Natural Organic Matter Solutions Research Articles

Sunlight-Mediated Reductive Transformation of Thallium(III) in Acidic Natural Organic Matter Solutions: Mechanisms and Kinetic Modeling.

Thallium (Tl) redox state determines its speciation and fate in aqueous environments. Despite the high potential of natural organic matter (NOM) providing the reactive groups to complex and reduce Tl(III), the kinetics and mechanisms by which NOM influences the Tl redox transformation have remained insufficiently understood. Here, we studied the reduction kinetics of Tl(III) in acidic Suwannee River fulvic acid (SRFA) solutions under dark and solar-irradiated conditions. Our results show that the thermal Tl(III) reduction occurs by the reactive organic moieties in SRFA, with the electron-donating capacities of SRFA increased with pH and decreased with [SRFA]/[Tl(III)] ratios. Solar irradiation promoted Tl(III) reduction in SRFA solutions as a result of ligand-to-metal charge transfer (LMCT) within the photoactive Tl(III) species as well as an additional reduction process mediated by a photogenerated superoxide. We demonstrated that the formation of Tl(III)-SRFA complexes decreased the reducibility of Tl(III), with the kinetics dependent on the nature of the binding component and SRFA concentrations. A "three ligand class" kinetics model has been developed and satisfactorily describes Tl(III) reduction kinetics over a range of experimental conditions. The insights presented here should assist in understanding and predicting the NOM-mediated speciation and redox cycle of Tl in a sunlit environment.

Amorphous cobalt oxide decorated halloysite nanotubes for efficient sulfamethoxazole degradation activated by peroxymonosulfate

In this study, a new hollow nanotube material, 30% Co–CHNTs was prepared by the impregnation–chemical reduction–calcination method. This material can be used as a peroxymonosulfate (PMS) activator to catalyse the degradation of sulfamethoxazole (SMX). The best reaction conditions that correspond to the degradation rate of SMX, up to 97.5%, are as follows: the concentration of SMX is 10 mg L−1, the amount of catalyst is 0.20 g L−1, the dosage is 1.625 mM, and the solution pH is 6.00. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectrometry (ICP-OES) show that the calcined composites mainly stimulate an increase in the content of bivalent cobalt in PMS and reduce the leaching of cobalt ions after the reaction. Additionally, the 30% Co–CHNTs + PMS reaction system exhibits a reasonable SMX degradation rate in a natural organic matter solution and excellent stability after three repeated experiments. Furthermore, the possible degradation mechanism in the 30% Co–CHNTs + PMS reaction system was analysed through electron paramagnetic resonance (EPR) and free-radical capture experiments, and it was observed that the non-radical degradation of 1O2 plays a leading role in SMX degradation. Finally, according to the nine degradation intermediates detected by liquid chromatography-mass spectrometry (LC–MS), four possible SMX degradation routes were proposed. This study proved that a 30% Co–CHNTs heterogeneous catalyst is easily prepared, inexpensive, and environmentally friendly and has potential application in antibiotic wastewater treatment.

Effect of superfine pulverization of powdered activated carbon on adsorption of carbamazepine in natural source waters

The purpose of this study is to investigate adsorptive removal of carbamazepine from natural source waters by superfine pulverized powdered activated carbon. Superfine pulverization is becoming an increasingly attractive approach to decrease the diffusion path of a target adsorbate molecule and improve the overall the kinetics of activated carbon adsorption. Here we report the impact of pulverization on powdered activated carbon characteristics, and carbamazepine adsorption behavior in distilled and deionized water and natural organic matter solutions. The superfine pulverization decreased the particle size of activated carbon by 50 folds and the specific surface area by 24%. In addition, the micropore volume of the activated carbon decreased from 0.23 cm3/g to 0.14 cm3/g, while mesopore and macropore volumes increased from 0.15 cm3/g and 0.11 cm3/g to 0.18 cm3/g and 0.48 cm3/g, respectively. In terms of surface chemistry, the oxygen and iron contents of the activated carbon increased notably after pulverization. Despite the decrease in surface area and increase in surface polarity, the pulverization improved the adsorption kinetics especially for short contact times i.e., < 6-h. In general, the dissolved organic carbon concentration negatively influenced the kinetic advantage of superfine pulverized activated carbon. Isotherm results indicated that the parent adsorbent has a higher adsorption capacity than superfine activated carbon in distilled and deionized water and in natural waters. This was attributed to the losses in specific surface area and favorable sorption sites inside micropores. Our literature analysis indicated that unlike the small molecular weight hydrophilic organic compounds, the pseudo-equilibrium adsorption capacity could be increased or at least not deteriorated for hydrophobic molecules (Kow > 3). Therefore, superfine pulverization of PAC can serve as a promising approach to remove micropollutants from natural source waters with a kinetic advantage.

