Many antibiotics, including sulfonamides, are being frequently detected in soil and groundwater. Livestock waste is an important source of antibiotic pollution, and sulfonamides may be present along with organic-rich substances. This study aims to investigate the sorption reaction of two sulfonamides, sulfamethoxazole (SMZ) and sulfapyridine (SPY) in two organic-rich sorbents: a commercial peat soil (38.41% carbon content) and a composted manure (24.33% carbon content). Batch reactions were conducted to evaluate the impacts of pH (4.5–9.5) and background ions (0.001 M–0.1 M CaCl2) on their sorption. Both linear partitioning and Freundlich sorption isotherms fit the reaction well. The n values of Freundlich isotherm were close to 1 in most conditions suggesting that the hydrophobic partition is the major adsorption mechanism. In terms of SMZ, Kd declined with increases in the pH. SPY has a pyridine group that is responsible for adsorption at high pH values, and thus, no significant trend between Kd and pH was observed. At high pH ranges, SPY sorption deviated significantly from linear partitioning. The results suggested the sorption mechanism of these two sulfonamide antibiotics tended to be hydrophobic partitioning under most of the experimental conditions, especially at pH values lower than their corresponding pKa2. The fluorescence excitation emission matrix and dissolved organic carbon leaching test suggested composted manure has higher fulvic acid organics and that peat soil has higher humus-like organics. Small organic molecules showed stronger affinity toward sulfonamide antibiotics and cause the composted manure to exhibit higher sorption capacity. Overall, this study suggests that the chemical structure and properties of sulfonamides antibiotics and the type of organic matter in soils will greatly influence the fate and transport of these contaminants into the environment.

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction.Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water.

The sorption of three organic contaminants with different structure and polarity including non-polar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), and polar 1,2-dichlorobenzene (DCB) onto original kaolinite, smectite, vermiculite, and fulvic acid (FA)/humic acid (HA)–clay complexes were investigated, and possible sorption mechanisms were inferred from sorption isotherms and characteristics of humic substances (HS) and HS–mineral complexes. Results showed smectite and vermiculite had stronger sorption ability than kaolinite, and the adsorbed amount of DCB was much higher than that of PHEN and TeCB on each clay. Due to FA/HA-facilitated hydrophobic interaction, FA/HA–clay complexes except FA–vermiculite complex showed a stronger affinity for PHEN and TeCB than the original clays, particularly for HA–clay complexes. The non-linearity parameter values of n for all the Freundlich sorption isotherms of DCB were greater than 1, indicating that clays possessed some unique sites with strong affinity and capacity to sorb DCB from aqueous solutions. FA/HA did not significantly affect the sorption of polar DCB on clays, implying sorption of DCB on clays was probably due to polar interactions between the polar group of DCB and clays. Cation-π bonding between PHEN and iron cation was directly evidenced by X-ray photoelectron spectroscopy, and FA impeded the sorption of PHEN on vermiculite by occupation of iron cation sites. This study will benefit understanding behaviors of contaminants in the soil environments.

The purpose of this study was to determine the different kinds and concentrations of intermediates, and investigate on the effects of contact time and ozone (O₃) doses on the removal of humic acid (HA), which is served as the main disinfection by-product (DBP) precursor. Based on that, the knowledge gap of DBPs generated was made up. The results showed that HA was the major precursor material for aldehydes and carboxylic acids. The concentrations of aldehydes increased as contact time and O₃ doses, and reached up maximum at 2~10 min but approached a plateau at the higher O₃ doses. The concentrations of formic and acetic acids increased as contact time and O₃ doses. However, aromatic acids, including protocatechuic, 3-hydroxybenzoic, and benzoic acids, declined rapidly at longer reaction time and higher O₃ doses. It was worth mentioning that aromatic acids had been rarely reported. Besides, a possible formation pathway was proposed: (a) HA was degraded into fulvic acid (FA)-like compounds; (b) FA-like compounds were further converted into aromatic acids; (c) aromatic acids were transformed into low-molecular-weight organic matters; (d) chlorine reacted with aldehydes and/or carboxylic acids by addition, hydrolysis, and decarbonylation reactions, leading to DBP formation. Furthermore, not only HA were the main DBPs precursors, but also the oxidation intermediates of HA could be the DBPs precursors, and they gave a certain amount of DBPs. Consequently, aldehydes and carboxylic acids should be under control in drinking water treatment plants.

