Halogenated aliphatic and phenolic disinfection byproducts in chlorinated and chloraminated dairy wastewater: Occurrence and ecological risk evaluation.

The increasing demand for dairy products has led to the production of a large amount of wastewater in dairy plants, and disinfection is an essential treatment process before wastewater discharge. Disinfection byproducts (DBPs) in disinfected dairy wastewater may negatively influence the aquatic organisms in receiving water. During chlorine and chloramine disinfection of dairy wastewater, the concentrations of aliphatic DBPs increased from below the detection limits to 485.1 µg/L and 26.6 µg/L, respectively. Brominated and iodinated phenolic DBPs produced during chlor(am)ination could further react with chlorine/chloramine to be transformed. High level of bromide in dairy wastewater (12.9 mg/L) could be oxidized to active bromine species by chlorine/chloramine, promoting the formation of highly toxic brominated DBPs (Br-DBPs), and they accounted for 80.3% and 71.1% of the total content of DBPs in chlorinated and chloraminated dairy wastewater, respectively. Moreover, Br-DBPs contributed 49.9-75.9% and 34.2-96.4% to the cumulative risk quotient of DBPs in chlorinated and chloraminated wastewater, respectively. The cumulative risk quotient of DBPs on green algae, daphnid, and fish in chlorinated wastewater was 2.8-11.4 times higher than that in chloraminated wastewater. Shortening disinfection time or adopting chloramine disinfection can reduce the ecological risks of DBPs.

High efficiency removal of organic and inorganic iodine with ferrate[Fe(VI)] through oxidation and adsorption.

I- is a halogen species existing in natural waters, and the transformation of organic and inorganic iodine in natural and artificial processes would impact the quality of drinking water. Herein, it was found that Fe(VI) could oxidize organic and inorganic iodine to IO3-and simultaneously remove the resulted IO3- through Fe(III) particles. For the river water, wastewater treatment plant (WWTP) effluent, and shale gas wastewater treated by 5 mg/L of Fe(VI) (as Fe), around 63 %, 55 % and 71 % of total iodine (total-I) had been removed within 10 min, respectively. Fe(VI) was superior to coagulants in removing organic and inorganic iodine from the source water. Adsorption kinetic analysis suggested that the equilibrium adsorption amount of I- and IO3- were 11 and 10.1 µg/mg, respectively, and the maximum adsorption capacity of IO3- by Fe(VI) resulted Fe(III) particles was as high as 514.7 µg/mg. The heterogeneous transformation of Fe(VI) into Fe(III) effectively improved the interaction probability of IO3- with iron species. Density functional theory (DFT) calculation suggested that the IO3- was mainly adsorbed in the cavity (between the γ-FeOOH shell and γ-Fe2O3 core) of Fe(III) particles through electrostatic adsorption, van der Waals force and hydrogen bond. Fe(VI) treatment is effective for inhibiting the formation of iodinated disinfection by-products in chlor(am)inated source water.

Anthracite Releases Aromatic Carbons and Reacts with Chlorine to Form Disinfection Byproducts in Drinking Water Production.

Anthracite is globally used as a filter material for water purification. Herein, it was found that up to 15 disinfection byproducts (DBPs) were formed in the chlorination of anthracite-filtered pure water, while the levels of DBPs were below the detection limit in the chlorination of zeolite-, quartz sand-, and porcelain sandstone-filtered pure water. In new-anthracite-filtered water, the levels of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and ammonia nitrogen (NH3-N) ranged from 266.3 to 305.4 µg/L, 37 to 61 µg/L, and 8.6 to 17.1 µg/L, respectively. In aged anthracite (collected from a filter at a DWTP after one year of operation) filtered water, the levels of the above substances ranged from 475.1 to 597.5 µg/L, 62.1 to 125.6 µg/L, and 14 to 28.9 µg/L, respectively. Anthracite would release dissolved substances into filtered water, and aged anthracite releases more substances than new anthracite. The released organics were partly (around 5%) composed by the µg/L level of toxic and carcinogenic aromatic carbons including pyridine, paraxylene, benzene, naphthalene, and phenanthrene, while over 95% of the released organics could not be identified. Organic carbon may be torn off from the carbon skeleton structure of anthracite due to hydrodynamic force in the water filtration process.