Nontargeted identification of chlorinated disinfection byproducts formed from natural organic matter using Orbitrap mass spectrometry and a halogen extraction code

Natural organic matter is a major source of precursors of hazardous chlorinated disinfection byproducts (Cl-DBPs) formed during water treatment, but the majority of Cl-DBPs are still unidentified. In this study, we used a self-written halogen extraction code to identify halogen isotopic patterns in combination with the R package MFAssignR, to identify Cl-DBPs from Orbitrap mass spectra. One hundred and eighty-nine Cl-DBPs were detected during chlorination of a Suwannee River natural organic matter solution, and the structures of 20 of these compounds are reported for the first time. Kendrick mass defect analysis and structural identification confirmed that chlorinated carboxylic acids are common and likely to form during chlorination. A toxicity prediction using quantitative structure-activity relationship models indicated that most of the chlorinated carboxylic acids may be highly toxic. Our analytical strategy can identify Cl-DBPs accurately from complex mixtures and may also be applicable to the identification of other halogenated disinfection byproducts formed during water treatment.

Fouling resistant, high flux, charge tunable hybrid ultrafiltration membranes using polymer chains grafted graphene oxide for NOM removal

The unprecedented performance of fouling resistant, high flux and high rejection hybrid ultrafiltration polysulfone membranes with charge tunable channels using functionalized polymer chains grafted graphene oxide (SPK-g-GO) nanosheets for natural organic matter removal from aqueous feed is herein reported. The novel SPK-g-GO nanosheets were first prepared by esterification reaction at 55 °C using hydroxylated sulfonated poly(ether ether ketone) and graphene oxide. Then, polysulfone blend hybrid membranes with charge tunable channels were produced via the non-solvent induced phase separation method and optimized by varying the SPK-g-GO concentration from 1 to 8 wt.% in the casting solution. The membranes were characterized using scanning electron microscopy, Raman spectroscopy, atomic force microscopy, surface zeta potential and contact angle measurements. The surface texture and hydrophilicity of the membranes were altered due to the incorporation of SPK-g-GO. The hybrid membrane’s water flux was highly dependent on the amount of SPK-g-GO incorporated within the membrane matrix. The maximum water flux (485.7 L m−2 h−1), obtained using the membrane with 4 wt.% SPK-g-GO, was almost 270% higher than that of the membrane without SPK-g-GO (181.1 L m−2 h−1). The fouling resistance and natural organic matter retention capabilities of the membranes were examined via UF tests of synthetic natural organic matter solution at 1 bar feed pressure and neutral pH. The hybrid membrane with 4 wt.% SPK-g-GO loading exhibited remarkable improvement over the pristine one, rejecting more than 86% of the and recovering ~90% of its initial water flux after washing with a stable retention rate during a long-term filtration test.

Photochemical degradation of nebivolol in different natural organic matter solutions under simulated sunlight irradiation: Kinetics, mechanism and degradation pathway

