary cell bioassays both follow the order chloramination > prechlorination-chloramination > chlorination. This trend is in contrast to additive toxicity calculations based on the concentrations of measured DBPs since some toxic iodinated DBPs were not identified and quantified, suggesting the necessity of experimentally analyzing the toxicity of disinfected waters. During seasonal HAB events, disinfection practices warrant optimization for iodide-enriched waters to reduce the toxicity of finished waters.

Natural organic matter composition and nanomaterial surface coating determine the nature of platinum nanomaterial-natural organic matter corona

Natural organic matter corona (NOM corona) is an interfacial area between nanomaterials (NMs) and the surrounding environment, which gives rise to NMs' unique surface identity. While the importance of the formation of natural organic matter (NOM) corona on engineered nanomaterials (NMs) to NM behavior, fate, and toxicity has been well-established, the understanding of how NOM molecular properties affect NOM corona composition remains elusive due to the complexity and heterogeneity of NOM. This is further complicated by the variation of NOMs from different origins. Here we use eight NOM isolates of different molecular composition and ultrahigh resolution Fourier-transform ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) to determine the molecular composition of platinum NM-NOM corona as a function of NOM composition and NM surface coating. We observed that the composition of PtNM-NOM corona varied with the composition of the original NOM. The percentage of NOM formulas that formed PVP-PtNM-NOM corona was higher than those formed citrate-PtNM-NOM corona, due to increased sorption of NOM formulas, in particular condensed hydrocarbons, to the PVP coating. The relative abundance of heteroatom formulas (CHON, CHOS, and CHOP) was higher in the PVP-PtNM-NOM corona than in citrate-PtNM-corona which was in turn higher than those in the original NOM isolate, indicating preferential partitioning of heteroatom-rich molecules to NM surfaces. The relative abundance of CHO, CHON, CHOS, CHOP and condensed hydrocarbons in PtNM-NOM corona increased with their increase in NOM isolates. Furthermore, PtNM-NOM corona is rich with compounds with high molecular weight. This study demonstrates that the composition and properties of PtNM-NOM corona depend on NOM molecular properties and PtNM surface coating. The results here provide evidence of molecular interactions between NOM and NMs, which are critical to understanding NM colloidal properties (e.g., surface charge and stability), interaction forces (e.g., van der Waals and hydrophobic), environmental behaviors (e.g., aggregation, dissolution, sulfidation, etc.), and biological effects (e.g., uptake, bioaccumulation, and toxicity).

Molecular insights into the reactivity of aquatic natural organic matter towards hydroxyl (•OH) and sulfate (SO4•−) radicals using FT-ICR MS

The higher scavenging capacity of natural organic matter (NOM) to hydroxyl radical (•OH) than sulfate radical (SO4•−) has been long-acknowledged. However, the difference in reactivity and the influence of initial characteristics, especially at the molecular-level, remain unaddressed. In this study, the reactivities of different NOM isolates to •OH and SO4•− were compared based on the determined second-order rate constants following the depletion of UV254-absorbing moieties. Three NOM isolates with varying characteristics were selected to investigate the influence of initial characteristics on their reactivities. With the identified reactive molecules using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), the distinct reactivity between the radicals and the influence of the initial characteristics were illustrated. The reactivity towards SO4•− was dominated by the electron density of the molecules (i.e., double bond equivalent (DBE)), while that of •OH was also shaped by molecular size (i.e., m/z) and composition (i.e., N- or S-incorporation). The examination on the exclusively reactive molecules (accounting for 10–20%) reflected a preferred H-abstraction by •OH and decarboxylation by SO4•−. Moreover, the analysis on the shared reactive molecules (80–90%) based on the UV254 versus electron-donating capacity (EDC) dependency revealed a prevalent •OH addition while single electron transfer to SO4•−. The different reaction rates associated with the proposed transformation pathways supported the observed higher reactivity of NOM to •OH than SO4•−.

Importance of origin and characteristics of biopolymers in reversible and irreversible fouling of ultrafiltration membranes

The present work compares the chemical properties of isolated biopolymers of different origins and their fouling potential during ultrafiltration (UF). The biopolymers were extracted from secondary wastewater effluent as effluent organic matter (EfOM) and from surface water as natural organic matter (NOM). Multiple analytical techniques were used to characterize the isolates. The characterization results revealed that EfOM biopolymers were more enriched in protein-type structures compared to the NOM organics, and they presented significant differences in the reversibility of membrane fouling. Dissolved in pure water, EfOM biopolymers led to more irreversible fouling than that caused by NOM isolates. Dosing divalent cations (e.g., Ca2+) into the solutions increased the irreversibility of both types of fouling, while aggravating NOM fouling more significantly. Further investigation was conducted to understand the interaction between EfOM and NOM biopolymers during formation of the fouling layer. The results showed that the interaction between these two types of organics was negligible in the absence of salts. These findings highlight the importance of a comprehensive understanding of biopolymers from different origins, considering their chemical properties and water chemistry, which have valuable implications for selecting suitable membrane fouling control strategies for treating water from different origins.

