Structure Of Natural Organic Matter Research Articles

Macronutrient and PFOS bioavailability manipulated by aeration-driven rhizospheric organic nanocapsular assembly

Ubiquitous presence of the extremely persistent pollutants, per- and polyfluoroalkyl substances, is drawing ever-increasing concerns for their high eco-environmental risks which, however, are insufficiently considered based on the assembly characteristics of those amphiphilic molecules in environment. This study investigated the re-organization and self-assembly of perfluorooctane sulfonate (PFOS) and macronutrient molecules from rhizospheric organic (RhO) matter induced with a common operation of aeration. Atomic force microscopy (AFM) with infrared spectroscopy (IR)-mapping clearly showed that, after aeration and stabilization, RhO nanocapsules (∼ 1000 nm or smaller) with a core of PFOS-protein complexes coated by “lipid-carbohydrate” layers were observed whereas the capsule structure with a lipid core surrounded by “protein-carbohydrate-protein” multilayers was obtained in the absence of PFOS. It is aeration that exerted the disassociation of pristine RhO components, after which the environmental concentration PFOS restructured the self-assembly structure in a conspicuous “disorder-to-order” transition. AFM IR-mapping analysis of faeces combined with quantification of component uptake denoted the decreased ingestion and utilization of both PFOS and proteins compared with lipids and carbohydrates when Daphnia magna were fed with RhO nanocapsules. RhO nanocapsules acted as double-edged swords via simultaneously impeding the bioaccessibility of hazardous PFOS molecules and macronutrient proteins; and the latter might be more significant, which caused a malnutrition status within merely 48 h. Elucidating the assembly structure of natural organic matter and environmental concentration PFOS, the finding of this work could be a crucial supplementation to the high-dose-dependent eco-effect investigations on PFOS.

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.

The estimation of DBPs formation potential depending on the molecular structure of natural organic matter

Objectives:Since natural organic matter(NOM) is generated from an ecosystem, it has various characteristics depending on its origin. Especially, aquatic NOM reduces an efficiency of water treatment system and forms disinfection-by-products(DBPs) as a precursor. In this study, DBP formation potential was estimated according to the molecular structure of NOMs resulted by pyrolysis-gas chromatography-mass spectrometer(py-GC-MS). Methods:Five NOM samples were characterized: Suwannee River NOM(SRNOM), Mississippi River NOM(MRNOM), Nakdong River NOM(NR), NOM in effluent of Jinhae wastewater treatment plant(WP), and NOM in a small stream(SG) in Changwon city. The various analytical instruments were used including TOC analyzer, UV spectrometer, fluorescence spectrometer, and size-exclusion chromatography. After freeze drying of NOMs, molecular structure of samples was identified by py-GC-MS. Results and Discussion:Molecular weights of SRNOM and MRNOM were similar each other (~1400Da). The others(NR,WP,SG) were larger than the SRNOM and MRNOM. Hydrophobicity of the samples followed the order: SRNOM≒MRNOM > NR > WP > SG. Py-GC-MS results showed that SRNOM and MRNOM contain high portion of humic components. Otherwise, NR, WP, SG have protein which is originated from microbials. The DBP formation potential of SRNOM and MRNOM were the highest.Conclusion:This research shows the different characteristics of NOMs originated from different source. The results confirmed that NOM contained high portion of humic components results in the formation of high concentration of DBPs.

Magnetic visible-light activated photocatalyst CuFe2O4/Bi2WO6/mpg-C3N4 for the treatment of natural organic matter

