Natural Organic Matter Complexes Research Articles

Methane emissions and the microbial community in flooded paddies affected by the application of Fe-stabilized natural organic matter

Redox chemistry involving the quinone/phenol cycling of natural organic matter (NOM) is known to modulate microbial respiration. Complexation with metals or minerals can also affect NOM solubilization and stability. Inspired by these natural phenomena, a new soil amendment approach was suggested to effectively decrease methane emissions in flooded rice paddies. Structurally stable forms of NOM such as lignin and humic acids (HAs) were shown to decrease methane gas emissions in a vial experiment using different soil types and rice straw as a methanogenic substrate, and this inhibitory behavior was likely enhanced by ferric ion–NOM complexation. A mechanistic study using HAs revealed that complexation facilitated the slow release of the humic components. Interestingly, borohydride-based reduction, which transformed quinone moieties into phenols, caused the HAs to lose their inhibitory capacity, suggesting that the electron-accepting ability of HAs is vital for their inhibitory effect. In rice field tests, the humic–metal complexes were shown to successfully mitigate methane generation, while carbon dioxide emissions were relatively unchanged. Microbial community analysis of the rice fields by season revealed a decrease in specific cellulose-metabolizing and methanogenic genera associated with methane emissions. In contrast, the relative abundance of Thaumarchaeota and Actinomycetota, which are associated with NOM and recalcitrant organics, was higher in the presence of Fe-stabilized HAs. These microbial dynamics suggest that the slow release of humic components is effective in modulating the anoxic soil microbiome, possibly due to their electron-accepting ability. Given the simplicity, cost-effectiveness, and soil-friendly nature of complexation processes, Fe-stabilized NOM represents a promising approach for the mitigation of methane emissions from flooded rice paddies.

Improved Dynamic Range, Resolving Power, and Sensitivity Achievable with FT-ICR Mass Spectrometry at 21 T Reveals the Hidden Complexity of Natural Organic Matter.

Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) is the only mass analyzer that can resolve the molecular complexity of natural organic matter at the level of elemental composition assignment. Here, we leverage the high dynamic range, resolving power, resistance to peak coalescence, and maximum ion number and ion trapping duration in a custom built, 21 tesla hybrid linear ion trap /FT-ICR mass spectrometer for a dissolved organic matter standard (Suwanne River Fulvic Acid). We compare the effect of peak-picking threshold (3σ, 4σ, 5σ, and 6σ) on number of elemental composition assignments, mass measurement accuracy, and dynamic range for a 6.3 s transient across the mass range of m/z 200-1200 that comprises the highest achieved resolving power broadband FT-ICR mass spectrum collected to date. More than 36 000 species are assigned with signal magnitude greater than 3σ at root-mean-square mass error of 36 ppb, the most species identified reported to date for dissolved organic matter. We identify 18O and 17O isotopologues and resolve isobaric overlaps on the order of a few electrons across a wide mass range (up to m/z 1000) leveraging mass resolving powers (3 000 000 at m/z 200) only achievable by 21 T FT-ICR MS and increased by ∼30% through absorption mode data processing. Elemental compositions unique to the 3σ span a wide compositional range of aromaticity not detected at higher peak-picking thresholds. Furthermore, we leverage the high dynamic range at 21 T FT-ICR MS to provide a molecular catalogue of a widely utilized reference standard (SRFA) to the analytical community collected on the highest performing mass analyzer for complex mixture analysis to date. This instrument is available free of charge to scientists worldwide.

Data-Based Chemical Class Regions for Van Krevelen Diagrams.