Overlooked Role of Carbonyls of Natural Organic Matter on the Dissolution of Zinc Oxide Nanoparticles

Zinc oxide nanoparticles (ZnO NPs) are harmful because of the release of cytotoxic Zn2+ during dissolution. The dissolution process of ZnO NPs is affected by natural organic matter (NOM) in the water environment. In this study, we investigated the role of carbonyl functional groups of NOM isolates in the dissolution of ZnO NPs. Sodium borohydride (NaBH4) can selectively reduce the carbonyls in NOM. We treated seven types of NOMs with NaBH4. The experimental results show that the NOM treated by NaBH4 has a significantly reduced ability to dissolve ZnO NPs. A series of model aromatic ketones and quinones were used to simulate NOM, and these model small-molecule mixtures were selectively reduced by NaBH4 and sodium dithionite (Na2S2O4). The ability of the treated model small-molecule mixture to dissolve ZnO NPs was reduced. These results further demonstrate that carbonyls play an important role in the dissolution of ZnO NPs. The results of the study allow us to better understand the transfer process of ZnO N...

Formation of iodinated trihalomethanes and noniodinated disinfection byproducts during chloramination of algal organic matter extracted from Microcystis aeruginosa

The increasing occurrence of harmful algal blooms in surface waters may increase the input of algal organic matter (AOM) to the dissolved organic matter pool. The formation of iodinated trihalomethanes (I-THMs) and noniodinated disinfection byproducts (DBPs) in synthetic waters containing AOM extracted from Microcystis aeruginosa was investigated in chloramination (preformed and in-situ formed chloramine, NH2Cl and Cl2-NH2Cl, respectively) and chlorination (Cl2) processes. AOM is much more favorable for iodine incorporation than natural organic matter (NOM). For example, the formation of I-THM from AOM is much higher than NOM isolate extracted from treated water (e.g., 3.5 times higher in the NH2Cl process), and thus higher iodine utilization and substitution factors from AOM were observed. Short contact time (2 min) chlorination in Cl2-NH2Cl process leading to the formation of halogenated intermediates favored I-THM formation, compared with NH2Cl process. However, further increasing chlorine contact time from 5 min to 24 h facilitated the conversion from iodide to iodate and thus I-THM formation decreased. Meanwhile, the formation of noniodinated THM4, haloacetonitriles (HANs), and haloacetaldehydes (HALs) increased. Factors including concentrations of AOM and bromide, pH, and chlorine/nitrogen ratios influenced the formation of I-THMs and noniodinated DBPs. To evaluate the benefit of mitigating I-THM formation over the risk of noniodinated DBP formation, measured DBPs were weighed against their mammalian cell toxicity indexes. Increasing the chlorine exposure increased the calculated cytotoxicity based on concentrations of measured I-THMs and noniodinated DBPs since unregulated HANs and HALs were the controlling agents.

Comparing three Australian natural organic matter isolates to the Suwannee river standard: Reactivity, disinfection by-product yield, and removal by drinking water treatments

Water treatments that provide efficient removal of organic and inorganic disinfection by-product (DBP) precursors across variable natural organic matter (NOM) sources are desirable. Treatments that effectively remove inorganic DBP precursors such as bromide, which significantly shift the speciation of DBP formation towards more toxic DBPs, are of particular interest and have been less investigated.This study characterised NOM isolated from three major drinking water sources in Southeast Queensland (SEQ), Australia, and compared it to the International Humic Substances Society (IHSS) Suwannee River NOM isolate (SR) in terms of DBP precursor removal treatments and DBP formation. Each NOM isolate was used to make synthetic water samples with otherwise identical water quality parameters, that were treated with enhanced coagulation (EC) or EC followed by; anion exchange (MIEX® resin), powdered activated carbon (PAC), granular activated carbon (GAC) or silver impregnated activated carbon (SIAC), to investigate the removal of DBP precursors (bromide and DOC), minimisation of DBPs, as well as the change in specific chlorine demand. EC/SIAC treatment was the most effective method of DBP control studied, due to the efficient simultaneous NOM and bromide adsorption of the SIAC (99 ± 1% bromide removal regardless of NOM source). This treatment also resulted in >92% removal of each of the measured DBPs across all NOM sources, with the exception of DBAN and 1,1-DCP, which achieved >80% removal across all NOM sources. Increases in tribromomethane (TBM) and dibromoacetonitrile (DBAN) formation were observed after all other treatment/NOM-isolate combinations, due to increased Br:DOC ratio after treatment, whereas chlorinated DBPs were generally well-controlled by all treatment/NOM-isolate combinations. Differences in reactivity of the individual NOM isolates were found to be related to both the origin of the isolate and the treatment employed, however, bromide removal capacity for each treatment was independent of NOM source.