Despite growing interest in research on visible-light-driven photocatalysts, reusable photocatalysts have not been extensively developed for the treatment of natural organic matter (NOM), because such development requires an understanding of the complex NOM structures. In this study, we combined the individual benefits of CuFe2O4, Bi2WO6, and mesoporous graphitic carbon nitride (mpg-C3N4) to prepare a magnetic, visible-light-driven photocatalytic composite, CBC-5, for effectively removing NOM in a short period of time. The degradation mechanisms were further explored at the molecular level through ultra-high-resolution mass spectrometry. Broad light absorbance and charge transmission based on a dual S-scheme pathway allowed CBC-5 to generate multiple active agents, OH (49.7 %), O2− (27.6 %), and h+ (24.8 %), which ultimately led to the removal of 7.9 mgC of NOM per 0.9 g of CBC-5 in 6 h. Humic-like fluorophores were preferentially degraded, followed by the generation of simple phenolic components as by-products. Molecular-level investigation revealed that the NOM structures with high degree of unsaturation and functionalization were preferentially attacked by the radicals. Oxygenic groups were formed upon the oxidation of the unsaturated bonds and the functional groups having a low oxidation state of carbon (OSc) before the degradation of the carboxyl-rich alicyclic molecules. NOM degradation was prioritized in the following order: CHON > CHO > CHOS. Oxidative deamination is attributed to the preferential degradation of N-containing compounds, which are partially transformed to CHO compounds. CHOS compounds enriched with aliphatic organosulfates were recalcitrant to photocatalytic oxidation. Thus, CBC-5 demonstrated convenient magnetic recovery, stable performance, and high recyclability and can be applied as a promising NOM treatment agent.

Chemical Oxidation and Reduction Pathways of Mercury Relevant to Natural Waters: A Review

Mercury (Hg) pollution in the environment is a global issue and the toxicity of mercury depends on its speciation. Chemical redox reactions of mercury in an aquatic environment greatly impact on Hg evasion to the atmosphere and the methylation of mercury in natural waters. Identifying the abiotic redox pathways of mercury relevant to natural waters is important for predicting the transport and fate of Hg in the environment. The objective of this review is to summarize the current state of knowledge on specific redox reactions of mercury relevant to natural waters at a molecular level. The rate constants and factors affecting them, as well as the mechanistic information of these redox pathways, are discussed in detail. Increasing experimental evidence also implied that the structure of natural organic matter (NOM) play an important role in dark Hg(II) reduction, dark Hg(0) oxidation and Hg(II) photoreduction in the aquatic environment. Significant photooxidation pathways of Hg(0) identified are Hg(0) photooxidation by hydroxyl radical (OH•) and by carbonate radical (CO3−•). Future research needs on improving the understanding of Hg redox cycling in natural waters are also proposed.

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water, ozone (O3) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br−). Considering the risk of bromate (BrO3−) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H2O2) and ammonia (NH3) on BrO3− formation during ozonation process were compared. The addition of H2O2 effectively inhibited BrO3− formation at an initial Br− concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H2O2/O3 was 0.25 and > 0.5, respectively. The UV254 and total organic carbon (TOC) also decreased after adding H2O2, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H2O2. To control the formation of both BrO3− and THMs, a relatively large dose of O3 and a high ratio of H2O2/O3were generally needed. NH3 addition inhibited BrO3− formation when the background ammonia nitrogen (NH3N) concentration was low. There was no significant correlation between BrO3− inhibition efficiency and NH3 dose, and a small amount of NH3N (0.2 mg/L) could obviously inhibit BrO3− formation. The oxidation of NOM seemed unaffected by NH3 addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH3. Considering the formation of BrO3− and THMs, the optimal dose of NH3 was suggested to be 0.5 mg/L.

Carbon Budget and Molecular Structure of Natural Organic Matter in Bank Infiltrated Groundwater.