Ultrahigh resolution mass spectrometry (UHR-MS) is commonly used to characterize natural organic matter (NOM). The complexity of both NOM and the data set produced make data visualization challenging. Van Krevelen diagrams─plots of component hydrogen/carbon (H/C) against oxygen/carbon (O/C) elemental ratios─have become a popular way to visualize the chemical formulas identified by UHR-MS. Different regions on the van Krevelen diagram have been attributed to different chemical classes; however, the classifications vary between studies and the regions lack standard definitions. Here, chemical formulas were obtained from public databases to create H/C and O/C ranges for amino sugar, carbohydrate, lignin, lipid, peptide, and tannin chemical classes on van Krevelen diagrams. The recommended H/C and O/C ranges are presented in a table and can be adapted to any data analysis software programs. The regions recommended here agreed reasonably well with previous literature for amino sugar, carbohydrate, lignin, lipid, and peptide regions. However, the recommended tannin region appears at lower H/C ratio values and with a wider range of O/C ratio values compared to previous studies. The regions presented herein are strongly recommended for use as consistent reference points in future NOM characterization studies to aid in the discussion of data and to readily compare studies.

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).

Labilization and diversification of pyrogenic dissolved organic matter by microbes

Abstract. With the increased occurrence of forest fires around the world, interest in the chemistry of pyrogenic organic matter (pyOM) and its fate in the environment has increased. Upon leaching from soils by rain events, significant amounts of dissolved pyOM (pyDOM) enter the aquatic environment and interact with microbial communities that are essential for cycling organic matter within the different biogeochemical cycles. To evaluate the bio-reactivity of pyDOM, aqueous extracts of laboratory-produced chars were incubated with soil microbes and the molecular changes to the composition of pyDOM were probed using ultrahigh resolution mass spectrometry (Fourier transform – ion cyclotron resonance – mass spectrometry). Given that photo-degradation also affects the composition and reactivity of pyDOM during terrigenous-to-marine export, the effects of photochemistry were also evaluated in the context of the bio-reactivity of pyDOM. Ultrahigh resolution mass spectrometry revealed that, after incubation, many different (both aromatic and aliphatic) compounds were degraded, and new labile compounds, 22–40 % of which were peptide-like, were produced. This indicated that a portion of pyDOM has been labilized into microbial biomass during the incubations. Fluorescence excitation-emission matrix spectra revealed that some fraction of these new molecules is associated with fluorophores from proteinaceous and/or autochthonous/microbial biomass origin. Two-dimensional 1H-1H total correlation NMR spectroscopy identified a peptidoglycan-like backbone within the microbially produced compounds. These results are consistent with previous observations of nitrogen from peptidoglycans within the soil and ocean nitrogen cycles. Interestingly, the exact nature of the bio-produced organic matter was found to vary drastically among samples indicating that the used microbial consortium may produce different exudates based on the composition of the initial pyDOM. Another potential explanation for the vast diversity of molecules is that microbes only consume low molecular weight compounds, but they also produce reactive oxygen species (ROS), which initiate oxidative and recombination reactions that produce new molecules. The observed microbially-mediated diversification of pyDOM suggests that pyDOM contributes to the observed large complexity of natural organic matter. More broadly, pyDOM can be substrate for microbial growth and be incorporated in environmental food webs.

Geochemical Controls on Release and Speciation of Fe(II) and Mn(II) From Hyporheic Sediments of East River, Colorado

Hyporheic zones act as critical ecological links between terrestrial and aquatic systems where redox-sensitive metals of iron (Fe) and manganese (Mn) significantly impact nutrient cycling and water quality. However, the geochemical controls on the release and speciation of Fe(II) and Mn(II) in these biogeochemical hotspots are still poorly understood. Here we conducted batch incubation experiments and analyzed Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy data using sediment samples from a hyporheic zone of the East River floodplain in Colorado to understand the production, release and speciation of Fe(II) and Mn(II) in groundwater. Our results indicate that the production and release of Fe(II) and Mn(II) vary with sediment reducing conditions and subsurface positions, and the rates were determined either by a zero- or first-order rate equation. The sediments with higher Fe(II) production did not necessarily result in higher release of dissolved Fe(II), and ≥97% Fe(II) is accumulated in solid phase. We found that the majority of Fe(II) exists as siderite (FeCO3), Fe(II)-natural organic matter (NOM) complexes and ferrosmectite, and the equilibrium concentrations of dissolved Fe(II) are controlled primarily by siderite solubility, and enhanced greatly by formation of strong Fe(II)-NOM complexes as dominant aqueous Fe(II) species. By contract, dissolved Mn(II) increases slowly and linearly, and an equilibrium concentration was not reached during the incubation period, and the roles of rhodochrosite (MnCO3) and Mn(II)-NOM complexes are insignificant. Furthermore, we reviewed and calibrated the literature reported binding constants (log K) of Fe(II)-NOM complexes which successfully predicted our experimental data. This work reveals that siderite and dissolved NOM are the controlling phases in release and speciation of dissolved Fe(II), and the finding is expected to be applicable in many hyporheic zones and subsurface environments with similar geochemical conditions.

