Search

Soil in the vadose zone is an important sink for antibiotics. However, previous studies have examined only the degradation of antibiotics in soil slurry systems, which were largely different from real-world unsaturated soil environments. Whether the same transformation mechanisms apply to unsaturated soil systems has been a question. Here, the degradation of sulfamethoxazole (SMX) by manganese dioxide (γ-MnO 2 ) in both suspension systems and evaporation processes were examined. Results show that the slow degradation of SMX in the suspension system can be significantly promoted as the water gradually evaporates. SMX degraded differently in evaporation as compared to suspension systems because of the quenching effect of generated Mn 2+ . Transformation products of SMX in both systems also showed different toxicity toward Escherichia coli because of different evolutions of intermediates. This study has strong implications for the assessment and prediction of the transformation and fate of antibiotics in natural soil environments.

There is increasing concern about the severe endocrine-related health problems because of the discharge of estrogenic disrupting chemicals (EDCs) into the natural environment. In this study, we investigated the activation of monochloramine (NH 2 Cl) by biochar [pyrolyzed by cotton straw at 350 °C (Cot350), wheat straw at 350 and 700 °C (WS350 and WS700), and corn straw at 350 and 700 °C (CS350 and CS700)] for the degradation of estradiol (E2) and ethinylestradiol (EE2). Approximately 95% of parent E2 and EE2 was removed by Cot350/NH 2 Cl in buffered solution, and 87% of E2 and 75% of EE2 were removed in urine within 24 h. Electronic paramagnetic resonance analysis and radical-quenching experiments showed that biochar activated NH 2 Cl and primarily generated • NO radicals for the degradation of the EDCs. The nitrogen and silicon elements of Cot350 served as primary catalytic sites for NH 2 Cl activation, whereas the sp 2 -hybridized carbon on WS700 and CS700 played a major role. The effect of major urine components (i.e., ammonia species, chloride, and bicarbonate) on the reaction pathways of biochar/NH 2 Cl was also elucidated. This study provides new insights into the reaction pathways of NH 2 Cl activation by biochar and suggests potential applications for other carbonaceous materials for NH 2 Cl activation.

Monochloramine (NH 2 Cl) can be irradiated by UV to create an advanced oxidation condition (i.e., UV/NH 2 Cl) for the elimination of organic micropollutants (OMPs) from source water. However, information in retrospective studies was scarce on how UV/NH 2 Cl performance would be affected by the water matrix and OMP molecular structures. In this study, the degradation of five representative OMPs, including triclosan, carbamazepine, sulfamethoxazole, estradiol (E2), and ethinylestradiol (EE2), was examined in different water matrices. All OMPs were rapidly removed by UV/NH 2 Cl but exhibited different degradation mechanisms. Although •OH, •Cl, and direct photolysis mainly contributed to the overall degradation of OMPs in buffered nanopure water, the contribution of reactive nitrogen species (RNS) generated from the photolysis of NH 2 Cl was not negligible in the degradation of E2 and EE2. A phenolic group was identified as the moiety reactive toward RNS. Based on quantitative analysis of the impact on OMP degradation from cosolutes (including Cl - , HCO 3 - , NOM) as well as pH and NH 2 Cl doses, we developed a kinetic model for the prediction of OMP degradation in complex water matrices. In environmental water matrices, the performance and radical contributions in UV/NH 2 Cl and UV/H 2 O 2 systems were taken into comparison, which showed faster degradation of OMPs and a more significant contribution of CO 3 •- in the UV/NH 2 Cl process.