Managed aquifer recharge (MAR) provides means to remove natural organic matter (NOM) from surface waters. Recent studies have explored the degree of NOM removal in groundwater. In this study, we further elaborate the NOM removal at a lakeside natural bank infiltration site that functions as a surrogate for MAR. Our objective was to quantify the carbon budget in the aquifer based on concentration measurements of dissolved (in)organic carbon, and the molecular changes in NOM using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). According to the carbon budget, only 25% of the dissolved carbon entering the aquifer was organic, and it predominantly originated from lake water. Of the inorganic majority, on average 40% was produced in the vadose zone above the groundwater table, 31% in the lake bank, 22% in the aquifer as a result of degrading organic matter of lake water, and 7% in the lake. Seasonal concentration variations suggested that the lake bank was the main carbon source in the summer, increasing the carbon concentration of infiltrating lake water, that is, 3.0mg/L to 7.9mg/L. FT-ICR MS results showed 4960 to 5330 individual compounds in lake and groundwater. NOM removal in the aquifer was selective: the relative abundance of oxygen-containing species decreased from 75 to 31%, while the relative abundance of sulfur-containing species increased from 15 to 57%. The average molecular weights of both species remained unchanged. The study highlighted the role of lake bank processes and sulfur-containing species in groundwater quality.

Molecular characterization of transformation and halogenation of natural organic matter during the UV/chlorine AOP using FT-ICR mass spectrometry

UV/chlorine process, as an emerging advanced oxidation process (AOP), was effective for removing micro-pollutants via various reactive radicals, but it also led to the changes of natural organic matter (NOM) and formation of disinfection byproducts (DBPs). By using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), the transformation of Suwannee River NOM (SRNOM) and the formation of chlorinated DBPs (Cl-DBPs) in the UV/chlorine AOP and subsequent post-chlorination were tracked and compared with dark chlorination. In comparison to dark chlorination, the involvement of ClO•, Cl•, and HO• in the UV/chlorine AOP promoted the transformation of NOM by removing the compounds owning higher aromaticity (AImod) value and DBE (double-bond equivalence)/C ratio and causing the decrease in the proportion of aromatic compounds. Meanwhile, more compounds which contained only C, H, O, N atoms (CHON) were observed after the UV/chlorine AOP compared with dark chlorination via photolysis of organic chloramines or radical reactions. A total of 833 compounds contained C, H, O, Cl atoms (CHOCl) were observed after the UV/chlorine AOP, higher than 789 CHOCl compounds in dark chlorination, and one-chlorine-containing components were the dominant species. The different products from chlorine substitution reactions (SR) and addition reactions (AR) suggested that SR often occurred in the precursors owning higher H/C ratio and AR often occurred in the precursors owning higher aromaticity. Post-chlorination further caused the cleavages of NOM structures into small molecular weight compounds, removed CHON compounds and enhanced the formation of Cl-DBPs. The results provide information about NOM transformation and Cl-DBPs formation at molecular levels in the UV/chlorine AOP.

Change of disinfection byproducts formation potential of natural organic matter after exposure to persulphate and bicarbonate

Activated persulphate (PS) oxidation is a promising in situ remediation technology for groundwater and soils. Application of this technology to contaminated zones may result in a large quantity of PS residue in the subsurface environment due to inefficient activation and repeated injection. In this study, we demonstrated that natural organic matter (NOM) molecules could be reconfigured due to exposure to unactivated PS and bicarbonate, resulting in reduced disinfection byproducts formation potential in post chlorination process. Fourier transformed inferred spectrometry (FTIR), size exclusive chromotraghy (SEC), and mass spectrometry (MS) analysis revealed that hydroxylation and carboxylation of NOM occurred, followed by inter-molecular coupling via ether bonds. The change of both the reactivity toward free chlorine and molecular structure of NOM during PS/bicarbonate treatment was well mimicked by 3,5-dihydroxylbenzoic acid, suggesting that phenolic moieties in NOM molecules were the main sites underwent transformation in the PS/bicarbonate system. We propose that peroxymonocarbonate (HCO4−) formed upon the reaction between PS and bicarbonate was the main reactive species responsible for the reconfiguration of NOM. It selectively attacked the phenolic moieties via single-electron abstracting mechanism, leading to phenoxy radical intermediates which couple to each other via C–O–C bonds. The findings of this study shed light on the environmental behaviors and impacts of PS in groundwater environment.