A systematic investigation on the bactericidal transient species generated by photo-sensitization of natural organic matter (NOM) during solar and photo-Fenton disinfection of surface waters

In this work, the role of dissolved oxygen in the solar and the photo-Fenton-mediated E. coli inactivation process was put under scrutiny. The effect of transient species that were produced in the presence of various natural organic matter isolates (NOM), namely Suwannee River (SR) NOM, Nordic Reservoir (NR) NOM, SR Humic acid (SRHA), and SR Fulvic acid (SRFA) was studied in detail. The role of 1O2 in this reaction was systematically evaluated by modifying the O2 concentration (N2/O2 purging) and the matrix composition (10, 50, and 100% deuterium oxide (D2O) v/v). In the presence of NOM, 1O2 was generated and the enhancement of E. coli inactivation rate due to charge transfer from triplet state to molecular oxygen. The comparison between SR and NR NOM showed that for these compounds, triplet state of NOM (3NOM*), and 1O2 were the more favorable active species in E. coli inactivation, respectively. Also, the second order rate constants (kE. coli2nd) of E. coli with 3NOM*, and 1O2 were calculated by using the steady state approximation. The obtained results showed that the rate values of 1O2 related to NR NOM was ∼ 5.6 times higher than SR NOM, while the rate values of 3NOM* for SR NOM was ∼ 8.7 times higher than NR NOM. We also determined the effect of these organic matter isolates in the photo-Fenton process and its constituents (solar/Fe2+, solar/H2O2, and solar/Fe2+/H2O2). In presence of NOM, the photo-Fenton process inactivation rates increased which confirmed that the combined processes has additional pathways generated with disinfecting effect during solar exposure of bacteria.

Enhanced mineralization of atrazine by surface induced hydroxyl radicals over light-weight granular mixed-quartz sands with ozone

A light-weight granular mixed-quartz sand (denoted as L-GQS) combined with stirring-assisted bubble column reactor was firstly applied in catalytic ozonation of atrazine. The L-GQS, with a density of 2.36 g cm−3 and average diameter of ca. of 4 mm, was readily churned up and uniformly distributed within the solution in the reactor. The introduction of L-GQS was found to exhibit enhanced catalytic ozonation of atrazine, with the increase in degradation rate and the dissolved organic carbon (DOC) removal being more than 2-fold for the catalytic process (L-GQS dosage = 5 g L−1, [atrazine]0 = 50 μM, [O3] = 25 mg L−1, gas flow = 0.2 L min−1, at pH 7.0 and 293 K). The L-GQS settled at the bottom of the reactor after experimentation, allowing its easy separation from the solution. A complete characterization of the material (XRD, XPS, FTIR, FE-SEM/EDS, BET and pHpzc) revealed that L-GQS consisted of α-quartz, β-cristobalite, anorthoclase and small amount of iron oxy-hydroxides. Hydroxyl groups, Bronsted acid sites and Lewis acid sites on the surface of L-GQS all contributed to the atrazine adsorption, ozone decomposition and ·OH generation. The L-GQS catalyzed ozonation exhibited superior atrazine degradation and mineralization rates in a wide range of pH (3.0–9.0) and reaction temperatures (278 K–293 K). Also, an enhancement of DOC abatement was observed both in presence of natural organic matter isolates and natural water matrices (river water) when L-GQS was used. Finally, the degradation mechanism was proposed, based on the intermediates and by-products formation analyzed by LC-QTOF-MS/MS and ionic chromatography. Our results indicate that the L-GQS combined with stirring-assisted bubble column reactor could be utilized as an enhancement of ozone-based advanced oxidation processes.