The combination of chlorine and UV (i.e., chlorine-UV process) has been attracting more attention in recent years due to its ready incorporation into existing water treatment facilities to remove PPCPs. However, limited information is available on the impact of total ammonia nitrogen (TAN). This study investigated two model PPCPs, N,N-diethyl-3-toluamide (DEET) and caffeine (CAF), in the two stages of the chlorine-UV process (i.e., chlorination and UV/chlor(am)ine) to elucidate the impact of TAN. During chlorination, the degradation of DEET and CAF was positively correlated with the overall consumption of total chlorine by TAN. Reactive nitrogen intermediates, including HNO/NO - and ONOOH/ONOO - , along with • OH were identified as major contributors to the removal of DEET and CAF. During UV irradiation, DEET and CAF were degraded under UV/chlorine or UV/NH 2 Cl conditions. • OH and • Cl were the major reactive species to degrade DEET and CAF under UV/NH 2 Cl conditions, whereas • OCl played a major role for degrading CAF under UV/chlorine conditions. Numerical models were developed to predict the removal of DEET and CAF under chlorination-UV process. Chlorinated disinfection byproducts were detected. Overall, this study presented kinetic features and mechanistic insights on the degradation of PPCPs under the chlorine-UV process in ammoniacal water.

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br - and Cl - may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Elimination of pharmaceuticals in source-separated human urine is a promising approach to minimize the pharmaceuticals in the environment. Although the degradation kinetics of pharmaceuticals by UV/H2O2 and UV/peroxydisulfate (PDS) processes has been investigated in synthetic fresh and hydrolyzed urine, comprehensive evaluation of the advanced oxidation processes (AOPs), such as product identification and toxicity testing, has not yet been performed. This study identified the transformation products of two commonly used antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), by UV/H2O2 and UV/PDS in synthetic urine matrices. The effects of reactive species, including •OH, SO4(•-), CO3(•-), and reactive nitrogen species, on product generation were investigated. Multiple isomeric transformation products of TMP and SMX were observed, especially in the reaction with hydroxyl radical. SO4(•-) and CO3(•-) reacted with pharmaceuticals by electron transfer, thus producing similar major products. The main reactive species deduced on the basis of product generation are in good agreement with kinetic simulation of the advanced oxidation processes. A strain identified as a polyphosphate-accumulating organism was used to investigate the antimicrobial activity of the pharmaceuticals and their products. No antimicrobial property was detected for the transformation products of either TMP or SMX. Acute toxicity employing luminescent bacterium Vibrio qinghaiensis indicated 20-40% higher inhibitory effect of TMP and SMX after treatment. Ecotoxicity was estimated by quantitative structure-activity relationship analysis using ECOSAR.

To minimize environmental pharmaceutical micropollutants, treatment of human urine could be an efficient approach due to the high pharmaceutical concentration and toxic potential excreted in urine. This study investigated the degradation kinetics and mechanisms of sulfamethoxazole (SMX), trimethoprim (TMP) and N4-acetyl-sulfamethoxazole (acetyl-SMX) in synthetic fresh and hydrolyzed human urines by low-pressure UV, and UV combined with H2O2 and peroxydisulfate (PDS). The objective was to compare the two advanced oxidation processes (AOPs) and assess the impact of urine matrices. All three compounds reacted quickly in the AOPs, exhibiting rate constants of (6.09-8.53) × 10(9) M(-1)·s(-1) with hydroxyl radical, and (2.35-16.1) × 10(9) M(-1)·s(-1) with sulfate radical. In fresh urine matrix, the pharmaceuticals' indirect photolysis was significantly suppressed by the scavenging effect of urine citrate and urea. In hydrolyzed urine matrix, the indirect photolysis was strongly affected by inorganic urine constituents. Chloride had no apparent impact on UV/H2O2, but significantly raised the hydroxyl radical concentration in UV/PDS. Carbonate species reacted with hydroxyl or sulfate radical to generate carbonate radical, which degraded SMX and TMP, primarily due to the presence of aromatic amino group(s) (k = 2.68 × 10(8) and 3.45 × 10(7) M(-1)·s(-1)) but reacted slowly with acetyl-SMX. Ammonia reacted with hydroxyl or sulfate radical to generate reactive nitrogen species that could react appreciably only with SMX. Kinetic simulation of radical concentrations, along with products analysis, helped elucidate the major reactive species in the pharmaceuticals' degradation. Overall, the AOPs' performance was higher in the hydrolyzed urine than fresh urine matrix with UV/PDS better than UV/H2O2, and varied significantly depending on pharmaceutical's structure.