Application of heat-activated peroxydisulfate pre-oxidation for degrading contaminants and mitigating ultrafiltration membrane fouling in the natural surface water treatment

Membrane fouling is posing a critical obstacle limiting the widespread application of ultrafiltration (UF). Among the numerous membrane foulants, natural organic matter (NOM) is one of the most problematic since it exists ubiquitously in natural waters and can cause severe membrane fouling. This study investigated the removal of NOM in surface water and the mitigation of membrane fouling using heat-activated peroxydisulfate (PDS) as a pretreatment for UF process. The results demonstrated that the NOM was efficiently removed, with ultraviolet absorbance (UV254) and dissolved organic carbon (DOC) decreasing by approximately 71% and 52%, respectively, at a PDS dose of 0.8 mM within 60 min (80 °C). The chromatograms of high performance size exclusion chromatography (HPSEC) indicated that some high molecular weight humic substances with a peak at approximately 10 kDa were oxidized to low molecular weight organic matters distributed in the range of < 100 Da during the pretreatment process. Moreover, three-dimensional fluorescence parallel factor analysis (PARAFAC) indicated that humic-like substances were much more easily degraded by heat-activated PDS pretreatment than protein-like substances. These results indicated that some unsaturated NOM fractions were first degraded and then mineralized to carbon dioxide during pretreatment. Meanwhile, the destroyed structure of humic substances might hinder its binding with high valence cations to reduce the possibility of high valence cations deposited on the membrane surface, thereby reducing membrane fouling. Therefore, membrane fouling could be significantly mitigated due to the shifts of NOM concentration and structure by heat-activated PDS pretreatment in the surface water treatment.

Degradation of acetaminophen in photo-enzyme coupling system with natural organic matters from different sources

Acetaminophen (AAP) is one of the most commonly prescribed over-the-counter drugs with wide distribution in surface water, which has attracted great attention around the world. Photodegradation and enzymatic transformation are important processes for the removal of AAP in water. The influence of natural organic matter (NOM) from different sources on the transformation of AAP by horseradish peroxidase (HRP) in sunlit water was systematically studied. NOM can effectively promote the combined degradation rate of AAP in photo-enzyme coupling system (PECS), and the promotion extents of different NOMs were dependent on their aromaticity and average molecular weights. NOM with low aromaticity and low average molecular weight is more effective. In order to disclose the underlying effects of NOM clearly, the reaction mechanism was clarified through the determination of the photodegradation constant and enzymatic reaction constant. The effect of NOM structure on the photo-enzymatic transformation of AAP was quantified, which showed significant positive correlation with the SUVA254 and E2/E3 of NOM. Further investigation revealed that the amount of H2O2 generated by NOM from different sources was also closely related to SUVA254 and E2/E3 of NOM. The findings will facilitate understanding the environmental fate of AAP and other pharmaceutical products in natural water.

Correlations between slow pyrolysis characteristics and organic carbon structure of aquatic plant biomass.

Thermal analysis techniques have been widely used to characterize natural organic matter; in particular, thermal oxidation has been used to examine soil and sediment organic matter. However, few studies have characterized natural organic matter (NOM) by using slow thermal degradation under a N2 atmosphere. 13C nuclear magnetic resonance (NMR) spectroscopy, UV-Vis spectroscopy, and three-dimensional excitation and emission matrix (EEM) fluorescence spectroscopy were used to characterize aquatic plant biomass for the detailed interpretation of the structures of organic carbon during slow pyrolysis. There was a significant linear correlation between the absorption of heat (99-110°C) and the loss of mass (110-160°C) (r2 = 0.507, p = 0.01), which indicates that the initial slight loss in mass of the plant materials was due to the loss of less thermally stable components. The release of heat (277-311°C) and the ratio of the specific absorbances at 253 and 203nm (A253/203) were also correlated (r2 = 0.388, p = 0.008), which suggests that the release of plant biomass upon heating was associated with the proportion of substituent groups on aromatic rings and that the release of heat increased with the amount of substitution. The coefficient of determination (r2) between fulvic acid-like fluorescence peaks and the loss of mass (230-340°C) was 0.236 (p = 0.048). This result indicates that the loss of mass in the plant material samples was related to fulvic acid-like substances. More specifically, the reason for this result was the splitting of some aromatic functional groups, such as ether bonds, carbonyl groups, and oxygen heterocycles. In conclusion, these results suggest that the developed correlations between slow pyrolysis characteristics and organic carbon structures contribute to the investigation of the inner chemical structures of natural organic matter.