Occurrence of Iodophenols in Aquatic Environments and the Deiodination of Organic Iodine with Ferrate(VI).

Toxic and odorous iodophenols are commonly identified as disinfection by-products (DBPs) in drinking water. Herein, ng/L levels of iodophenols were identified in river water, wastewater treatment plant effluent, and medical wastewater, with the simultaneous identification of µg/L to mg/L levels of iodide (I-) and total organic iodine (TOI). Oxidation experiment suggested that the I-, TOI, and iodophenols could be oxidized by ferrate [Fe(VI)], and more than 97% of TOI had been transformed into stable and nontoxic IO3-. Fe(VI) initially cleaved the C-I bond of iodophenols and led to the deiodination of iodophenols. The resulted I- was swiftly oxidized into HOI and IO3-, with the intermediate phenolic products be further oxidized into lower molecular weight products. The Gibbs free energy change (ΔG) of the overall reaction was negative, indicating that the deiodination of iodophenols by Fe(VI) was spontaneous. In the disinfection of iodine-containing river water, ng/L levels of iodophenols and chloro-iodophenols formed in the reaction with NaClO/NH2Cl, while Fe(VI) preoxidation was effective for inhibiting the formation of iodinated DBPs. Fe(VI) exhibited multiple functions for oxidizing organic iodine, abating their acute toxicity/cytotoxicity and controlling the formation of iodinated DBPs for the treatment of iodide/organic iodine-containing waters.

Chlorination decreases acute toxicity of iodophenols through the formation of iodate and chlorinated aliphatic disinfection byproducts.

Highly toxic iodinated phenolic by-products were frequently detected in the oxidative treatment and disinfection of iodine-containing water. Herein, it was found that three model iodinated phenolic disinfection byproducts (DBPs), 2-iodophenol, 4-iodophenol and 2,4,6-triiodophenol, were reactive with HOCl, and the reaction rate constants (at pH 7.0 and 25℃) were 1.86 ×102, 1.62 ×102 and 7.5 ×101 M-1s-1, respectively. When HOCl was in excess (HOCl/iodophenol = 40/1, [iodophenol]0 = 20 µM), acute toxicity of water sample containing iodophenols could be largely eliminated (> 85%), with the conversion of iodophenols into stable and non-toxic iodate (IO3-) and iodinated and chlorinated aliphatic DBPs. Besides IO3-, seven kinds of aromatic intermediate products including iodophenols, chloroiodophenols, iodoquinones, chloroiodoquinones, chloroquinones, chlorophenols, and coupling products were detected. C-I bond of iodophenols was cleaved in the reaction and the resulted aromatic products were further transformed into chlorinated aliphatic DBPs [trichloromethane (TCM), trichloroacetic acid (TCAA), dichloroacetic acid (DCAA), and chloral hydrate (CH)] (mg/L level) and iodinated trihalomethanes (µg/L level). HOCl was effective for converting iodophenols into IO3- and less toxic chlorinated aliphatic DBPs. Considering that chlorine was widely used as disinfectant, transformation and toxicity alteration of emerging DBPs during chlorination/booster chlorination warrant further investigations.

Correction: Neuroinflammatory inhibitors from Gardneria nutans Siebold & Zuccarini.

[This corrects the article DOI: 10.1039/D1RA05204G.].

Neuroinflammatory inhibitors from Gardneria nutans Siebold & Zuccarini.