Photocatalytic oxidation of sulfamethoxazole in the presence of TiO2: Effect of matrix in aqueous solution on decomposition mechanisms

As water matrix, inorganic anions and natural organic matter (NOM) may impact the removal of pharmaceuticals not only on the kinetics but also on the transformation products formation. In this study, the effects of initial pH, inorganic anions and NOM on the transformation pathways of sulfamethoxazole (SMX) during photocatalytic decomposition were investigated. Three pathways including hydroxylation, hydrolysis and isoxazole ring oxidation were found during SMX photocatalysis. SMX in deionized water was degraded by hydroxylation principally in alkaline situation, while hydrolysis was the main pathway in acidic condition. Almost all the pathways for SMX decomposition were suppressed when anions were added, with the inhibitory effect followed the order of HPO42− > HCO3− > SO42− > Cl− > H2PO4−. The formation of products with larger energy barrier was affected more significantly when anions were added. The products formation was also impacted by the presence of NOM isolates including “Suwannee River Humic Acid” (SRHA), “Suwannee River Fulvic Acid” (SRFA) and “Suwannee River NOM” (SRNOM). The mechanisms of hydroxylation and isoxazole ring oxidation were inhibited by NOM, with the order of SRFA > SRHA > SRNOM, due to their hydroxyl radical scavenging abilities which were related to their aromaticity degree. Most of the hydrolysis products were favored in the presence NOM, and the enhancement effect was in accordance with the sequence of SRNOM > SRFA > SRHA due to the different photoinductive abilities of the NOM isolates.

Optical properties of straw-derived dissolved organic matter and growth inhibition of Microcystis aeruginosa by straw-derived dissolved organic matter via photo-generated hydrogen peroxide

Recent advances in research on algae inhibition by using low-cost straw proposed a possible mechanism that reactive oxygen species (ROS) generated by the solar irradiation of straw-derived dissolved organic matter (DOM) might contribute to cyanobacteria inhibition. However, this process is not clearly understood. Here, DOM from three types of straw (barley, rice, and wheat) and natural organic matter (NOM) isolates were investigated in terms of their photochemical properties and ROS generating abilities. Results demonstrated that the DOM derived from the aeration decomposition of barley straw (A-DOMbs) yielded the best formation efficiencies of hydrogen peroxide (H2O2) and hydroxyl radicals (•OH) under solar-simulated irradiation in all organic matter samples. Correlation analysis implies that optical parameters and phenolic hydroxyl group contents can signify ROS generating abilities of different DOM solutions. Bioassay results show that A-DOMbs possesses the highest inhibition performance for M. aeruginosa in all DOM samples, much higher than those of NOM isolates. The addition of catalase greatly relieves the inhibition performance, making the loss of chlorophyll a content decreased from 37.14% to 7.83% in 2 h for A-DOMbs, which implies that for cyanobacteria growth inhibition, photochemically-produced H2O2 from SOM is far more important than singlet oxygen (1O2), •OH, and even SOM itself. Our results show that H2O2 photochemically generated from straw-derived DOM is able to result in rapid inhibition of M. aeruginosa in a relatively short period, furthering the understanding of complicated mechanisms of cyanobacteria inhibition by using low-cost straw in eutrophic waters.

Transformation products formation of ciprofloxacin in UVA/LED and UVA/LED/TiO2 systems: Impact of natural organic matter characteristics.

The role of natural organic matter (NOM) in contaminants removal by photolysis and photocatalysis has aroused increasing interest. However, evaluation of the influence of NOM characteristics on the transformation products (TPs) formation and transformation pathways of contaminants has rarely been performed. This study investigated the decomposition kinetics, mineralization, TPs formation and transformation pathways of antibiotic ciprofloxacin (CIP) during photolysis and photocatalysis in the presence of three commercial NOM isolates (Sigma-Aldrich humic acid (SAHA), Suwannee River humic acid (SRHA) and Suwannee River NOM (SRNOM)) by using UVA light emitting diode (UVA/LED) as an alternative light source. NOM isolates insignificantly affected CIP photolysis but strongly inhibited CIP photocatalysis due to competitive radical quenching. The inhibitory effect followed the order of SAHA (49.6%) > SRHA (29.9%) > SRNOM (21.2%), consistent with their •OH quenching abilities, SUVA254 values and orders of aromaticity. Mineralization rates as revealed by F- release were negatively affected by NOM during CIP photocatalysis. TPs arising from hydroxylation and defluorination were generally suppressed by NOM isolates in UVA/LED and UVA/LED/TiO2 systems. In contrast, dealkylation and oxidation of piperazine ring were promoted by NOM. The enhancement in the apparent formation kinetics (kapp) of TP245, TP291, TP334a, TP334b and TP362 followed the order of SRNOM > SRHA > SAHA. kapp values were positively correlated with O/C ratio, carboxyl content, E2/E3 and fluorescence index (FI) of NOM and negatively related with SUVA254 values. The observed correlations indicate that NOM properties are important in determining the fate and transformation of organic contaminants during photolysis and photocatalysis.