Nebivolol (NEB) is widely used for the treatment of hypertension and chronic heart failure and has become an ubiquitous emerging organic pollutant. It has been shown to undergo direct photolysis, but the role of DOM in its degradation kinetics and mechanism is not well understood. In this study, we studied the photochemical behavior of NEB in the presence of seawater DOM (SW-DOM) and freshwater DOM (SRNOM) under simulated sunlight irradiation. SW-DOM had a promotion effect on NEB photodegradation, whereas SRNOM retarded its photolytic transformation. After eliminating the influence of light screening, we found that the indirect photodegradation rate of NEB in the presence of SRNOM was lower than that in the presence of SW-DOM. Results show that the indirect photodegradation pathway occurred by reaction with triplet-excited DOM (3DOM*). The second-order rate constants for 3SW-DOM* and 3SRNOM* reaction with NEB are 3.7 × 109 M−1 s−1 and 3.7 × 108 M−1 s−1, respectively. The electron donating capacity of SRNOM is higher than that of SW-DOM, indicating that SRNOM may contain more activated phenolic moieties. SRNOM may thus have higher antioxidant activity, leading a higher inhibitory effect on NEB photodegradation. A total of six degradation products were identified in the absence and presence of DOM by HPLC-ESI-MS/MS. The substitution of F by OH-groups and further oxidation a OH-group in the lateral chain to a ketone, and cleavage of N–C bond by the attack of 3DOM* are here proposed as the main degradation pathways.

Identification of important precursors and theoretical toxicity evaluation of byproducts driving cytotoxicity and genotoxicity in chlorination

Chlorination, the most widely used disinfection process for water treatment, is unfortunately always accompanied with the formation of hazardous disinfection byproducts (DBPs). Various organic matter species, like natural organic matter (NOM) and amino acids, can serve as precursors of DBPs during chlorination but it is not clear what types of organic matter have higher potential risks. Although regulation of DBPs such as trihalomethanes has received much attention, further investigation of the DBPs driving toxicity is required. This study aimed to identify the important precursors of chlorination by measuring DBP formation from NOM and amino acids, and to determine the main DBPs driving toxicity using a theoretical toxicity evaluation of contributions to the cytotoxicity index (CTI) and genotoxicity index (GTI). The results showed that NOM mainly formed carbonaceous DBPs (C-DBPs), such as trichloromethane, while amino acids mainly formed nitrogenous DBPs (N-DBPs), such as dichloroacetonitrile (DCAN). Among the DBPs, DCAN had the largest contribution to the toxicity index and might be the main driver of toxicity. Among the precursors, aspartic acid and asparagine gave the highest DCAN concentration (200 g/L) and the highest CTI and GTI. Therefore, aspartic acid and asparagine are important precursors for toxicity and their concentrations should be reduced as much as possible before chlorination to minimize the formation of DBPs. During chlorination of NOM, tryptophan, and asparagine solutions with different chlorine doses and reaction times, changes in the CTI and GTI were consistent with changes in the DCAN concentration.

High-Flux, Antifouling Hydrophilized Ultrafiltration Membranes with Tunable Charge Density Combining Sulfonated Poly(ether sulfone) and Aminated Graphene Oxide Nanohybrid.

In this work, a new protocol was developed for creating charge-tuned, hydrophilic hybrid ultrafiltration (UF) membranes with high flux, rejection rate, and fouling resistance. The membranes were fabricated using a combination of sulfonated poly(ether sulfone) (SPES) and aminated graphene (GO-SiO2-NH2) nanohybrid via the non-solvent-induced phase separation (NIPS) method. The GO-SiO2-NH2 nanohybrid was first synthesized using GO nanosheets and 3-aminopropyl triethoxysilane (APTES) through the covalent condensation reaction at 80 °C and was thoroughly characterized. Then, 2-8 wt% of the nanohybrid was incorporated into the matrix of SPES for the fabrication of the hybrid membranes. The resulting membranes were characterized using an electrokinetic analyzer, a contact angle goniometer, and Raman, field emission scanning electron microscopy-energy-dispersive X-ray spectrometry (FESEM-EDX), and atomic force microscopy experiments. The porosity, charge density, and surface morphology were altered, and the hybrid membranes became more hydrophilic after the incorporation of the nanohybrid. The pure water flux of the hybrid membranes systematically increased with the loading amount of the nanohybrid. The pure water flux of the hybrid membrane containing 6 wt% GO-SiO2-NH2 nanohybrid at a 2 bar feed pressure was 537 L m-2 h-1, about 3-fold that of pristine membrane (186 L m-2 h-1). The fouling resistance of the hybrid membranes was evaluated and confirmed using several representative foulants, including bovine serum albumin, humic acid, sodium alginate, and a synthetic solution of natural organic matter (NOM). The fabricated membranes were capable of removing more than 97% of NOM, without a compromise of their rejection rate.