Exploring the complex removal behavior of natural organic matter upon N-doped reduced graphene oxide-activated persulfate via excitation-emission matrix combined with parallel factor analysis and size exclusion chromatography

Metal-free oxidative degradation by persulfate (PS) is an emerging process as green chemistry without any toxic metal leaching to aquatic environments but has never been explored for natural organic matter (NOM) removal to date. In this study, nitrogen-doped reduced graphene oxide (NrGO) was applied as a catalyst first to investigate the degradation behavior of NOM. A parallel system was also examined without PS for non-oxidative interaction. For three tested NOM, the extent of the removal increased with the addition of NrGO, and the removal rates were consistently higher for the systems with versus without PS (by 25–102%). Specific ultraviolet absorbance (SUVA) exhibited declining trends with NrGO for both oxidative and non-oxidative systems. Up to 86.9%, 59.9%, and 60.3% reduction in SUVA values were found for the oxidative removal of Suwannee River natural organic matter, Suwannee River humic acid, and Suwannee River fulvic acid, respectively. The excitation-emission matrix combined with parallel factor analysis (EEM-PARAFAC) decomposed fluorescent NOM into two fulvic-like (C1 and C2) and two humic-like (C3 and C4) components. Results implied that more hydrophobic and more condensed aromatic NOM constituents might be preferably removed by both oxidation and adsorption with the greater removal tendency shown for the humic versus the fulvic-like components. Size exclusion chromatography (SEC) demonstrated that large size molecules were more effectively removed by the oxidative versus the non-oxidative interactions with NrGO. Comparative results revealed that adsorption likely played a critical role in determining the preferential removal tendency of the metal-free oxidation toward heterogeneous NOM structures.

Potential impact of natural organic ligands on the colloidal stability of silver nanoparticles

Interaction of natural organic matter (NOM) with engineered nanoparticles (NPs) determine NP fate, transport, and environmental persistence. However, the effect of NOM chemical composition, structure, and concentration on aggregation kinetics and dissolution behavior of silver nanoparticles (AgNPs) are still poorly understood because of heterogeneity and variability in NOM and AgNP properties. Here, aggregation behavior of citrate-coated silver nanoparticles (cit-AgNPs with a z-average diameter of 18nm) was investigated in the presence of l-cysteine (l-cys) and N-acetyl l-cysteine (NAL-cys) using UV–vis spectroscopy. We also investigated the effect of Suwannee River fulvic acid (SRFA) and a NOM isolated from the Yukon River (YRNOM) on the stability of cit-AgNPs. The dissolution of cit-AgNPs decreased with increased L-cys and NAL-cys concentration from 0 to 10μM. The critical coagulation concentration (CCC) of cit-AgNPs decreased in the presence of l-cys and increased in the presence of NAL-cys. Similarly, l-cys destabilizes cit-AgNPs in the presence of SRFA. The differences in the stability of cit-AgNPs in the presence of l-cys and NAL-cys can be attributed to the differences in the functional groups in these two cysteine molecules. l-cys has both negatively charged carboxylic group and a positively charged amine group, resulting in bridging between different particles. NAL-cys is a derivative of cysteine wherein an acetyl group is attached to the nitrogen atom thus shielding the positive charge on the amine group and therefore eliminating the bridging interaction mechanism. SRFA and YRNOM enhanced the stability of cit-AgNPs and increased the CCC value to higher counter ion concentrations. The concentration of SRFA (1–5mgL−1) did not affect the CCC, whereas the increased concentration of YRNOM increased the CCC of cit-AgNPs to high Na+ concentrations likely due to increased sorption of higher molecular weight compounds on the surface of cit-AgNPs. The outcome of this study suggests the importance of understanding the molecular properties of NOM (e.g. functional groups and molecular weight) in determining cit-AgNP environmental behaviors.