A feasible strategy to improve confident elemental composition determination of compounds in complex organic mixture such as natural organic matter by FTICR-MS without internal calibration

Confident elemental composition determination of compounds in complex samples such as natural organic matter (NOM) by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is challenging due to the interference between multiple components in these samples during detection. Here the performance of Solarix 15T-FTICR-MS in terms of accurate relative natural isotope abundance (RIA) and mass measurements for elemental composition determination of compounds in complex samples such as NOM was systematically evaluated. The optimal sweep excitation power values ranging from 20% to 22% was found to significantly diminish the underestimation of RIA measurement for 13C1 peaks of NOM components by FTICR-MS. Random error was found to be one of the main sources for the RIA errors of 13C1 peaks with S/N ratios <25. The mean averaged RIA errors of less than 10% could be obtained by averaging the measured RIAs of each 13C1 peaks in five replicated runs. By adjusting the total ion abundance of NOM complex sample between 3.8-E7 and 1.4-E8 which was simultaneously similar to that of external calibrant during detection, mass errors of lower than 1 ppm for NOM components with m/z lower than 700 Da could be obtained without internal calibration. Meanwhile, a linear correlation between mass errors of ions in NOM complex sample and their m/z values could be obtained. The mass error deviation derived from the linearity was firstly used as new criterion to reduce the number of false formula candidates. A novel strategy of combination of high mass accuracy, high spectral accuracy, and mass error deviation for elemental composition determination of unknown compounds in complex sample such as NOM by FTICR-MS was proposed and applied for different complex samples. Compared to the traditional method, about one fold increasement in the number of the unique formula assignments for measured ions was obtained by using our strategy.

Impact of different modes of adsorption of natural organic matter on the environmental fate of nanoplastics

Recently, the exposure of nanoplastics (NPs) in the environment has received extensive attention. Research concerning their fate and transport in the aquatic environment is very important and urgent. In this study, the influence of two sources of natural organic matter (NOM) on the behaviour of NPs were investigated in view of the complexity of NOM. Humic acid (HA), Suwannee River humic acid (SRHA) and Upper Mississippi River NOM (MRNOM) were chosen to represent pedogenic NOM, while bovine serum albumin (BSA) was on behalf of aquagenic NOM. The results showed that NOM could reduce the aggregation and sedimentation of NPs, exhibiting excellent stabilization effect. The stability effect was affected by the concentrations and the sources of NOMs. For pedogenic NOMs, the stabilization effect was caused by adsorption modes with different microscopic morphologies through specific functional groups, while it was induced by the mode of steric stabilization in the presence of BSA. Spectroscopic method and micromorphology study further provided a new insight into exploring the possible mechanism of the interaction between NPs and NOMs.