Freezing Facilitates Formation of Silver Nanoparticles under Natural and Simulated Sunlight Conditions.

Freezing is essential in the light-mediated transformation of organic pollutants. However, the effects of the freezing process on the reduction of Ag+ by natural organic matter (NOM) remains unclear, causing significant uncertainties in the natural formation of silver nanoparticles (AgNPs). This study investigated the sunlight-induced reduction of Ag+ by NOM under natural or controlled freezing processes. Natural (outdoor) freezing experiments demonstrated intense aggregation and precipitation of AgNPs in three aqueous media, including a NOM solution and two river water samples, under natural sunlight irradiation. Indoor experiments under simulated sunlight irradiation and controlled freezing processes showed that freezing at -20 °C and repeated freeze-thaw cycles (-20 to 4 °C) drastically accelerated the formation and growth of AgNPs compared to maintenance at 4 °C. Finally, under the natural freezing process, commercial AgNPs were found to influence the redox reduction of Ag+ probably through a reduction in dissolution rates and homoaggregation with AgNPs newly formed in the river water samples. Additionally, the enhancement effect of freezing on AgNP formation was confirmed in the presence of Ag+ and AgNPs both at environmentally relevant concentration levels, especially upon light irradiation. This work emphasizes the importance of freezing processes on the natural formation of AgNPs.

Impact of light and Suwanee River Fulvic Acid on O2 and H2O2 Mediated Oxidation of Silver Nanoparticles in Simulated Natural Waters.

In this work, we investigate the impact of natural organic matter (NOM) and light on silver nanoparticle (AgNP) dissolution kinetics with particular emphasis on determining the (i) mechanism via which NOM affects the oxidative dissolution of AgNPs, (ii) the role of photogenerated organic radicals and reactive oxygen species (ROS) in oxidative dissolution of AgNPs, and (iii) the mechanism of formation of AgNPs in NOM solution under dark and irradiated conditions. We measured the oxidation of citrate stabilized AgNPs by O2 and hydrogen peroxide (H2O2) in the dark and in irradiated Suwannee River fulvic acid (SRFA) solutions at pH 8.0. Results show that the reactivity of AgNPs toward O2 and H2O2 in the dark decreased in the presence of SRFA as a result of blocking of AgNP surface sites through either steric or electrostatic effects. Irradiation promoted dissolution of AgNPs by O2 and H2O2 in the presence of low concentrations (≤20 mg·L-1) of SRFA as a result of contribution from photogenerated H2O2 formed on irradiation of SRFA as well as photofragmentation of AgNPs. Furthermore, our results show that photogenerated superoxide can induce formation of AgNPs by reducing Ag(I) ions. Based on our experimental results, we have developed a kinetic model to explain AgNP transformation by O2 and H2O2 in the dark and in irradiated SRFA solutions with this model of use in predicting the transformation and fate of AgNPs in natural waters.

Adsorption kinetics and aggregation for three classes of carbonaceous adsorbents in the presence of natural organic matter

In this study, adsorption kinetics of phenanthrene (PNT) and trichloroethylene (TCE) by a graphene nanosheet (GNS), a graphene oxide nanosheet (GO), a single-walled carbon nanotube (SWCNT), a multi-walled carbon nanotube (MWCNT), and two coal based activated carbons (ACs) (F400 and HD3000) were examined in distilled and deionized water (DDW) and under natural organic matter (NOM) preloading conditions. The results showed the times needed for the adsorption of PNT and TCE to reach apparent equilibrium (i.e., ≤3% change per day) followed the order of GO ≥ MWCNT > GNS > SWCNT ∼ HD3000∼F400 and SWCNT > GNS ∼ HD3000 > F400 ∼ MWCNT > GO, respectively. The pseudo second order model successfully represented kinetics data for three classes of carbonaceous adsorbents. The Weber-Morris intraparticle diffusion model indicated three steps adsorption process for PNT and two step adsorption for TCE. In addition, the times needed to reach apparent equilibrium for the adsorption of PNT and TCE in the presence of hydrophobic (HPO) and hydrophilic (HPI) NOM solutions increased for all adsorbents (except for GO). In general, both NOM showed similar impacts on the adsorption rates of PNT and TCE. Aggregation of both GNS and CNTs rapidly occurred during initial couple hours of contact time during preloading, and spiking both PNT and TCE further increased their aggregation.