The oxidation of indometacin (IDM) by ferrate(VI) (Fe(VI)) was investigated to determine the reaction kinetics, transformation products, and changes in toxicity. The reaction between IDM and Fe(VI) followed first-order kinetics with respect to each reactant. The apparent second-order rate constants (k ₐₚₚ) decreased from 9.35 to 6.52 M⁻¹ s⁻¹, as the pH of the solution increased from 7.0 to 10.0. The pH dependence of k ₐₚₚ might be well explained by considering the species-specific rate constants of the reactions of IDM with Fe(VI). Detailed product studies using liquid chromatography-tandem mass spectrometry (LC-MS/MS) indicated that the oxidation products were primarily derived from the hydrolysis of amide linkages, the addition of hydroxyl groups, and electrophilic oxidation. The toxicity of the oxidation products was evaluated using the Microtox test, which indicated that transformation products exhibited less toxicity to the Vibrio fischeri bacteria. Quantitative structure-activity relationship (QSAR) analysis calculated by the ecological structure activity relationship (ECOSAR) revealed that all of the identified products exhibited lower acute and chronic toxicity than the parent pharmaceutical for fish, daphnid, and green algae. Furthermore, Fe(VI) was effective in the degradation IDM in water containing carbonate ions or fulvic acid (FA), and in lake water samples; however, higher Fe(VI) dosages would be required to completely remove IDM in lake water in contrast to deionized water.

Several organic phosphorus compounds (Po) in sediment from a representative eutrophic lake were surveyed using a sequential fractionation procedure, which included microbial biomass phosphorus (Biomass-P), fulvic acid phosphorus (FA-P), humic acid phosphorus (HU-P), and residual phosphorus (Res-P). In addition, several organic compounds including orthophosphate monoesters, orthophosphate diesters, and pyrophosphate were simultaneously measured using ³¹P nuclear magnetic resonance (³¹P NMR). Results showed that Po contributed over 50% of total phosphorus (TP), and the average concentration of Po species generally decreased from Res-P > FA-P > HU-P > Biomass-P. Additionally, the relative proportions of phosphorus compounds in the sediment followed the decreasing order of orthophosphate monoesters > orthophosphate diesters > pyrophosphate. In general, Po was the dominant phosphorus species. Residual P was not a single species but comprised of a group of species, and tended to be stable. Although orthophosphate monoesters had the highest concentrations and ratios in Po, orthophosphate diesters displayed a more distinct remineralization trend. Principal component analysis (PCA) coupled with correlation analysis suggested that a greater amount of orthophosphate diesters resided in Res-P, than HU-P or FA-P.

This study aimed to investigate the degradation of triclosan (TCS) in the presence of p-aminobenzoic acid (PABA) under simulated sunlight irradiation (λ ≥ 290 nm). The effect of PABA concentration, pH, dissolved organic matter (DOM), and DOM-hydrolytic Fe(III) species complexes on the photodegradation of TCS in the presence of PABA (TCS₋PABA) was also studied. The photolysis of TCS₋PABA obeyed pseudo-first-order kinetics well, and the degradation of TCS₋PABA enhanced with increasing solution pH (from 3.0 to 11.0). The presence of PABA inhibited the degradation of TCS₋PABA, and the weakest inhibitory effect was observed while the concentration of PABA was 5 mg L⁻¹. The addition of DOM (Suwannee River fulvic acid standard I [SRFA], Suwannee River HA standard II [SRHA], and Suwannee River natural organic matter [SRNOM]) showed different inhibition effects on TCS₋PABA degradation. However, higher Fe(III) concentration at the DOM concentration of 5 mg L⁻¹ could favor the formation of DOM-hydrolytic Fe(III) species complexes, further accelerating the degradation of TCS₋PABA. In comparison with deionized water (DI water), TCS₋PABA could be better photodegraded in river water nearby the effluent of a wastewater treatment plant. This study provides useful information for understanding the natural behavior of TCS in the presence of other organic contaminants.