Evaluating the transport of Hg(II) in the presence of natural organic matter through a diffusive gradient in a thin-film passive sampler

The effects of a model natural organic matter (NOM) on the transport of Hg(II) into diffusive gradient in thin-film devices (DGTs) was evaluated in order to better understand their ability to measure colloidal Hg species in porewater. The presence of NOM significantly reduced the diffusivity of the Hg(II) species and the reduction was dependent upon NOM to Hg(II) ratio. This relationship was modeled by determining the Hg(II) partition coefficients (Kd) of size fractionated NOM obtained by ultrafiltration and estimating the Hg diffusivity through the DGT for the different NOM size fractions across a range of Hg-NOM ratios. The estimated diffusivities were consistent with experimental observations of uptake into the DGT. Overall, this study indicated that Hg(II) associated with NOM passes into a DGT, however the transport is slowed in accordance with the diffusivity of the NOM to which the Hg(II) is associated. Thus, the Hg—NOM association and complex diffusivities need to be considered when relating DGT uptake to Hg porewater concentration. The results also suggest that Hg(II) associated with colloidal or larger particles of negligible diffusivity are unlikely to contribute significantly to DGT measurements.

Effects of fulvic acids on the electrochemical reactions and mass transfer properties of organic cation toluidine blue: Results of measurements by the method of rotating ring-disc electrode

This study examined effects of aquatic and soil natural organic matter (NOM) exemplified by standard Suwannee River fulvic acid (SRFA) and Pahokee Peat fulvic acid (PPFA), respectively, on the electrochemical (EC) reactivity and mass transfer properties of the cationic organic probe toluidine blue (TB) that forms complexes with NOM. EC measurements that were carried out using the method of rotating ring-disc electrode (RRDE) showed that for disc potentials below −0.4 V vs. the standard Ag/AgCl reference electrode, TB molecules undergo EC reduction accompanied by the formation of EC-active products that undergo oxidation at the ring electrode. EC reactions of TB in the range of potentials −0.2 to −0.4 V were determined to involve free TB+ cations and TB species adsorbed on the electrode surface. The EC reduction of TB species at the disc potentials < −0.4 V was controlled by the mass transfer of the free TB+ cations and TB/NOM complexes to the electrode surface. Formation of TB/NOM complexes caused the mass transfer-controlled TB currents to undergo a consistent decrease. The observed changes were correlated with the extent of TB/NOM complexation and decreases of the diffusion coefficients of TB/NOM complexes that have higher molecular weights (MW) than the free cations. Properties of the intermediates formed upon the reduction of TB+ cations were also affected by NOM. These results demonstrate that RRDE measurements of EC reactions of TB or possibly other EC active probes allow probing the complexation of EC-active organic species with NOM and mass transfer properties of NOM complexes and ultimately NOM itself.

Decomplexation of Cu(II)-natural organic matter complex by non-thermal plasma oxidation: Process and mechanisms

Heavy metals and natural organic matters (NOM) form very stable heavy metal-NOM complexes in aqueous, facilitating the migration of heavy metals and enhancing their potential risks. In this study, non-thermal plasma oxidation was attempted to destroy the heavy metal-NOM complexes, with Cu-humate (Cu-HA) as a model. The decomplexation efficiency reached 86.1 % within 50 min of plasma oxidation at 16 kV. The generated reactive species by the non-thermal plasma, including O2−, 1O2, OH, attacked the carboxyl and hydroxyl functional groups of HA, leading to cleavage of the Cu-O bonds, decomplexation of Cu-HA, and release of free Cu(II). Meanwhile, a variety of small molecular intermediates, including phenols, benzoic acids, esters, amines, ketones, acetic acid, formic acid, and oxalic acid, were generated due to attack by the oxidative species on the aromatic moiety and double bonds in Cu-HA. As a consequence of decomplexation, the residual toxicity of Cu-HA to Scenedesmus obliquus was distinctly reduced. This study provides a potential technique to decomplex heavy metal-NOM complexes, and reduces their toxicity to typical Scenedesmus obliquus.