Increased Electron-Accepting and Decreased Electron-Donating Capacities of Soil Humic Substances in Response to Increasing Temperature.

The electron transfer capacities (ETCs) of soil humic substances (HSs) are linked to the type and abundance of redox-active functional moieties in their structure. Natural temperature can affect the chemical structure of natural organic matter by regulating their oxidative transformation and degradation in soil. However, it is unclear if there is a direct correlation between ETC of soil HS and mean annual temperature. In this study, we assess the response of the electron-accepting and -donating capacities (EAC and EDC) of soil HSs to temperature by analyzing HSs extracted from soil set along glacial-interglacial cycles through loess-palaeosol sequences and along natural temperature gradients through latitude and altitude transects. We show that the EAC and EDC of soil HSs increase and decrease, respectively, with increasing temperature. Increased temperature facilitates the prevalence of oxidative degradation and transformation of HS in soils, thus potentially promoting the preferentially oxidative degradation of phenol moieties of HS or the oxidative transformation of electron-donating phenol moieties to electron-accepting quinone moieties in the HS structure. Consequently, the EAC and EDC of HSs in soil increase and decrease, respectively. The results of this study could help to understand biogeochemical processes, wherein the redox functionality of soil organic matter is involved in the context of increasing temperature.

Composition and structure of natural organic matter through advanced nuclear magnetic resonance techniques

Natural organic matter (NOM) plays important roles in biological, chemical, and physical processes within the terrestrial and aquatic ecosystem. Despite its importance, a clear and exhaustive knowledge on NOM chemistry still lacks. Aiming to prove that advanced solid-state 13C nuclear magnetic resonance (NMR) techniques may contribute to fill such a gap, in this paper we reported relevant examples of its applicability to NOM components, such as biomass, deposition material, sediments, and kerogen samples. It is found that nonhydrolyzable organic carbons (NHC), chars, and polymethylene carbons are important in the investigated samples. The structure of each of the NHC fractions is similar to that of kerogens, highlighting the importance of selective preservation of NOM to the kerogen origin in the investigated aquatic ecosystems. Moreover, during the artificial maturation experiments of kerogen, the chemical and structural characteristics such as protonated aromatic, nonprotonated carbons, and aromatic cluster size play important roles in the origin and variation of nanoporosity during kerogen maturation.Graphical abstractNMR parameters of thermally stimulated kerogens

Effects of composition and structure of natural organic matter on phosphorus fractions in sediment from Lake Yangzonghai, Yunnan Province

Effects of composition and structure of natural organic matter on phosphorus fractions in sediment from Lake Yangzonghai, Yunnan Province

Europium (III) and Uranium (VI) complexation by natural organic matter (NOM): Effect of source.

For the safe long-term storage of high-level radioactive waste (HLW), detailed information about geo-chemical behavior of radioactive and toxic metal ions under environmental conditions is important. Natural organic matter (NOM) can play a crucial role in the immobilization or mobilization of these metal ions due to its complexation and colloid formation tendency. In this study, the complexation of europium (as chemical homologue of trivalent actinides such as americium) and uranium (as main component of HLW) by ten humic acids (HA) from different sources and Suwannee NOM river extract has been analyzed. Capillary electrophoresis in combination with inductively coupled plasma mass spectrometry has been used for the evaluation of complex stability constants logβ. In order to determine the complex stability constants a conservative single site model was used in this study. In dependence of their source and thus of NOM structure the log β values for the analyzed humic acids are in the range of 6.1-7.0for Eu(III) and 5.2-6.4 for U(VI) (UO22+ ), respectively. In contrast to the results for HA the used Suwannee river NOM reveals logβ values in the range of nearly two orders of magnitude lower (4.6 for Eu3+ and 4.5 for UO22+ ) under the geochemical conditions applied in this study.

