The investigation of quenching conditions for the analysis of total organic halogen, aliphatic and aromatic halogenated disinfection byproducts formed from chlor(am)ination.

Total organic halogen (TOX) is used to describe total amount of halogenated DBPs. Typically, once a chlor(am)inated water sample is collected, it is necessary to add a quenching agent to quench the residual disinfectant so that further reactions to form more DBPs during the holding time can be prevented. In this study, we evaluated the effects of four quenching agents: ammonium chloride (NH4Cl), ascorbic acid, sodium sulfite (Na2SO3), and sodium thiosulfate (Na2S2O3) on the decomposition of TOX, aliphatic and aromatic halogenated DBPs under various quenching conditions (quenching time, pH, quenching ratio, temperature). The results showed that ascorbic acid had the least impact on TOX. Ascorbic acid appeared to be the most suitable quenching agent for aliphatic halogenated DBPs, especially since it could preserve more haloacetonitriles than other quenching agents. Both ascorbic acid and Na2SO3 could be used for the analysis of aromatic halogenated DBPs. The lower pH (pH 6.0), not excessive quenching agents and lower temperature (4 ºC) were all conducive to the preservation of TOX and halogenated DBPs. Importantly, unknown TOX (UTOX) also contained significantly toxic components. It was also found that addition of quenching agents might lead to underestimation of UTOX by researchers. SYNOPSIS: The quenching agents and quenching conditions for the analysis of total organic halogen, aliphatic and aromatic halogenated DBPs formed from chlor(am)ination were investigated.

Disinfection byproducts and their cytotoxicity contribution from dissolved black carbon in source water during chlor(am)ination.

Dissolved black carbon (DBC), the soluble component of black carbon, which mainly comes from the incomplete combustion of fossil fuels or biomass, is widely spread in source water and significantly contributes to the formation of dissolved organic matter (DOM). However, the origin of DBC in different types of source water in China has not been well studied, as well as its subsequent transformation and toxicity contribution during disinfection of source water DOM by chlor(am)ine. In this study, DBC from 17 different source water in East China at different seasons was collected. The δ13C compositions indicated that straw burning was the main origin of DBC in source water. After simulated chlor(am)ination of DBC, 5 categories of aliphatic disinfection byproducts (DBPs) including trihalomethanes, haloacetic acids, haloacetonitriles, haloketones, halonitromethanes and 6 categories of aromatic DBPs including halophenols, halonitrophenols, halohydroxybenzaldehyde, halohydroxybenzoic acid, halobenzoquinones and haloaniline were detected. Compared with chlorination of DBC, higher levels of nitrogenous DBPs and aromatic DBPs were generated during chloramination. Detected DBPs accounted for 42 % of total organic halogen. What's more, Chinese hamster ovary cells cytotoxicity tests showed that the cytotoxicity of DBPs formed by chlor(am)ination of DBC was 4 times higher than that by chlor(am)ination of DOM. Haloacetonitriles contributed to the highest cytotoxicity in the chloramination of DBC, and haloacetic acids contributed to the highest cytotoxicity in chlorination. 67 % of the total cytotoxicity attributed to the undetected DBPs. As a result, DBPs generated from DBC contributed to 11.7 % of the total cytotoxicity in the chlor(am)ination of the source water DOM although DBC only took up 2 % of DOC in the source water. Results obtained from this study systematically revealed the DBPs formation from DBC and their potential cytotoxicity contribution in the chlor(am)ination of source water DOM, which should not be ignored in drinking water treatment.

Evolutions of dissolved organic matter and disinfection by-products formation in source water during UV-LED (275 nm)/chlorine process.

Ultraviolet light-emitting diode (UV-LED) is a promising option for the traditional low-pressure UV lamp, but the evolutions of DOM composition, the formation of disinfection by-products (DBPs) and their toxicity need further study in raw water during UV-LED/chlorine process. In UV-LED (275 nm)/chlorine process, two-dimensional correlation spectroscopy (2DCOS) analysis on synchronous fluorescence and UV-vis spectra indicated the protein-like fractions responded faster than the humic-like components, the reactive sequence of peaks for DOM followed the order: 340 nm→240 nm→410 nm→205 nm→290 nm. Compared to chlorination for 30 mins, the UV-LED/chlorine process enhanced the degradation efficiency of three fluorescent components (humic-like, tryptophan-like, tyrosine-like) by 5.1%-46.1%, and the formation of carbonaceous DBPs (C-DBPs) significantly reduced by 43.8% while the formation of nitrogenous DBPs (N-DBPs) increased by 27.3%. The concentrations of C-DBPs increased by 17.8% whereas that of N-DBPs reduced by 30.4% in 24 h post-chlorination. The concentrations of brominated DBPs increased by 17.2% during UV-LED/chlorine process, and further increased by 18.5% in 24 h post-chlorination. According to the results of principal component analysis, the non-fluorescent components of DOM might be important precursors in the formation of haloketones, haloacetonitriles and halonitromethanes during UV-LED/chlorine process. Unlike chlorine treatment, the reaction of DOM in UV-LED/chlorine treatment generated fewer unknown DBPs. Compared with chlorination, the cytotoxicity of C-DBPs reduced but the cytotoxicity of both N-DBPs and Br-DBPs increased during UV-LED/chlorine process. Dichloroacetonitrile had the highest cytotoxicity, followed by monobromoacetic acid, bromochloroacetonitrile and trichloroacetic acid during 30 mins of UV-LED/chlorine process. Therefore, besides N-DBPs, the more toxic Br-DBPs formation in bromide-containing water is also not negligible in the practical applications of UV-LED (275 nm)/chlorine process.