Two new monoterpene indole alkaloid glycosides nutanoside A-B (1-2), two new phenolic glycoside esters nutanester A-B (6-7), together with five known compounds (3-5, 8-9) were isolated from the ethanol extract of Gardneria nutans Siebold & Zuccarini. Their structures were established on the basis of extensive spectroscopic analysis and TDDFT/ECD calculations. Compounds 1 and 2 are two rare monoterpene indole alkaloids with the glucosyl moiety located at C-12 and represent the first two examples of enantiomer of ajmaline type monoterpene indole alkaloids. Compounds 3, 4 and 6 displayed significant inhibitory effects on NO production in over-activated BV2 microglial cells, with the IC50 values of 2.29, 6.36, and 8.78 µM, respectively. Compounds 1, 5, 7 could significantly inhibit the mRNA expression of inflammatory factors TNF-α and IL-6 induced by LPS in BV2 microglial cells at the effective concentration. Moreover, compound 3 exhibited stronger cytotoxicities against U87 and HCT116 cell lines than taxol with IC50 values of 10.58 and 14.60 µM, respectively.

Ferrate Oxidation of Phenolic Compounds in Iodine-Containing Water: Control of Iodinated Aromatic Products.

Highly toxic iodinated products would form in oxidation and disinfection of iodine-containing water. Variation of iodinated aromatic products in ferrate [Fe(VI)] oxidation of phenolic compounds (phenol, bisphenol A (BPA), and p-hydroxybenzoic acid (p-HBA)) in iodine-containing water was investigated. At pH 5.0, oxidation of phenolic compounds was inhibited by competitive reaction of ferrate with I-, and no formation of iodinated aromatic products was detected. Almost all I- was converted into nontoxic IO3-. At pH 7.0, 8.0, and 9.0, HOI formed in ferrate oxidation of I- and further reacted with phenols, with the formation of iodinated aromatic products. Mass spectrometry analysis showed that both kinds and contents of iodinated aromatic products were raised with the increase in solution pH and the content of I-, and these iodinated aromatic products were further oxidized by ferrate. Ferrate deprived iodine from iodinated aromatic products and transferred highly toxic organic iodine into nontoxic IO3-. An electron-donating substituent (alkyl) increased the reactivity of phenol with ferrate and HOI and facilitated ferrate oxidation of iodinated phenols. An electron-drawing substituent (carboxyl) decreased the reactivity of phenol with ferrate and HOI and hindered the further oxidation of iodinated aromatic products. A kinetic model about the variation of phenol, BPA, and p-HBA in reaction with ferrate in iodine-containing water was developed, and the oxidation profile of phenolic compounds could be satisfactorily predicted at various iodide concentrations.

Enhanced Permanganate Oxidation of Sulfamethoxazole and Removal of Dissolved Organics with Biochar: Formation of Highly Oxidative Manganese Intermediate Species and in Situ Activation of Biochar.

Sulfamethoxazole (SMX) is a broad-spectrum antibiotic and was largely used in breeding industry. The reaction rate of SMX with KMnO4 is slow, and the adsorption efficiency of biochar for SMX was inferior (less than 11% in 30 min). By adding biochar powder into SMX solution with the addition of permanganate, the oxidation ratio of SMX surged to 97% in 30 min, and over 58% of the total organic carbon (TOC) was simultaneously removed. KMnO4 interacted with biochar and resulted in the formation of highly oxidative intermediate manganese species, which transformed SMX into hydrolysis products, oxygen-transfer products, and self-coupling products. Brunauer-Emmett-Teller (BET) analysis showed that surface area, total pore volume, and micropore volume of biochar increased by 32.1%, 36.4%, and 80.6%, respectively, after reaction process. This in situ activation of biochar with KMnO4 enhanced its adsorption capacity and led to great improvement of TOC removal. Besides KMnO4 oxidation, biochar also enhanced TOC removal in Mn(III) oxidation (KMnO4+ bisulfite) and ozonization of SMX. Considering that KMnO4 could react with biochar and result in the formation of intermediate manganese species, while biochar can be simultaneously activated and exhibit high capacity for organic adsorption, the combination of biochar with the chemical/advanced oxidation could be a promising process for the removal of environmental pollutants.