Combined effects of PAC adsorption and in situ chlorination on membrane fouling in a pilot-scale coagulation and ultrafiltration process

The goal of this study was to quantify and demonstrate the combined effects of powdered activated carbon (PAC) adsorption and in situ chlorination on the performance of a coagulation and submersed hollow-fiber ultrafiltration (UF) membrane system at the pilot scale. The real-time levels of natural organic matter (NOM), including dissolved organic carbon (DOC) and trichloromethane formation potential (TCMFP), were quantified to evaluate NOM removal in different hybrid UF systems. The fouling behavior of the UF membranes after combined adsorption pre-treatment and in situ chlorination was systematically investigated in terms of membrane filtration resistance. The results showed that the presence of PAC during the coagulation–flocculation process increased the removal of NOM, particularly the fractions of proteinaceous substances and humic-like substances, as indicated by excitation emission matrix (EEM) spectroscopy, which contributed to the retardation of membrane fouling. In situ chlorination postponed membrane fouling to some extent owing to small modifications to the molecular structure of NOM, which demonstrated that the portion of humic acid (HA) that reacted with sodium hypochlorite penetrated the UF membrane, avoiding adsorption to the membrane pores. Combining adsorption enhancing coagulation pre-treatment and in situ chlorination in the hybrid UF system led to further alleviation of membrane fouling.

Characterization of natural organic matter in bentonite clays for potential use in deep geological repositories for used nuclear fuel

The Nuclear Waste Management Organization (NWMO) is developing a Deep Geological Repository (DGR) to contain and isolate used nuclear fuel in a suitable rock formation at a depth of approximately 500m. The design concept employs a multibarrier system, including the use of copper-coated used fuel containers, surrounded by a low-permeability, swelling clay buffer material within a low permeability, stable host rock environment. The natural organic matter (NOM) composition of the bentonite clays being considered for the buffer material is largely uncharacterized at the molecular-level. To gain a better understanding of the NOM in target clays from Wyoming and Saskatchewan, molecular-level methods (biomarker analysis, solid-state 13C NMR and solution-state 1H nuclear magnetic resonance (NMR)) were used to elucidate the structure and sources of NOM. Organic carbon content in three commercially available bentonites analyzed was low (0.11–0.41%). The aliphatic lipid distribution of the clay samples analyzed showed a predominance of higher concentration of lipids from vascular plants and low concentrations of lipids consistent with microbial origin. The lignin phenol vanillyl acid to aldehyde ratio (Ad/Al) for the National sample indicated an advanced state of lignin oxidation and NOM diagenesis. The 13C NMR spectra were dominated by signals in the aromatic and aliphatic regions. The ratio of alkyl/O-alkyl carbon ranged from 7.6 to 9.7, indicating that the NOM has undergone advanced diagenetic alteration. The absence lignin-derived phenols commonly observed in CuO oxidation extracts from contemporary soils and sediments as well as the lack of amino acids suggests that the material corresponding to the aromatic signal is not composed of lignin or proteins but may be derived from another source such as black carbon or some other non-extractable aromatic-rich NOM. The aliphatic signal appears to correspond to long-chain compounds with little side branching based on the results of the one-dimensional (1D) and two-dimensional (2D) solution-state 1H NMR analyses. Overall, the organic geochemical analyses suggest that the NOM is composed mainly of plant-derived waxes and highly aromatic carbon with low contributions from small molecules. The compounds identified by the molecular-level analysis of NOM in the clay samples are hypothesized to be recalcitrant but future studies should examine if these compounds may serve as a microbial substrate to further test the observations of this study. Furthermore, our study suggests that the NOM has undergone diagenesis and that marine NOM signatures are no longer recognizable or detectable. As such, future work may also examine the diagenesis of these deposits to further understand the NOM geochemistry and paleoenvironmental conditions in bentonite deposits.