Degradation of natural organic matter and disinfection byproducts formation by solar photolysis of free available chlorine.

Environment disinfection effectively curbs transmission of the Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2). However, elevated concentration of free available chlorine (FAC) in disinfectants can be discharged into surface water, generating toxic disinfection byproducts (DBPs). The impact of solar photolysis of FAC on natural organic matter (NOM) to form DBPs has not been well studied. In this work, solar photolysis of FAC was found to result in higher formation of DBPs, DBPs formation potential (DBPsFP), total organic chlorine (TOCl) and lower specific ultraviolet absorbance at 254 nm (SUVA254), compared to dark chlorination. In solar photolysis of FAC, formation of total DBPs was promoted by pH=8, but hindered by the addition of HCO3-, radical scavenger or deoxygenation, while addition of NO3-and NH4+both enhanced the formation of nitrogenous DBPs. Differences in the formation of DBPs in solar photolysis of FAC under various conditions were influenced by reactive species. The formation of trichloromethane (TCM) and haloacetic acids (HAAs) in solar photolysis of FAC positively correlated with the steady-state concentrations of ClO• and O3. The steady-state concentrations of •NO and •NH2 positively correlated with the formation of halonitromethanes (HNMs). HAAs and haloacetonitriles (HANs) mainly contributed to calculated cytotoxicity of DBPs. This study demonstrates that solar photolysis of FAC may significantly impact the formation of DBPs in surface water due to extensive use of disinfectants containing FAC during SARS-CoV-2 pandemic.

The effects of exogenous amino acids on production of microcystin variants in Microcystis aeruginosa.

Dissolved free amino acids are a significant component of dissolved organic nitrogen (DON) in natural waterbodies. The effects of four amino acids (glutamic acid, phenylalanine, leucine, and arginine) on the growth and microcystins (MCs) production of Microcystis aeruginosa were studied in batch culture. The profiles of five MCs variants and the expression levels of target genes involved in MCs biosynthesis and nitrogen metabolism were measured. When amino acids were used as the sole nitrogen source instead of nitrate at different levels (0.5, 2.0 and 8.0 mg/L based on N) in BG-11 medium, algal cell growth and intracellular MCs quotas were inhibited slightly by the treatments with glutamic acid and arginine. The treatments with phenylalanine and leucine, on the other hand, had a strong inhibitory effect on algal cell growth and MCs production. Moreover, the concentrations of Chlorophyll a, phycocyanin and allophycocyanin in cells cultured in glutamic acid, leucine and phenylalanine were lower than those in the control group with nitrate as nitrogen source. The existence of leucine or phenylalanine can lead to a significant increase in the relative abundance of MCs variants structured with the corresponding amino acids. The expression of microcystin-producing gene mcyD was downregulated while the gene pipX associated with nitrogen metabolism was upregulated during the cultivation of M. aeruginosa with amino acids as sole nitrogen source. M. aeruginosa undergoes significant alterations due to exogenous amino acids and exhibits advanced strategies for MCs production.

Occurrence of dissolved black carbon in source water and disinfection byproducts formation during chlorination.

Dissolved black carbon (DBC), the water-soluble component of black carbon, which is formed by incomplete combustion of fossil fuels or biochar, takes up about 10% of dissolved organic matter (DOM) in river water. However, the distribution of DBC in water environment especially in source water is not clear and as an important component of DOM, whether DBC can produce disinfection byproducts (DBPs) like other DOM during disinfection remains unknown. In this study, the DBC concentrations in seventeen source water samples from East China were measured. The concentrations of DBC in the source water samples ranged from 60 to 270 µg/L, which were positively correlated with UV254 absorbance and chemical oxygen demand. The levels of DBC in wet season were higher than that in dry season. The average concentrations of DBC in different types of source water samples followed the order of reservoir > canal > lake > river. DBC could only be removed by 20% during the simulated coagulation, and further generate different categories of DBPs during chlorination, among which the concentrations of haloacetic acids (HAA) were the highest. The results indicated that DBC widely distributes in source water and is an important precursor of HAAs and THMs during chlorination.

Noncovalent interactions between fluoroquinolone antibiotics with dissolved organic matter: A 1H NMR binding site study and multi-spectroscopic methods.