2D kaolin ultrafiltration membrane with ultrahigh flux for water purification

Membrane separation technology is an important option for the treatment of contaminated surface waters but the relatively high cost of materials and membrane fabrication represent a significant obstacle to the wider use of membrane processes. In this study, we describe the development and testing of a new kind of membrane made from two-dimensional (2D) kaolin nanosheets. The fabrication involved a layer-by-layer stacking of the nanosheets with a cationic polyacrylamide cross-linking agent, assembled on a cellulose acetate supporting layer. The kaolin membrane exhibited an ultrahigh flux (∼4000 L.m-2.h−1.bar−1) which was almost ten times greater than that of a commercial polyether sulfone (PES) ultrafiltration (UF) membrane. The membrane was tested using a range of influent water types, including samples of a lake water, river water and three natural organic matter solutions. The results showed that the kaolin membrane was stable and behaved as an UF membrane, in terms of its pore size distribution (peak distribution at 20–35 nm) and comparable treatment performance to the PES UF membrane. The kaolin membrane showed a substantially reduced rate of fouling, compared to PES membrane, despite a much greater flux, which was partly attributed to its highly hydrophilic nature. The advantages of lower cost, much higher flux and lower fouling propensity make the 2D-kaolin membrane a potentially important development in UF membrane technology for drinking water treatment, and possibly other applications.

Analyzing Solid-Phase Natural Organic Matter Using Laser Desorption Ionization Ultrahigh Resolution Mass Spectrometry.

Extensive sample preparation procedures are required to analyze natural organic matter (NOM) in soil and sediment samples due to the mineral matrix. The preparation procedure not only requires a large amount of sample (typically more than 50 mg), but NOM extraction is frequently incomplete. In this study, 2-5 μg of solid NOM or 500 μg of unprocessed soil samples were fixed on a metal plate using double-sided adhesive tape and analyzed directly using laser desorption ionization (LDI) and ultrahigh resolution mass spectrometry (UHR-MS). Most of the peaks reported in previous LDI UHR-MS studies using NOM solutions were observed, and an additional ∼2200 unique peaks were found by analyzing the fulvic acids direct solid phase. Differences in the molecular composition of NOM in solid samples were seen clearly with minimum sample preparation. Lignin- and tannin-type molecules were detected in both Elliott soil and topsoil from Kyungpook National University campus. The data presented in this study demonstrate a proof-of-principle that highly sensitive, direct, molecular level analysis of solid-phase NOM from unprocessed soil samples and minimum sample preparation is possible.

Dynamic Intermolecular Interactions Control Adsorption from Mixtures of Natural Organic Matter and Protein onto Titanium Dioxide Nanoparticles.

Engineered nanoparticles (NPs) will obtain macromolecular coatings in environmental systems, changing their subsequent interactions. The matrix complexity inherent in natural waters and wastewaters greatly complicates prediction of the corona formation. Here, we investigate corona formation on titanium dioxide (TiO2) NPs from mixtures of natural organic matter (NOM) and a protein, bovine serum albumin (BSA), to thoroughly probe the role of mixture interactions in the adsorption process. Fundamentally different coronas were observed under different NP exposure conditions and time scales. In mixtures of NOM and protein, the corona composition was kinetically determined, and the species initially coadsorbed but were ultimately limited to monolayers. On the contrary, sequential exposure of the NPs to pure solutions of NOM and protein resulted in extensive multilayer formation. The intermolecular complexation between NOM and BSA in solution and at the NP surface was the key mechanism controlling these distinctive adsorption behaviors, as determined by size exclusion chromatography (SEC) and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Overall, this study demonstrates that dynamic intermolecular interactions and the history of the NP surface must be considered together to predict corona formation on NPs in complex environmental media.

