Microcystin-LR (MC-LR), one of the most common cyanotoxins, is produced by harmful cyanobacteria. The current study focuses on the photosensitized transformation of MC-LR in dissolved organic matter (DOM) enriched solutions under solar simulated irradiation. It appears that the direct energy transfer of triplet excited state DOM with MC-LR plays a key role and leads to photosensitized isomerization of Adda side chain. Furthermore a micro-heterogeneous mechanism has been proposed. Size exclude chromatograph (SEC) has been applied to explore the adsorption of MC-LR on the DOM. The adsorption phenomenon supported the fact that the pseudo first-order photodegradation rates showed positive correlation with the adsorption. The photo-transformation rate of MC-LR increases as pH decreases which is also the result of the adsorptive interaction of MC-LR with DOM. Finally two bulk water parameters (TOC and UV350 nm) have been applied to predict the photodegradation rates of MC-LR in the varied water matrixes.

Binding of polycyclic aromatic hydrocarbons (PAHs) to dissolved organic matter (DOM) can reduce the freely dissolved concentration, increase apparent solubility or enhance diffusive mass transfer. To study the effects of DOM on biodegradation, we used phenanthrene and pyrene as model PAHs, soil humic acids as model DOM and a soil Mycobacterium strain as a representative degrader organism. Humic acids enhanced the biodegradation of pyrene when present as solid crystals but not when initially dissolved or provided by partitioning from a polymer. Synchronous fluorescence spectrophotometry, scintillation counting and a microscale diffusion technique were applied in order to determine the kinetics of dissolution and diffusive mass transfer of pyrene. We suggest that humic acids can enhance or inhibit biodegradation as a result of the balance of two opposite effects, namely, solubilization of the chemicals on the one hand and inhibition of cell adhesion to the pollutant source on the other.

This work investigated the binding behavior of phenanthrene by humic acids (HA-2 and HA-5), proteins (bovine serum albumin (BSA)), lysozyme and pepsin), and their complexes using a passive dosing technique. All sorption isotherms were fitted well with Freundlich model and the binding capability followed an order of HA-5 > HA-2 > BSA > pepsin > lysozyme. In NaCl solution, phenanthrene binding to HA-BSA complexes was much higher than the sum of binding to individual HA and BSA, while there was no enhancement for HA-pepsin. Positively charged lysozyme slightly lowered phenanthrene binding on both HAs due to strong aggregation of HA-lysozyme complexes, leading to reduction in the number of binding sites. The binding enhancement by HA-BSA was observed under all tested ion species and ionic strengths. This enhancement can be explained by unfolding of protein, reduction of aggregate size and formation of HA-BSA complexes with favorable conformations for binding phenanthrene.

Dissolved organic matter (DOM) may alter the sorption of hydrophobic organic contaminants (HOC) to metal oxide nanoparticles (NPs), but the role of DOM and NP types is poorly understood. Here, phenanthrene sorption was quantified on four types of nano-TiO2 (three rutile, one anatase), and a bulk, raw TiO2 powder. Prior to the sorption experiments, these nanoparticles were coated using four different organic materials: Lignin (LIG), tannic acid (TAN), Congo red (CON), and capsorubin (CAP). Lignin, tannic acid, congo red and capsorubin coating substantially enhanced phenanthrene sorption to various TiO2 particles. After coating with a specific DOM, Kd values by the DOM-coated TiO2 particles on percent organic carbon content and surface area (SA) basis (Koc/SA) generally followed the order: TiO2 NPs with hydrophobic surfaces > bulk TiO2 particles > other TiO2 NPs. Different Koc/SA values of various DOM-TiO2 complexes resulted from distinct conformation of the coated DOM and aggregation.

Modeling oil biodegradation is an important step in predicting the long term fate of oil on beaches. Unfortunately, existing models do not account mechanistically for environmental factors, such as pore water nutrient concentration, affecting oil biodegradation, rather in an empirical way. We present herein a numerical model, BIOB, to simulate the biodegradation of insoluble attached hydrocarbon. The model was used to simulate an experimental oil spill on a sand beach. The biodegradation kinetic parameters were estimated by fitting the model to the experimental data of alkanes and aromatics. It was found that parameter values are comparable to their counterparts for the biodegradation of dissolved organic matter. The biodegradation of aromatics was highly affected by the decay of aromatic biomass, probably due to its low growth rate. Numerical simulations revealed that the biodegradation rate increases by 3–4 folds when the nutrient concentration is increased from 0.2 to 2.0mgN/L.