Fluoroquinolone antibiotics (FQs) are considered to be emerging environmental contaminants that have been detected extensively in aquatic environment. It is of quite importance to explore FQs interacting with dissolved organic matter (DOM). The interactions of FQs with DOM were examined by nuclear magnetic resonance (NMR) spectroscopy, fluorescence quenching, UV-vis, Fourier transform infrared (FT-IR) spectroscopic techniques. The bindings of FQs to DOM had one single binding site and their quenching mechanisms were static, which were evaluated by the Stern-Volmer and Site-binding equations. Addition of DOM could result in micro-environmental changes of fluorophores groups in FQs. The location adjacent oxygen right of Ofloxacin (OFL) and the aromatic ring (the adjacency replaced by two nitrogen-containing groups) of Ciprofloxacin (CIP), Enrofloxacin (ENR), Norfloxacin (NOR) might be highly affected by DOM molecule. The negative enthalpy change (ΔH0), negative entropy change (ΔS0) and the positive Gibbs' energy change (ΔG0) figured out that the binding processes were exothermic but not thermodynamic favorable, the formation of HA-FQs complexes would be powered chiefly by the ΔS0. H-bonding, electrostatic effect, van der Waals force were the acting force in the binding reactions and the π-π stacking effect was the major binding force under alkaline conditions. Moreover, the protonated, deprotonated, or partially protonated state of FQs were found to have different binding capacity to DOM, and the binding reactions for FQs-HA system were suppressed as the ionic strength increased. Meanwhile, alterations of FQs conformation in the presence of DOM were evaluated by FT-IR and UV-vis spectra.

Magnetic biochar-based manganese oxide composite for enhanced fluoroquinolone antibiotic removal from water.

Magnetic biochar-based manganese oxide composite (MMB) and raw biochar (BC) were synthesized via pyrolysis at a temperature of 500 °C under anoxic conditions of potato stems and leaves, characterized, and successfully used for the removal of norfloxacin (NOR), ciprofloxacin (CIP), and enrofloxacin (ENR) as representative compounds of fluoroquinolone antibiotics (FQs). Characterization results suggested that Fe3O4 and MnOx are the dominant crystals in MMB. MMB possessed large surface area and pore volume than BC. Batch adsorption experiments showed that the maximum adsorption abilities of MMB for norfloxacin (NOR), ciprofloxacin (CIP), and enrofloxacin (ENR) were 6.94, 8.37, and 7.19 mg g-1. In comparison to BC, the adsorption abilities of MMB increased 1.2, 1.5, and 1.6 times for NOR, CIP, and ENR, respectively. The pseudo-second-order kinetic model and the Langmuir model correlated satisfactorily to the experimental data. Thermodynamic studies revealed that the adsorption processes were spontaneous and endothermic. The adsorption capacity of MMB decreased with increasing solution pH (between 3.0 and 10.0) and increasing ionic strength (0.001-0.1). The MMB with high FQ removal efficiency, easy separation, and desirable regeneration ability may have promising environmental applications for the removal of fluoroquinolone antibiotics from water environment.

[Composition, Spatial Distribution Characteristics and Source Analysis of Chromophoric Dissolved Organic Matter in the Lanzhou Reach of the Yellow River].

Chromophoric dissolved organic matter (CDOM) in riverine systems can be affected by environmental conditions and land-use, and can thus provide important information regarding anthropogenic activities in surrounding landscapes. It can modify the optical properties of waters and affect the balance and availability of dissolved nutrients and metals in water bodies. However, the characteristics of CDOM in the Lanzhou reach of the Yellow River have not yet been reported. In this study, the optical properties of water samples collected at 32 locations during April 2017 across the Lanzhou reach of the Yellow River were examined using UV-VIS and excitation-emission matrix fluorescence spectroscopy-parallel factor analysis (EEM-PARAFAC), to determine CDOM compositional changes, spatial distribution characteristics, and sources. Cluster analysis was used to categorize samples into groups of similar pollution levels within a study area. Results showed that CDOM was primarily comprised of low molecular weight organic substances with aromatic structure belonging to complex "protein-like-humic-like" substances, and dominated by protein-like substances (organism sources). Two humic-like components (C1, C4), one tryptophan-like component (C2), and one non-humic-like component (C3) were identified by PARAFAC. Tryptophan-like substances were predominant in the components of CDOM, accounting for 51.06% of average total fluorescence intensity. Humic-like materials and non-humic-like substances accounted for 36.74% and 12.20%, respectively. Weak correlations were observed between protein-like substances and humic-like substances, indicating different sources of these components. The distribution of total fluorescence intensity showed a distinct spatial pattern; trends in fluorescence intensity were weak-strong-weak along an upstream to downstream continuum, mainly affected by changes in the content of protein-like substances. The spatial variation of the CDOM in the Lanzhou reach of the Yellow River can therefore be assessed based on protein-like materials dynamics. Public spaces along rivers offer opportunities for community gatherings and recreational activities. However, high-intensity anthropogenic activities strongly influence CDOM concentration and composition in this area in different ways; sources include increased residential/commercial wastewater, catering, water recreation facilities pollution, shipping, and a small amount of industrial discharge. In addition, it was concluded that endogenetic pollution may become the main source of internal loading in the Lanzhou reach of the Yellow River, implying that stronger endogenetic pollution control is needed to alleviate CDOM pollution and improve water quality.