The antifouling performance of an ultrafiltration membrane with pre-deposited carbon nanofiber layers for water treatment

In order to improve the performance of the ultrafiltration (UF) membrane process in drinking water treatment, in terms of permeate flux and natural organic matter (NOM) removal, a new form of carbon nanofiber (CNF) layer derived from bacterial cellulose (BC) was prepared and applied as a pre-deposited coating on the UF membrane surface. Using bench-scale, dead-end filtration tests, both CNF and CNF modified by ethanol treatment (M-CNF), were evaluated for the treatment of two model NOM solutions, namely bovine serum albumin (BSA) and sodium alginate (SA). The results showed that both types of coating were effective in mitigating membrane fouling (lower flux decline), with the mitigation increasing with the coating quantity, and also enhanced the removal of BSA and SA. In particular, the M-CNF layer at the greater loading (24 g/m2) was able to reduce membrane fouling to a very substantial degree and achieve > 90% removal of BSA and SA. Characterization of the CNF and M-CNF layers showed significant differences in their morphological and structural properties which may explain the observed differences in their ability to reduce membrane fouling; protection of the UF membrane by the carbon nanofiber layers may be attributed to both physical separation and surface adsorption of the NOM biopolymers.

Complexation and Redox Buffering of Iron(II) by Dissolved Organic Matter

Iron (Fe) bioavailability depends upon its solubility and oxidation state, which are strongly influenced by complexation with natural organic matter (NOM). Despite observations of Fe(II)-NOM associations under conditions favorable for Fe oxidation, the molecular mechanisms by which NOM influences Fe(II) oxidation remain poorly understood. In this study, we used X-ray absorption spectroscopy to determine the coordination environment of Fe(II) associated with NOM (as-received and chemically reduced) at pH 7, and investigated the effect of NOM complexation on Fe(II) redox stability. Linear combination fitting of extended X-ray absorption fine structure (EXAFS) data using reference organic ligands demonstrated that Fe(II) was complexed primarily by carboxyl functional groups in reduced NOM. Functional groups more likely to preserve Fe(II) represent much smaller fractions of NOM-bound Fe(II). Fe(II) added to anoxic solutions of as-received NOM oxidized to Fe(III) and remained organically complexed. Iron oxidation experiments revealed that the presence of reduced NOM limited Fe(II) oxidation, with over 50% of initial Fe(II) remaining after 4 h. These results suggest reduced NOM may preserve Fe(II) by functioning both as redox buffer and complexant, which may help explain the presence of Fe(II) in oxic circumneutral waters.

Trivalent metal cation cross-linked graphene oxide membranes for NOM removal in water treatment

This paper summarizes the development and testing of novel graphene oxide (GO) membranes for the removal of natural organic matter (NOM) from raw water sources used for drinking water supply. In this work, two trivalent cations, Al3+ and Fe3+, were employed as crosslinking agents to stack GO nanosheets layer by layer on a PVDF membrane support, in order to fabricate a suitable GO membrane. The trivalent cations greatly improve the bonding strength between the GO nanosheets through electrostatic forces and coordination bonds, and thus enhance the stability of the GO membrane; the integrity of the membrane in a range of solutions could be maintained for over a month. The initial interlayer spacing of GO nanosheets (0.80nm) could be increased up to 0.86–0.95nm by changing the Al3+ or Fe3+ ion concentration. It was found that the GO membrane flux ranged between 79 and 902 LMH/MPa when treating three representative NOM solutions and a real surface water. A relatively low thickness of the GO layer induced a higher flux of the GO membrane when prepared with the same cation concentration, while increasing the cation concentration resulted in a decline in flux. The flux of the Fe3+ cross-linked GO membrane was approximately 1.1–2.3 times that of the Al3+ cross-linked GO membrane, while both cation-modified GO membranes achieved a similar separation efficiency of the organic contaminants. The study has demonstrated a facile approach to the fabrication of a novel, stable GO membrane employing Al3+/Fe3+ ions as crosslinking species, in order to utilize the excellent properties of GO and produce a GO membrane with a high flux and organic removal performance for water treatment.

