Suyan Pang

Degradation of sulfamethoxazole by UV, UV/H2O2 and UV/persulfate (PDS): Formation of oxidation products and effect of bicarbonate

The frequent detection of sulfamethoxazole (SMX) in wastewater and surface waters gives rise of concerns about their ecotoxicological effects and potential risks to induce antibacterial resistant genes. UV/hydrogen peroxide (UV/H2O2) and UV/persulfate (UV/PDS) advanced oxidation processes have been demonstrated to be effective for the elimination of SMX, but there is still a need for a deeper understanding of product formations. In this study, we identified and compared the transformation products of SMX in UV, UV/H2O2 and UV/PDS processes. Because of the electrophilic nature of SO4-, the second-order rate constant for the reaction of sulfate radical (SO4-) with the anionic form of SMX was higher than that with the neutral form, while hydroxyl radical (OH) exhibited comparable reactivity to both forms. The direct photolysis of SMX predominately occurred through cleavage of the NS bond, rearrangement of the isoxazole ring, and hydroxylation mechanisms. Hydroxylation was the dominant pathway for the reaction of OH with SMX. SO4- favored attack on NH2 group of SMX to generate a nitro derivative and dimeric products. The presence of bicarbonate in UV/H2O2 inhibited the formation of hydroxylated products, but promoted the formation of the nitro derivative and the dimeric products. In UV/PDS, bicarbonate increased the formation of the nitro derivative and the dimeric products, but decreased the formation of the hydroxylated dimeric products. The different effect of bicarbonate on transformation products in UV/H2O2 vs. UV/PDS suggested that carbonate radical (CO3-) oxidized SMX through the electron transfer mechanism similar to SO4- but with less oxidation capacity. Additionally, SO4- and CO3- exhibited higher reactivity to the oxazole ring than the isoxazole ring of SMX. Ecotoxicity of transformation products was estimated by ECOSAR program based on the quantitative structure-activity relationship analysis as well as by experiments using Vibrio fischeri, and these results indicated that the oxidation of SO4- or CO3- with SMX generated more toxic products than those of OH.

Activation of peroxymonosulfate by phenols: Important role of quinone intermediates and involvement of singlet oxygen

In this study, the kinetics of reactions of peroxymonosulfate (PMS) with ten model phenols (including phenol, methylphenols, methoxyphenols, and dihydroxybenzenes) were examined. The oxidation kinetics of these phenols by PMS except for catechol and resorcinol showed autocatalysis in alkaline conditions (pH 8.5 and 10), due to the contribution of singlet oxygen (1O2) produced from PMS activation by quinone intermediates formed from their phenolic parents. The oxidation rates of ortho- and meta-substituted methylphenols and methoxyphenols by PMS were much higher than their para-substituted counterparts under similar conditions. This was attributed to the relatively low yields of quinone intermediates from para-substituted phenols. SMX could be efficiently degraded by PMS in the presence of phenols which showed great autocatalysis when they individually reacted with PMS, and the addition of methanol in excess had negligible influence suggesting that 1O2 rather than hydroxyl radical and sulfate radical played an important role. Transformation of SMX by 1O2 underwent three pathways including hydroxylation of aniline ring, oxidation of aromatic amine group to generate nitro-SMX, and oxidative coupling to generate azo-SMX and hydroxylated azo-SMX. These results obtained in this work improve the understanding of in situ chemical oxidation using PMS for remediation of subsurface, where phenolic and quinonoid moieties are ubiquitous.

Chlorination of bisphenol S: Kinetics, products, and effect of humic acid

Bisphenol S (BPS), as a main alternative of bisphenol A for the production of industrial and consumer products, is now frequently detected in aquatic environments. In this work, it was found that free chlorine could effectively degrade BPS over a wide pH range from 5 to 10 with apparent second-order rate constants of 7.6-435.3 M-1s-1. A total of eleven products including chlorinated BPS (i.e., mono/di/tri/tetrachloro-BPS), 4-hydroxybenzenesulfonic acid (BSA), chlorinated BSA (mono/dichloro-BSA), 4-chlorophenol (4CP), and two polymeric products were detected by high performance liquid chromatography and electrospray ionization-tandem quadrupole time-of-flight mass spectrometry. Two parallel transformation pathways were tentatively proposed: (i) BPS was attacked by stepwise chlorine electrophilic substitution with the formation of chlorinated BPS. (ii) BPS was oxidized by chlorine via electron transfer leading to the formation of BSA, 4CP and polymeric products. Humic acid (HA) significantly suppressed the degradation rates of BPS even taking chlorine consumption into account, while negligibly affected the products species. The inhibitory effect of HA was reasonably explained by a two-channel kinetic model. It was proposed that HA negligibly influenced pathway i while appreciably inhibited the degradation of BPS through pathway ii, where HA reversed BPS phenoxyl radical (formed via pathway ii) back to parent BPS.