Impact of phosphate, silicate and natural organic matter on the size of Fe(III) precipitates and arsenate co-precipitation efficiency in calcium containing water

Removal of arsenic (As) from water by co-precipitation with Fe(III) (oxyhydr)oxides is a widely used technique in water treatment. Nevertheless, As removal efficiency appears to be sensitive to the composition of the water matrix. The aim of this study was to gain a deeper understanding of the independent and combined effects of silicate (Si), phosphate (P), natural organic matter (NOM) and calcium (Ca) on arsenate [As(V)] co-precipitation efficiency and the size of Fe(III) precipitates. We found that, in complex solutions, containing multiple solutes and high levels of Ca, (variations in) Si and P concentrations reduce As(V) removal to some extent, mainly due to a decreased adsorption of As(V) onto Fe(III) precipitates. On the other hand, NOM concentrations reduced As(V) removal to a much greater extent, due to possible formation of mobile Fe(III)–NOM complexes that were difficult to remove by filtration. These findings have a great significance for predicting As(V) removal as a function of seasonal and process-related water quality changes at water treatment plants.

Interactions between Organic Model Compounds and Ion Exchange Resins.

Ion exchange (IEX) can successfully remove natural organic matter (NOM) from surface water. However, the removal mechanism is not well understood due to the complexity and variability of NOM in real source waters as well as the influence of multiple parameters on the removal behavior. For example, this includes the physicochemical properties of the NOM and IEX resin, and the presence of competing anions. Model compounds with a range of physical and chemical characteristics were therefore used to determine the mechanisms of NOM removal by IEX resins. Fifteen model compounds were selected to evaluate the influence of hydrophobicity, size, and charge of organic molecules on the removal by ion exchange, both individually and in mixtures. Three different resins, comprising polystyrene and polyacrylic resin of macroporous and gellular structure, showed that charge density (CD) was the most important characteristic that controlled the removal, with CD of >5 mequiv mgDOC-1 resulting in high removal (≥89%). Size exclusion of compounds with high MW (≥8 kDa) was evident. The hydrophobicity of the resin and model compound was particularly important for removal of neutral molecules such as resorcinol, which was best removed by the more hydrophobic polystyrene resin. Relationships were identified that provided explanations of the interactions observed between NOM and IEX resin in real waters.

Geochemical scaling potential simulations of natural organic matter complexation with metal ions in cooling water at Eskom power generation plants in South Africa

The modified database in the pH, redox equilibrium calculations code (PHREEQC) with a Tipping and Hurley database (T_H.DAT) coupled with the Windermere’s humic acid model (WHAM) was used to simulate scale formation potential in cooling water circuitry, at Eskom power generating stations in South Africa. This study reports a semi-empirical simulative approach in which organic matter fractions, metals and anions in raw and cooling water were used as modelling experimental inputs. By using the saturation index profiles of Ca2+/ Mg2+ with fulvic acid in a modified Tipping and Hurley (T_H.DAT) database, fulvate complex species such as CaFulvate, MgFulvate, and geochemical modelling predictions, mineral phases that potentially precipitate are discussed. Speciation calculations showed that the increase in fulvic acid levels decreased saturation indices of scaling metal phases due to reduced levels of Ca2+ and Mg2+ in the water. Furthermore, if the concentrations of fulvic acid are known, semi-empirical calculations using the geochemical PHREEQC code with a modified T_H.DAT arepossible. Consequently, mineral phase equilibria outputs may give an indication of how the pH and temperature is to be manipulated to optimally predict and control the incidence of scaling.

Thermodynamics of Hg(II) Bonding to Thiol Groups in Suwannee River Natural Organic Matter Resolved by Competitive Ligand Exchange, Hg LIII-Edge EXAFS and 1H NMR Spectroscopy.

