Phenolic endocrine disrupting chemicals (EDCs) in an estuarine water column in a depth profile of five water layers (0.05 D, 0.20 D, 0.60 D, 0.80 D and 0.90 D, D = Depth, 10.7 ± 0.7 m) and their corresponding environmental parameters (tide, salinity and particle size) were investigated over a year. Water sample from each layer was further separated into three fractions, which were dissolved, coarse (SPM-D, Φ ≥ 2.7 μm) and fine (SPM-F, 2.7 μm > Φ ≥ 0.7 μm) suspended particulate matters. Most of EDCs in the water column were presented in the dissolved fraction. Vertical profiles of salinity fluctuations showed that the upper water layer was most influenced by upstream flow. Estriol (E3), mestranol (Mes) and 17α-ethynylestradiol (EE2) concentrations were significantly higher in ebb tide than in flood tide, indicating that EDCs mainly came from terrestrial source, the upstream flow. Dissolved EDCs also exhibited high levels in the surface layer (0.05 D) due to the upstream source and atmosphere deposition, followed by the bottom layer (0.90 D) owing to the re-suspension of EDCs-containing sediment. Compared to the dissolved phase, the contents of BPA, Mes and EE2 in the solid phase were affected by particle size and exhibited a trend of SPM-F > SPM-D > sediment. On the other hand, the concentrations of octylphenol (OP) and t-nonylphenol (NP), the degradation products from common nonionic surfactants, in sediment were higher than those in suspended particles, and NP concentration was higher in flood tide than that in ebb tide. For both SPM-D and SPM-F, their corresponding EDCs concentrations were negatively related to SPM concentrations due to particle concentration effect (PCE). Owing to the “salting-out effect”, salinity pushed EDCs from dissolved fraction to particulate or sedimentary phase.

The contributions of abiotic and biotic processes in an estuarine aquatic environment to the removal of four phenolic endocrine-disrupting chemicals (EDCs) were evaluated through simulated batch reactors containing water-only or water-sediment collected from an estuary in South China. More than 90% of the free forms of all four spiked EDCs were removed from these reactors at the end of 28 days under aerobic conditions, with the half-life of 17α-ethynylestradiol (EE2) longer than those of propylparaben (PP), nonylphenol (NP) and 17β-estradiol (E2). The interaction with dissolved oxygen contributed to NP removal and was enhanced by aeration. The PP and E2 removal was positively influenced by adsorption on suspended particles initially, whereas abiotic transformation by estuarine-dissolved matter contributed to their complete removal. Biotic processes, including degradation by active aquatic microorganisms, had significant effects on the removal of EE2. Sedimentary inorganic and organic matter posed a positive effect only when EE2 biodegradation was inhibited. Estrone (E1), the oxidizing product of E2, was detected, proving that E2 was removed by the naturally occurring oxidizers in the estuarine water matrixes. These results revealed that the estuarine aquatic environment was effective in removing free EDCs, and the contributions of abiotic and biotic processes to their removal were compound specific.

Objective To investigate the distribution of typical EDCs in Pearl River estuaries.Methods Sur-face sediment were collected, and EDCs were extracted by accelerated solvent extraction (ASE) from sediment matrix and cleaned up by centrifugation, the target compounds were finally analyzed by GC-MS after derivati-zation by BSTFA.Results Industrial EDCs such as OP, NP, BPA, and PP, steroidal EDCs such as natural es-trogens E1, E2, and synthetical estrogen EE2 were widely detected. Except the detection percent was 88.2% for EE2, the other EDCs were detected in all the collected samples, and the concentration ranges (ng/g dw) were in the following order: NP(565.28~812.6)>BPA(42.55~248.25)>PP (93.44~109.96)>OP (3.62~11.52), E1(14.13~ 23.13), E2(6.86~15.42), and EE2(ND~23.45).Conclusion Spatial distribution of the 4 industrial EDCs and EE2 were similar, concentration in the east four outlets were higher than that in the west four outlets, and espe-cially higher in Humen estuary. Moreover, EDCs concentrations in each estuary decreased gradually with stream direction from river to ocean. Except possible point pollution source in Jitimen, E1 and E2 concentration in the other seven outlets were in the same magnitude.