Molecular characterization of natural organic matter using complementary liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry techniques.

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

Correlating the chemical and spectroscopic characteristics of natural organic matter with the photodegradation of sulfamerazine

Differences relating to the ability of various types of humic substances (HS) to influence toxicity of pollutants have been reported in the literature, but there still remains a gap in understanding whether various HS will have the same influence on the toxicity of acid mine drainage (AMD). This study investigated differences in the ability of Aldrich humic acid (AHA), Suwannee River humic acid and Suwannee River fulvic acid to decrease toxicity of AMD to the freshwater shrimp (Caridina sp. D). Toxicity tests were conducted over 96 h and used Mount Morgan open pit water as source of AMD and Dee River water as control/diluents. Concentrations of 0-4 % AMD at 0 mg/L HS, 10 mg/L AHA, 10 mg/L Suwannee River humic acid and 10 mg/L Suwannee River fulvic acid were used. Significantly higher survival of shrimp was recorded in the HS treatments compared with the treatment containing no HS. No significant differences were found among HS type. HS considerably increased LC50 values irrespective of type, from 1.29 (0 mg/L HS) to 2.12 % (AHA); 2.19 (Suwannee River humic acid) and 2.22 % (Suwannee River fulvic acid). These results support previous work that HS decrease the toxicity of AMD to freshwater organisms, but with the novel finding that this ability occurs irrespective of HS type. These results increase the stock of knowledge regarding HS and may contribute to a possible remediation option for AMD environments.

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

Natural organic matter (NOM) is ubiquitous in surface water and groundwater and interacts strongly with mineral surfaces. The details of these interactions, as well as their impacts on mineral surface reactivity, are not well understood. In this work, both the reactivity and aggregation of goethite (α-FeOOH) nanoparticles were quantified in the presence of well-characterized humic substances. Results from monitoring the kinetics of reductive degradation of 4-chloronitrobenzene (4-ClNB) by Fe(II) adsorbed onto the goethite nanoparticles with and without added humic substances demonstrates that, in all cases, humic substances suppressed Fe(II)-goethite reactivity. The ranking of the standards from the least to most inhibitive was Pahokee Peat humic acid, Elliot Soil humic acid, Suwannee River humic acid, Suwannee River NOM, Suwannee River fulvic acid I, Suwannee River fulvic acid II, and Pahokee Peat fulvic acid. Correlations between eight characteristics (molecular weight, carboxyl concentration, and carbon, oxygen, nitrogen, aliphatic, heteroaliphatic, and aromatic content) and 4-ClNB degradation rate constants were observed. Faster kinetic rates of reductive degradation were observed with increased molecular weight and nitrogen, carbon, and aromatic content, and slower rates were observed with increased carboxyl concentration and oxygen, heteroaliphatic, and aliphatic content. With these correlations, improved predictions of the reactivity of Fe(II)-goethite with pollutants based on properties of the humic substances are possible.

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

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

Interpreting the effects of natural organic matter on antimicrobial activity of Ag2S nanoparticles with soft particle theory

The aggregation of 12 nm citrate-stabilized gold nanoparticles (cit-AuNPs) in the presence of four different natural organic matter (NOM) isolates and a monovalent electrolyte (KCl) was evaluated using time-resolved dynamic light scattering. All four NOM isolates stabilized the cit-AuNPs with respect to aggregation. However, specific effects varied among the different NOM isolates. At pH = 6 in 80 mM KCl, low concentrations (<0.25 mg C per L) of large molecular weight Suwannee River Humic Acid (SRHA) was required to stabilize cit-AuNPs, while larger concentrations (>2 mg C per L) of smaller Suwannee River Fulvic Acid (SRFA) were necessary at the same ionic strength. Suwannee River NOM (SRNOM) which contains both SRHA and SRFA behaved in a manner intermediate between the two. Pony Lake Fulvic Acid (PLFA), an autochthonous NOM isolate, provided substantial stability at low concentrations, yet aggregation was induced at NOM concentrations > 2 mg C per L, a trend that is hypothesized to be the result of favourable hydrophobic interactions between coated particles induced at increased surface coverage. For all NOM isolates, it appears that NOM adsorption or conformational changes at the AuNP surfaces result in significant increases in the hydrodynamic diameter that aren't attributable to NP-NP aggregation.