A molecular level understanding of the thermodynamics and kinetics of the chemical bonding between mercury, Hg(II), and natural organic matter (NOM) associated thiol functional groups (NOM-RSH) is required if bioavailability and transformation processes of Hg in the environment are to be fully understood. This study provides the thermodynamic stability of the Hg(NOM-RS)2 structure using a robust method in which cysteine (Cys) served as a competing ligand to NOM (Suwannee River 2R101N sample) associated RSH groups. The concentration of the latter was quantified to be 7.5 ± 0.4 μmol g-1 NOM by Hg LIII-edge EXAFS spectroscopy. The Hg(Cys)2 molecule concentration in chemical equilibrium with the Hg(II)-NOM complexes was directly determined by HPLC-ICPMS and losses of free Cys due to secondary reactions with NOM was accounted for in experiments using 1H NMR spectroscopy and 13C isotope labeled Cys. The log K ± SD for the formation of the Hg(NOM-RS)2 molecular structure, Hg2+ + 2NOM-RS- = Hg(NOM-RS)2, and for the Hg(Cys)(NOM-RS) mixed complex, Hg2+ + Cys- + NOM-RS- = Hg(Cys)(NOM-RS), were determined to be 40.0 ± 0.2 and 38.5 ± 0.2, respectively, at pH 3.0. The magnitude of these constants was further confirmed by 1H NMR spectroscopy and the Hg(NOM-RS)2 structure was verified by Hg LIII-edge EXAFS spectroscopy. An important finding is that the thermodynamic stabilities of the complexes Hg(NOM-RS)2, Hg(Cys)(NOM-RS) and Hg(Cys)2 are very similar in magnitude at pH values <7, when all thiol groups are protonated. Together with data on 15 low molecular mass (LMM) thiols, as determined by the same method ( Liem-Ngyuen et al. Thermodynamic stability of mercury(II) complexes formed with environmentally relevant low-molecular-mass thiols studied by competing ligand exchange and density functional theory . Environ. Chem. 2017 , 14 , ( 4 ), 243 - 253 .), the constants for Hg(NOM-RS)2 and Hg(Cys)(NOM-RS) represent an internally consistent thermodynamic data set that we recommend is used in studies where the chemical speciation of Hg(II) is determined in the presence of NOM and LMM thiols.

A novel photodegradation approach for the efficient removal of natural organic matter (NOM) from water

The presence of natural organic matter (NOM) in water can negatively affect water quality if NOM is present in excessive amounts during certain stages of water treatment. It is known that NOM constituents serve as precursors for DBPs (disinfection by-products) during the disinfection step of the water treatment process. Removal of natural organic matter (NOM) before disinfection is therefore essential to control DBP formation; however, owing to the heterogeneity and complexity of NOM, most water treatment processes are unable to attain complete removal of NOM from water sources. There is therefore a great need to develop methods that can effectively degrade NOM into smaller and relatively harmless compounds that are easily removed during water treatment processes. In this study, multi-walled carbon nanotubes/nitrogen, palladium co-doped titanium dioxide (MWCNT/N, Pd co-doped TiO2) (0.5–5% MWCNTs) were fabricated for the enhancement of NOM degradation under visible-light illumination. Different MWCNT/N, Pd co-doped TiO2 (also referred to as CT) nanocomposites were synthesised via a modified sol-gel method and characterised using ultraviolet visible (UV-Vis), X-ray diffraction spectroscopy (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) Spectroscopy and energy-dispersive X-ray spectroscopy (EDS) analysis. The UV-Vis results showed that introducing the MWCNTs on the nanocomposites was accompanied by a red shift, with CT (0.5% MWCNTs) occurring at a longer wavelength than the others. The efficiency and effectiveness of the synthesised nanocomposites was quantified through measuring the NOM degradation rate in raw water samples collected from two South African water treatment plants. These two drinking water treatment plants were selected as the raw water treated in these plants contains different NOM fractions: the raw water treated at Midvaal (MV) Water Company contains transphilic NOM fractions, while that treated at Plettenberg Bay (P) Water Treatment Plant contains high amounts of hydrophobic NOM. The changes in the amount of NOM in a sample were monitored by measuring the UV absorbance at 254 nm (UVA254) as there is a strong correlation between absorbance at this wavelength and the aromatic content. The highest photocatalytic activity was observed with CT (0.5% MWCNTs) which attained 69.4% UVA254 reduction for MV and 97.7% UVA254 reduction for P raw waters. Compared to conventional methods applied by the two water treatment plants of interest, NOM removal efficiency (in terms of UVA254 reduction) by CT (0.5% MWCNTs) increased by up to 9.4% and 11.5% for MV and P water treatment plants, respectively. The enhanced photocatalytic activity of this CT nanocomposite (0.5% MWCNTs) is attributable to the large surface area of the synthesised nanocomposites which allows huge amounts of NOM to be adsorbed onto the surface of the TiO2, thereby increasing their photodegradation. It is also due to the synergistic effect of N and Pd which enhanced the photoactivity of the TiO2 in the MWCNT/N, Pd co-doped TiO2 composite. Overall, it is clear that the use of the conventional processes is not effective in removing NOM from water. Findings obtained show that CT (0.5% MWCNTs) nanocomposite is a promising future NOM removal method that could complement the available water treatment processes in enhancing the removal of the aromatic component of NOM in water.