Factors affecting formation of deethyl and deisopropyl products from atrazine degradation in UV/H2O2 and UV/PDS

In this study, the formation of deethyl products (DEPs) (i.e., atrazine amide (Atra-imine) and deethylatrazine (DEA)) and deisopropyl product (i.e., deisopropylatrazine (DIA)) from parent atrazine (ATZ) degraded in UV/H2O2 and UV/PDS processes under various conditions was monitored. It was found that SO4˙− displayed a more distinctive preference to the ethyl function group of ATZ than HO˙, leading to the higher ratio of DEPs/DIA in UV/PDS system than that in UV/H2O2 system in pure water. The effects of water matrices (i.e., natural organic matter (NOM), carbonate/bicarbonate (HCO3−/CO32−), and chloride ions (Cl−)) on ATZ degradation as well as formation of DEPs and DIA were evaluated in detail. The degradation of ATZ by UV/PDS was significantly inhibited in the presence of NOM, HCO3−/CO32− or Cl−, because these components could competitively react with SO4˙− and/or HO˙ to generate lower reactive secondary radicals (i.e., organic radicals, carbonate radicals (CO3˙−) or reactive chlorine radicals (RCs)). The yields of these DEPs and DIA products from ATZ degradation were not impacted by NOM or HCO3−/CO32−, possibly due to the low reactivity of organic radicals and CO3˙− toward the side groups of ATZ. Howbeit, the increase of DIA yield companied with the decrease of DEPs yield was interestingly observed in the presence of Cl−, which was attributed to the promotion of Cl− at moderate concentration (mM range) for the conversion of SO4˙− into HO˙. Comparatively, in the UV/H2O2 process, NOM and HCO3−/CO32− exhibited a similar inhibitory effect on ATZ degradation, while the influence of Cl− was negligible. Differing from UV/PDS system, all these factors did not change DEPs and DIA yields in UV/H2O2 process. Moreover, it was confirmed that RCs had a greater selectivity but a lower reactivity on attacking the ethyl function group than that of SO4˙−. These findings were also confirmed by monitoring the degradation of ATZ as well as the formation of DEPs and DIA in three natural waters.

Comparative study on degradation of propranolol and formation of oxidation products by UV/H2O2 and UV/persulfate (PDS)

The frequent detection of propranolol, a widely used β-blocker, in wastewater effluents and surface waters has raised serious concern, due to its adverse effects on organisms. UV/hydrogen peroxide (UV/H2O2) and UV/persulfate (UV/PDS) processes are efficient in eliminating propranolol in various waters, but the formation of oxidation products in these processes, as well as the assessment of their toxicity, has not been systematically addressed. In this study, we identified and compared transformation products of propranolol produced by hydroxyl radical (•OH) and sulfate radical (SO4•-). The electrostatic attraction enhances the reaction between SO4•- and the protonated form of propranolol, while •OH shows non-selectivity toward both protonated and neutral propranolol species. The hydroxylation of propranolol by •OH occurs at either amine moiety or naphthalene group while SO4•- favors the oxidation of the electron-rich naphthalene group. Further oxidation by •OH and SO4•- results in ring-opening products. Bicarbonate and chloride exert no effect on propranolol degradation. The generation of CO3•- and Cl-containing radicals is favorable to oxidizing naphthalene group. The acute toxicity assay of Vibrio fischeri suggests that SO4•- generates more toxic products than •OH, while CO3•- and Cl-containing radicals produce similar toxicity as SO4•-. High concentrations of bicarbonate in UV/H2O2 increase the toxicity of treated solution.