Influence of humic substances on the transport of indium and gallium in porous media

Electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been widely used for the characterization of dissolved organic matter (DOM) extracted by solid-phase extraction (SPE) from various environmental waters. It is known that common SPE generally has a relatively low recovery and the non-polar and weakly polar components are less likely to be ionized due to ionization discrimination. However, the molecular selectivity during SPE is not clear so far. In this study, the Suwannee River natural organic matter (SRNOM) was fractionated by multi-step SPE with different solvents and the fractions were characterized by negative ESI FT-ICR MS and trapped ion mobility spectrometry-mass spectrometry (IMS-MS). The sequential solvent elution increased the extraction recovery of DOM in water by SPE and enabled the characterization of a weakly polar component, which cannot be detected in common SPE separation. The weakly polar component accounts for 5.7% in TOC for the SRNOM, which has complex but different molecular composition with methanol- and/or water-eluted fractions. Lipid-like compounds were enriched in this fraction. Compared with the polar molecules directly eluted by one-step SPE from the SRNOM, the weakly polar fractions exhibit larger molecular size. The results are helpful for understanding of the molecular composition of SRNOM, as well as other environmental waters. In addition, the study demonstrates that the combination of FT-ICR MS and IMS-MS has potential to characterize the chemical composition of a complex mixture, like DOM, to a new depth. Graphical abstract.

Sunlight-induced photoformation of silver nanoparticles (nAg), mediated by natural organic matter (NOM), is significantly affected by the concentration of Ag(I) and chloride. The initial photoformation rates of nAg in Suwannee River humic acid (SRHA) and Suwannee River natural organic matter (SRNOM) solutions were examined under simulated sunlight irradiation. A critical induction concentration (CIC) of Ag(I) (10 mg/L for SRHA and 5 mg/L for SRNOM, respectively) was observed, below which the nAg formation was minimal. The threshold is attributed to the interplay of reduction and oxidation reactions mediated by NOM, reflecting the need to achieve sufficiently fast growth of silver clusters to outcompete oxidative dissolution. The CIC can be reduced by scavenging oxidative radicals or be increased by promoting singlet oxygen and hydrogen peroxide generation. The presence of chloride effectively reduced the CIC by forming AgCl, which facilitates reduction reactions and provides deposition surfaces. SRNOM is more efficient in mediating photoformation of nAg than SRHA, owing to their differed phototransient generation. These results highlight prerequisites for the photoformation of nAg mediated by NOM, in which the photochemistry and solution chemistry are both important.

A multifactorial experimental design was employed to quantify and rank the effects of a series of ligands on the rate of Fe(II) (18 microM) oxidation in a system containing chloride, sulfate, carbonate/bicarbonate, fluoride, and natural organic matter (NOM) at pH 8.34 +/- 0.13. Several factors and combinations thereof correlated with the rate of Fe(II) oxidation at the 95% level of confidence. Presented in decreasing order of significance, those factors were carbonate/bicarbonate, NOM, sulfate, chloride, the sulfate/fluoride interaction, and fluoride. The center point of the experimental design was repeated with different organic matters substituted, including Nordic Reservoir NOM, fulvic and humic acids; Suwannee River NOM, fulvic and humic acids; and Pony Lake fulvic acid. Despite the widely differing geographical origins of these organic materials, their overall impact on the oxidation rate of Fe(II) was consistent with the observed rate varying no more than a factor of 2 as a function of different organic matters (on a milligrams of carbon per liter basis). The utility of the pentafactorial response surface model (based on Nordic Lake NOM) to predict Fe(II) oxidation rates was evaluated for different natural water samples, including two seawater and one freshwater.

The fate of estrogenic compounds in the aquatic environment: sorption onto organic colloids

Partitioning of dissolved organic matter-bound mercury between a hydrophobic surface and polysulfide-rubber polymer