Optical properties and molecular composition of humic substances (HS) can provide valuable information on the sources and the history of the associated biogeochemical processes. In this study, many well-known spectral and molecular characteristics were examined in eight different HS samples, which were extracted from soils and sediments located in a forested watershed, via two advanced tools including fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC) and high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Two humic-like (C1 and C2) and one protein-like (C3) components were identified from EEM-PARAFAC. Irrespective of the origins, humic acid (HA) fractions were distinguished from fulvic acid (FA) fractions by the HS characteristics of specific UV absorbance (SUVA), the number of formulas, maximum fluorescence intensities of C1 and C2, condensed aromatics, tannins, and CHON, CHOS, and CHONS classes. In contrast, only five HS indices, including C3 intensity, H%, modified aromatic index (AIₘₒd), the percentages of carbohydrates, and unsaturated hydrocarbons, were found to be significant factors in discriminating between the two HS origins (i.e., soils and sediments). The ordination of the Bray-Curtis dissimilarity matrix further confirmed that the HS chemical fraction (i.e., HA or FA) was the more important factor to determine the measured HS characteristics than the HS origin. Our results provided an in-depth insight into the chemical and structural heterogeneity of bulk HS, which could be even beyond the differences observed along the two HS origins. This study also delivers a cautious message that the two operationally defined HS chemical fractions should be carefully considered in tracking the origins of different HS samples.

Swine wastewater is one of the most serious pollution sources, and it has attracted a great public concern in China. Anaerobic digestion technology is extensively used in swine wastewater treatment. However, the anaerobic digestion effluents are difficult to meet the discharge standard. The results from batch experiments showed that plenty of refractory organic matter remained in the effluents after mesophilic anaerobic digestion for 30 days. The effluent total COD (tCOD) and soluble COD (sCOD) were 483 and 324 mg/L, respectively, with the sCOD/tCOD ratio of 0.671. Fluorescence excitation–emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) revealed that the dissolved organic matter in the effluents was tryptophan-like substance, humic acid substance, and fulvic acid substance. Based on the appearance time during anaerobic digestion, tryptophan-like substance and humic acid substance were inferred to originate from the raw swine wastewater, and the fulvic acid substance was inferred to be formed in the anaerobic digestion. This work has revealed the source of residual organic matter in anaerobic digestion of swine wastewater and has provided some valuable information for the post-treatment.

Dissolved organic matter (DOM), as a very fine colloidal suspension, could inevitably affect the transformation process of dissolved organic nitrogen (DON) in drinking water treatment. Tryptophan and tyrosine were used as representatives of DON to investigate the interactions between amino acids and fulvic-like components of fluorescent DOM using titration experiments. The fluorescence intensity decreased significantly with the increasing fulvic acid (FA) concentration, suggesting that FA could greatly quench the intrinsic fluorescence of amino acids such as tryptophan and tyrosine. The absolute spectrum peaks of amino acids (AA) were changed in the presence of FA, possibly being resulted from non-covalent interactions between amino acids and FA. The specific hydrogen bonding and van der Waals forces played dominant roles in the interactions according to the results of theoretical analysis and thermodynamic calculation. The distance between donor and acceptor was 1.25 and 1.14 nm for the FA–tyrosine and FA–tryptophan system, indicating the energy transfer from tyrosine or tryptophan to FA. The association constant (K) decreased with the increase of temperature and pH value, while the change of ionic strength had no obvious influence on K value.