Ferrate(VI) decomposition in water in the absence and presence of natural organic matter (NOM)

The kinetics of ferrate(VI) decomposition in natural water were assessed in the absence and presence of natural organic matter (NOM) (pH = 7.50, [Fe(VI)] = 54 µM, DOC = 0.00–10.00 and 1.00–8.57 mg/L for a simulated natural water and six real natural waters, respectively). Without NOM, Fe(VI) decomposition in simulated natural water exhibited a biphasic kinetics pattern, i.e. a 2nd-order reaction with respect to Fe(VI) concentration followed by a 1st-order reaction. However, an additional instant Fe(VI) loss was observed at the onset in the presence of NOM for both simulated and real natural waters, thereby rendering Fe(VI) decay with NOM a unique three-stage kinetics pattern. The initial instant Fe(VI) loss was caused due to the homogenous Fe(VI) self-decay and the rapid reactions between Fe(VI) and NOM. The latter accounted for a major fraction of the initial Fe(VI) loss and was in direct proportion with the initial DOC (DOC0) (Δ[Fe(VI)]0DOC = αNOM DOC0; αNOM = 1.45 µM Fe(VI)·L/mg DOC for the simulated natural water, and 0.66–1.35 µM Fe(VI)·L/mg DOC for the six natural waters). Fe(VI) decomposition experiments with different Suwannee River NOM isolates revealed that hydrophobic NOM fractions (i.e. fulvic acid (FA) and humic acid (HA)) caused a more significant initial Fe(VI) loss than the hydrophilic group (HPI), suggesting that Fe(VI) preferentially reacted with hydrophobic NOM molecules rather than hydrophilic compounds. Furthermore, an approach developed for the estimation of αNOM revealed a linear correlation between αNOM and specific UV absorbance (SUVA) (αNOM = 0.27SUVA + 0.18, R2 = 0.71). This study provides essential information regarding Fe(VI) decomposition for the determination of Fe(VI) dose and exposure for effective water treatment.

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.

Redox properties of clay-rich sediments as assessed by mediated electrochemical analysis: Separating pyrite, siderite and structural Fe in clay minerals

Redox reactions with Fe-containing minerals in clay-rich sediments largely affect the speciation, mobility, and (bio-) availability of redox-sensitive contaminants. Here, we use mediated electrochemical oxidation (MEO) and reduction (MER), to quantify the electron accepting and donating capacities (EAC and EDC) of Boom Clay, a potential host formation for radioactive waste disposal. The relevant redox-active minerals pyrite, siderite, smectite and illite were first studied separately. MEO and MER of smectites and illites resulted in sharp current peak responses, reflecting fast electron transfer kinetics. Conversely, broad current peaks were obtained from MEO of pyrite. The current response to MEO of siderite was very small. Under the applied electrochemical conditions in MEO, pyrite was not completely oxidized and only a marginal fraction of siderite was oxidized. All structural Fe (Festruct) in smectites SWa-1 and SWy-1 was redox-active in MER and MEO, whereas in Fithian Illite and IMt-1 only 12–22% of the total Festruct was available. An empirical equation was used to describe the current curves of the tested minerals. This equation allowed to delineate the relative contributions of these minerals to MEO of their mixtures. The EDC of Boom Clay determined by MEO was 0.2±0.05mmol e−/g and predominantly consisted of contributions of pyrite, Festruct in clays and natural organic matter (NOM). Applying the empirical equation allowed to separate the oxidative current response into the contribution of pyrite with slower oxidation kinetics and the combined contribution of faster reacting Festruct and natural organic matter (NOM). Due to the absence of NOM isolates from Boom Clay, the EDC of NOM was estimated based on MEO measurements of dissolved organic matter in Boom Clay pore water and the organic carbon content of Boom Clay. The EDC of Festruct in clays was then obtained by subtracting the contributions of NOM and pyrite from the measured EDC. About 14% of the measured EDC can be attributed to Festruct which implies that about 50% of the structural FeII in Boom Clay is redox-active. In contrast, EAC measurements indicate that FeIIIstruct in Boom Clay is electrochemically inactive.