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state 13C nuclear magnetic resonance (13C NMR) was used to quantitatively evaluate the compositions and constituents of DOM, which are compared with previous investigations on marine DOM. Results indicated that concentration factor (CF) was a key metric controlling yield and sorption of DOM on the RO system. The sorption was likely non-selective, based on the 13C NMR and δ13C analyses. Carbohydrates and lipids accounted for 25.0–41.5% and 30.2–46.3% of the identifiable DOM, followed by proteins (18.2–19.8%) and lignin (7.17–12.8%). The freshwater DOM contained much higher alkyl and aromatic C but lower alkoxyl and carboxyl C than marine DOM. The structural difference was not completely accounted for by using structure of high molecular weight (HMW) DOM, suggesting a size change involved in transformations of DOM during the transport from rivers to oceans.

The adsorption of microcystin-LR (MCLR) by biochar has never been well understood. For the first time, the unconventional adsorption of hydrophilic MCLR on wood-based biochars was comprehensively investigated as a function of biochar properties, environmental temperature, solution pH, coexisting dissolved organic matter (DOM), and polar organic competitors. High-temperature-prepared biochar from 700 °C (BC-700) and low-temperature-prepared biochar from 300 °C (BC-300) were characterized with significantly different surface areas but similar alkaline nature. Despite a very low surface area, BC-300 exhibited very high adsorption capacity, which implies the important contribution of surface groups to biochar. MCLR adsorption on biochars was pH dependent and was strongly reduced by macromolecular DOM. Polycarboxylic aliphatic acids and 2-(2-hydroxyethyl) guanidinium cation, which are similar to specific structural groups in MCLR, exhibited an evident competitive effect. The results indicated that both carboxylic and guanidino groups of MCLR serve significant functions in MCLR adsorption to biochar. The adsorption mechanisms may be primarily related to the columbic attractions and the hydrogen bonding interactions between MCLR and biochar surface. In particular, the irreversible adsorption enhancement of MCLR was observed on BC-700, which suggests that biochar amendment can aid in immobilizing MCLR from water to sediment, thereby prolonging MCLR environmental fate in biochar-amended sediment.

This study systematically investigated the interactive effects of dissolved organic matter (DOM) and biosurfactant (rhamnolipid) on the biodegradation of phenanthrene (PHE) and pyrene (PYR) in soil–water systems. The degradations of two polycyclic aromatic hydrocarbons (PAHs) were fitted well with first order kinetic model and the degradation rates were in proportion to the concentration of biosurfactant. In addition, the degradation enhancement of PHE was higher than that of PYR. The addition of soil DOM itself at an environmental level would inhibit the biodegradation of PAHs. However, in the system with co-existence of DOM and biosurfactant, the degradation of PAHs was higher than that in only biosurfactant addition system, which may be attributed to the formation of DOM–biosurfactant complex micelles. Furthermore, under the combined conditions, the degradation of PAH increased with the biosurfactant concentration, and the soil DOM added system showed slightly higher degradation than the compost DOM added system, indicating that the chemical structure and composition of DOM would also affect the bioavailability of PAHs. The study result may broaden knowledge of biosurfactant enhanced bioremediation of PAHs contaminated soil and groundwater.

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log Kₒc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log Kₒcand HA having the highest log Kₒc. Log Kₒcis negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P ᵢ,ₙ) of protein-like region (PI,ₙ) and the P ᵢ,ₙof microbial byproduct-like region (PII,ₙ) of DOM EEMs, while it is correlated positively with humification index and the P ᵢ,ₙof UVC humic-like region (PIII,ₙ). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.

Selected water quality parameters and spectroscopic characteristics of dissolved organic matter (DOM) were examined during two different seasons for an artificial coastal lake (Shiwha Lake in South Korea), which are affected by seawater exchange due to the operation of a tidal power plant and external organic loadings from the upstream catchments. The coastal lake exhibited much lower concentrations of organic matter and nutrients than the upstream sources. The spectroscopic properties of the lake DOM were easily distinguished from those of the catchment sources as revealed by a lower absorption coefficient, lower degree of humification, and higher spectral slopes. The observed DOM properties suggest that the lake DOM may be dominated by smaller molecular size and less condensed structures. For the lake and the upper streams, higher absorption coefficients and fluorescence peak intensities but lower spectral slopes and humification index were found for the premonsoon versus the monsoon season. However, such seasonal differences were less pronounced for the industrial channels in the upper catchments. Three distinctive fluorophore groups including microbial humic-like, tryptophan-like, and terrestrial humic-like fluorescence were decomposed from the fluorescence excitation-emission matrix (EEM) of the DOM samples by parallel factor analysis (PARAFAC) modeling. The microbial humic-like component was the most abundant for the industrial channels, suggesting that the component may be associated with anthropogenic organic pollution. The terrestrial humic-like component was predominant for the upper streams, and its relative abundance was higher for the rainy season. Our principal component analysis (PCA) results demonstrated that exchange of seawater and seasonally variable input of allochthonous DOM plays important roles in determining the characteristics of DOM in the lake.