Highly effective oxidation of roxarsone by ferrate and simultaneous arsenic removal with in situ formed ferric nanoparticles

Roxarsone (ROX) is used in breeding industry to prevent infection by parasites, stimulate livestock growth and improve pigmentation of livestock meat. After being released into environment, ROX could be bio-degraded with the formation of carcinogenic inorganic arsenic (As) species. Here, ferrate oxidation of ROX was reported, in which we studied total-As removal, determined reaction kinetics, identified oxidation products, and proposed a reaction mechanism. It was found that the apparent second-order rate constant (kapp) of ferrate with ROX was 305 M-1s-1 at pH 7.0, 25 °C, and over 95% of total As was removed within 10 min when ferrate/ROX molar ratio was 20:1. Species-specific rate constants analysis showed that HFeO4- was the dominant species reacting with ROX. Ferrate initially attacked AsC bond of ROX and resulted in the formation of arsenate and 2-nitrohydroquinone. The arsenate was simultaneously removed by ferric nanoparticles formed in the reduction of ferrate, while 2-nitrohydroquinone was further oxidized into nitro-1,4-benzoquinone. These results suggest that ferrate treatment can be an effective method for the control of ROX in water treatment.

Oxidation of steroid estrogens by peroxymonosulfate (PMS) and effect of bromide and chloride ions: Kinetics, products, and modeling

Recently, in situ chemical oxidation (ISCO) using peroxymonosulfate (PMS) for environmental decontamination has received increasing interest. In this study, oxidation kinetics and products of four steroid estrogens (i.e., estrone, 17β-estradiol, estriol, and 17α-ethinylestradiol) by PMS under various conditions were investigated. PMS could fairly degrade steroid estrogens over the pH range of 7-10, and the degradation rate increased with the increase of solution pH. This pH-dependence was well described by parallel reactions between individual acid-base species of steroid estrogens (E and E-) and PMS (HSO5- and SO52-), where specific second-order rate constants for E- with HSO5- and SO52- were in the range of 2.11-5.58 M-1s-1 and 0.77-1.25 M-1s-1, respectively. Identification of oxidation products by liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometer showed that PMS readily oxidized the phenolic group of steroid estrogens, leading to the generation of hydroxylated and ring-opening products. The presence of bromide and chloride ions (Br- and Cl-) at environmentally relevant levels could greatly accelerate the degradation of steroid estrogens by PMS with the formation of halogenated aromatic products. This effect was quantitatively estimated by a kinetic model, where the formation of free bromine and chorine and their rapid electrophilic substitution with steroid estrogens were taken into consideration. Eco-toxicity of transformation products of 17α-ethinylestradiol by PMS treatment in the absence and presence of bromide and chloride was estimated by quantitative structure-activity relationship analysis using ECOSAR. These findings advance the understanding of ISCO using PMS.

Effect of iodide on transformation of phenolic compounds by nonradical activation of peroxydisulfate in the presence of carbon nanotube: Kinetics, impacting factors, and formation of iodinated aromatic products

Our recent study has demonstrated that iodide (I-) can be easily and almost entirely oxidized to hypoiodous acid (HOI) but not to iodate by nonradical activation of peroxydisulfate (PDS) in the presence of a commercial carbon nanotube (CNT). In this work, the oxidation kinetics of phenolic compounds by the PDS/CNT system in the presence of I- were examined and potential formation of iodinated aromatic products was explored. Experimental results suggested that I- enhanced the transformation of six selected substituted phenols, primarily attributed to the generation of HOI that was considerably reactive toward these phenolic compounds. More significant enhancement was obtained at higher I- concentrations or lower pH values, while the change of PDS or CNT dosages exhibited a slight impact on the enhancing effect of I-. Product analyses with liquid chromatography tandem mass spectrometry clearly revealed the production of iodinated aromatic products when p-hydroxybenzoic acid (p-HBA, a model phenol) was treated by the PDS/CNT/I- system in both synthetic and real waters. Their formation pathways probably involved the substitution of HOI on aromatic ring of p-HBA, as well as the generation of iodinated p-HBA phenoxyl radicals and subsequent coupling of these radicals. Given the considerable toxicity and harmful effects of these iodinated aromatic products, particular attention should be paid when the novel PDS/CNT oxidation technology is applied for treatment of phenolic contaminants in iodide-containing waters.