ABSTRACT
The photoexcited dissolved organic matter (DOM) could produce reactive intermediates, affecting chemical oxidant transformation in UV based advanced oxidation processes (AOPs). This study confirmed the critical role of triplet state DOM (3DOM*), generated from DOM photoexcitation, in the transformation of monochloramine (NH2Cl), a commonly used chemical oxidant and disinfectant in water treatment. NH2Cl (42.25 µM, as Cl2) was decayed by 17.4-73.4 % within 60 min, primarily due to 3DOM* , in DOM (2-30 mgC L-1) solutions irradiated by 365 nm, where NH2Cl has no absorption. The second-order quenching rate constants of triplet state model photosensitizers by NH2Cl were determined to be 0.95(± 0.04)-4.49(± 0.04)× 108 M-1 s-1 by using laser flash photolysis. As a reductant, 3DOM* reacted with NH2Cl through one-transfer mechanism, leading to amino radical (NH2â¢) generation, which then transferred to ammonia (NH4+, pKa 9.25) through H-abstraction by the phenolic moieties in DOM. Additionally, the intermediate product of 3DOM* oxidized by NH2Cl or those triplet state quinones can hydrolyze to form phenolic moieties, elevating NH4+ yield to higher than 99% upon 365 nm irradiation. These findings suggest that the widespread DOM can be applied to convert NH2Cl via 3DOM* with minimal toxic risks.
ABSTRACT
The aquaculture area in China's coastal waters has increased rapidly from 6000 km2 in 1990 to 22,000 km2 in 2020. Despite extensive research regarding the effect of coastal aquaculture on water and sediment pollution, evaluating the quantitative relationship between aquaculture and pollutants remains challenging. Sansha Bay, the world's largest cage aquaculture base for Pseudosciaena crocea, is a typical enclosed bay used for investigating aquaculture pollution. A cage culture database is established from 2000 to 2020 in Sansha Bay. Meanwhile, 236 sediment samples from 3 sediment cores and 67 water samples from 4 transects are obtained from the bay for experiments. The main indicators are five nutrients (NO3-, SiO32-, PO43-, NH4+, and NO2-) in the water samples, the grain size, the heavy metal (Zn, Cu, Pb, Cr, Cd, and As) content, and the 210Pb radioactivity in sediment samples. Based on data obtained and a new calculation method, the annual increment in Zn, Cu, As, Cd, Pb, and Cr contents in the cultured zone is shown to increase by 2137 %, 1881 %, 506 %, 300 %, 202 %, and 118 % in 2000-2018, respectively, as compared with the levels in a noncultured zone. The activities of the cage culture increased NO3- by 9 %, PO43- by 30 %, NH4+ by 115 %, and NO2- by 232 %, compared with natural conservative mixing processes, such as the mixing of SiO32-, in 2020. A novel quantitative approach with broad applicability is proposed to evaluate the magnitude of anthropogenically induced environmental contamination. The effectiveness of the proposed technique is demonstrated through a case study conducted in Sansha Bay, China.