Effects of natural organic matter with different properties on levofloxacin adsorption to goethite: Experiments and modeling

Adsorption of levofloxacin (LEV) to goethite in the pH range of 3–10, and in the absence or presence of natural organic matter (NOM) represented by nine types of humic acid (HA) and fulvic acid (FA), was studied using batch experiments. The adsorption of LEV to goethite was weak and showed a maximum around pH 5.8. Adding NOM to goethite strongly increased LEV adsorption to goethite, but hardly affected its pH dependency. The adsorption envelopes were well fitted to a linear additive model, in which LEV adsorption to goethite was simulated with the Charge Distribution Multi-Site Complexation (CD-MUSIC) model, and LEV adsorption to NOM was simulated with the Langmuir model. The fitted affinity constants (log K) for LEV adsorption to NOM were significantly and positively correlated with the SUVA (specific ultraviolet absorbance at 280 nm) values of NOM, and negatively correlated with E2/E3 (absorbance ratio at 250 nm and 365 nm) values, carboxyl contents, and the polarity of NOM. The results indicated that aromatic moieties of NOM play a key role in the interactions between LEV and NOM, and hydrophobic interactions and π-π interactions were the major mechanisms for LEV adsorption to NOM, whereas H-bond or surface complexation might not play an important role. Results show that both the concentrations and properties of NOM have a significant effect on the distribution or treatment of antibiotics in soils and waters, which will eventually affect the influence of antibiotics on microorganisms in the environmental systems.

Application of graphene oxide membranes for removal of natural organic matter from water

Changes in the complexity of natural organic matter (NOM) have impacted the performance of direct filtration plants of water industries, resulting in reduced treatment capacity, and can lead to increased disinfection by-products. Hence, the need to identify new materials in future can be converted into more effective technologies and processes. We report a laboratory scale innovative use of graphene oxide membranes to remove NOMs from water that had been treated and still contained 5 mg/L DOC. Our study shows that graphene oxide based membranes can reject ∼100% of NOM while maintaining high water flux of 65 L m−2 h−1 bar−1 at atmospheric pressure. Our results indicate that it is possible to develop a graphene oxide-based water filtration technology.

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.

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0–835ppm) or Suwanee River Fulvic Acid (SRFA) (0–955ppm). No evidence was found for reduction of uranyl by either form of NOM after 24h of exposure. The following three size fractions were considered in this study: (1) ≥0.2μm (Fh–NOM aggregates), (2) 0.02–0.2μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh–NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl–Fh–NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0–500ppm); at the highest NOM concentrations (500–955ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII–edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh–NOM aggregates. In the absence of NOM, uranyl formed dominantly inner–sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the proportion of uranyl–Fh inner-sphere sorption complexes decreased relative to uranyl–ESHA or uranyl–SRFA complexes, which comprised up to ∼60% of the total uranyl in the systems studied. At pH 7.0, uranyl–NOM complexes were also present in the Fh–NOM aggregates in the concentration ranges of ESHA or SRFA considered; however, the proportion of these complexes was smaller at pH 7.0 than at pH 4.6 and did not increase significantly with increasing NOM concentration.