The abiotic degradation of methyl parathion in anoxic sulfur-containing system mediated by natural organic matter

Although the kinetics and transformation of methyl parathion have been investigated extensively, its abiotic degradation mechanism in anoxic sulfur-containing groundwater system is still not clear. In this work, the abiotic degradation of methyl parathion in anoxic sulfur-containing system mediated by natural organic matter (NOM) was investigated in batch experiments. It was found that the removal of methyl parathion (up to 80.7%) was greatly improved in sulfide containing NOM compared to those in sulfide alone (with 15.5%) and in NOM alone (almost negligible). Various sulfur species presented significant differences in behaviors methyl parathion degradation, but followed by the pseudo-first-order model well. No facilitated degradation of methyl parathion was observed in sulfite (SO32-) or thiosulfate (S2O32-) containing NOM such as anthraquinone. Although elemental sulfur (S0) and cysteine could further improve the degradation rate of methyl parahtion, their impacts was very limited. The removal efficiency of methyl parathion in anoxic sulfur-containing system were related remarkably with NOM concentration and solution pH. Based on the transformation products identified by gas chromatography-mass spectrometer (GC/MS) and liquid chromatography high resolution mass spectrometer (LC/HRMS), both the nitro group reduction and hydrolysis (SN@C) processes by sulfide (HS−) were further proved to be two predominant reaction mechanisms for the abiotic degradation of methyl parathion in anoxic sulfur-containing system. The results of this study help to understand the natural attenuation of methyl parathion under anoxic sulfide-containing groundwater system mediated by NOM.

Formation of known and unknown disinfection by-products from natural organic matter fractions during chlorination, chloramination, and ozonation

Natural organic matter (NOM) is the main precursor of disinfection by-products (DBPs) formed during drinking water treatment processes. Previous studies of the relationships between DBP formation and NOM fractionation have mainly been focused on currently regulated DBPs and a few certain emerging DBPs. In this work, the Suwannee River NOM solution was fractionated into groups with different hydrophobicities using DAX-8 resins, and volatile and semi-volatile DBPs formed during the chlorination, chloramination and ozonation of the NOM fractions were examined by a nontargeted screening of comprehensive two-dimensional gas chromatography-quadrupole mass spectrometry procedure. The results showed that a total of 302 DBPs representing nine chemical classes were detected, of which 266 were possibly newly detected, based on library searching with NIST 08 library (using similarity and reverse values of at least 600 and 700, respectively) and linear retention indices. The characterization of DBP precursors suggests that hydrophobic (HPO) NOM contains the major fraction of precursor for the formation of nitrogenous DBPs (contributing about 60% of the total nitrogenous DBPs) during all three disinfection processes. Much larger amounts of heterocyclic DBPs were formed from the HPO fraction than from the hydrophilic fraction during chlorination. During chloramination and ozonation, 5–15 times more ketones were formed from the hydrophilic fraction than from the HPO fraction. During ozonation, more than twice the amounts of esters and alcohols were formed from the hydrophilic fraction than from the HPO fraction. Three-dimensional excitation-emission matrix spectra suggest that similar to the formation of regulated DBPs, humic acid-like substances are probably the precursors of halogen-containing DBPs. Relatively higher nitrogenous DBPs formation from the HPO fraction might be because of the existence of protein-like materials.

Photosensitized degradation of acetaminophen in natural organic matter solutions: The role of triplet states and oxygen

The photolysis of acetaminophen, a widely used pharmaceutical, in simulated natural organic matter solutions was investigated. The triplet states of natural organic matter (3NOM*) were found to play the dominant role in its photodegradation, while the contributions from hydroxyl radicals and singlet oxygen were negligible. Dissolved oxygen (DO) plays a dual role. From anaerobic to microaerobic (0.5 mg/L DO) conditions, the degradation rate of acetaminophen increased by 4–fold. That suggests the involvement of DO in reactions with the degradation intermediates. With increasing oxygen levels to saturated conditions (26 mg/L DO), the degradation rate became slower, mainly due to DO's quenching effect on 3NOM*. Superoxide radical (O2-) did not react with acetaminophen directly, but possibly quenched the intermediates to reverse the degradation process. The main photochemical pathways were shown to involve phenoxyl radical and N-radical cations, finally yielding hydroxylated derivatives, dimers and nitrosophenol. A reaction mechanism involving 3NOM*, oxygen and O2- is proposed.