RESUMEN
Polychlorinated diphenyl ethers (PCDEs) are detected in aquatic environments and demonstrate adverse effects in aquatic organisms. However, data regarding the environmental behavior of PCDEs in aquatic ecosystems are lacking. In the present study, a simulated aquatic food chain (Scenedesmus obliquus-Daphnia magna-Danio rerio) was constructed in a lab setting, and the bioaccumulation, trophic transfer, and biotransformation of 12 PCDE congeners were quantitatively investigated for the first time. The log-transformed bioaccumulation factors (BCFs) of PCDEs in S. obliquus, D. magna, and D. rerio were in the range of 2.94-3.77, 3.29-4.03, and 2.42-2.89 L/kg w.w., respectively, indicating the species-specific bioaccumulation of PCDE congeners. The BCF values increased significantly with the increasing number of substituted Cl atoms, with the exception of CDE 209. The number of Cl atoms at the para and meta positions were found to be the major positive contributing factors for BCFs in the case of the same number of substituted Cl. The lipid-normalized biomagnification factors (BMFs) of S. obliquus to D. magna, D. magna to D. rerio, and the whole food chain for the 12 PCDE congeners ranged at 1.08-2.27, 0.81-1.64, and 0.88-3.64, respectively, suggesting that some congeners had BMFs comparable to PBDEs and PCBs. Dechlorination was the only metabolic pathway observed for S. obliquus and D. magna. For D. rerio, dechlorination, methoxylation, and hydroxylation metabolic pathways were observed. 1H nuclear magnetic resonance (NMR) experiments and theoretical calculations confirmed that methoxylation and hydroxylation occurred at the ortho position of the benzene rings. In addition, reliable quantitative structure-property relationship (QSPR) models were constructed to qualitatively describe the relationships between molecular structure descriptors and BCFs for PCDEs. These findings provide insights into the movement and transformation of PCDEs in aquatic ecosystems.
Asunto(s)
Éteres Difenilos Halogenados , Contaminantes Químicos del Agua , Animales , Éteres Difenilos Halogenados/química , Cadena Alimentaria , Bioacumulación , Ecosistema , Pez Cebra , Biotransformación , Contaminantes Químicos del Agua/metabolismoRESUMEN
Due to wide applications, halophenols (HPs), especially bromophenols, chlorophenols, and fluorophenols, are commonly detected but resistant to biological removal in wastewater treatment plants (WWTPs). This study investigated the overall transformation behaviors of three representative HPs (2,4-dichlorophenol: 24-DCP, 2,4-dibromophenol: 24-DBP, 2,4-difluorophenol: 24-DFP) in six chemical oxidative systems (KMnO4, K2FeO4, NaClO, O3, UV, and persulfate (PS)). The results revealed fast removal of selected HPs by O3, PS and K2FeO4, while a large discrepancy in their removal efficiencies occurred under UV irradiation, KMnO4 oxidation and particularly chlorination. Based on the analysis of the identified intermediates and products, coupling among the five routes was the general route, and dimers were the main intermediates for HP oxidation. The effect of the halogen atom on the transformation pathways of HPs was highly reaction type dependent. Among the six chemical treatments, PS could induce HPs to yield relatively low-molecular-weight polymers and obtain the highest coupling degree. Transition state (TS) calculations showed that the H atom linked to the phenoxy group of HPs was the most easily abstracted by hydroxyl radicals to form the coupling precursor, i.e., phenoxy radicals. This high coupling behavior further resulted in the increased toxicity to green algae. Characterization revealed that HP reaction solutions treated with PS had a severely negative effect on algae growth, photosynthetic pigment synthesis, and the antioxidant enzyme system. These findings can shed light on the reaction mechanisms of advanced oxidation technologies and some risk management and control of PS technique may be considered when treating phenolic pollutants.
RESUMEN
Considering the frequent detection of polychlorinated dibenzothiophenes (PCDTs) in various environmental matrices and the potential ecological health risks, the environmental behavior of such compounds needs to be elucidated further. In this work, the sorption behavior of 2,3,7,8-tetrachlorodibenzothiophene (2,3,7,8-TCDT) onto three sediments and paddy soil from Chaohu Lake were investigated via batch equilibration experiments. From the perspective of sorption kinetics and isotherms, the sorption characteristics and mechanism of 2,3,7,8-TCDT on the above four carriers were compared, and the relationship between their structural characteristics and soil sorption capacity was discussed. Results suggested that rapid sorption played the primary role during the sorption process of 2,3,7,8-TCDT and the corresponding sorption isotherms were well fitted using the Freundlich logarithmic model. Moreover, the effects of pH and dissolved organic matter (DOM) on the sorption of 2,3,7,8-TCDT were investigated. The maximum sorption capacity of 2,3,7,8-TCDT on sediment was under acidic pH condition (pH = 4.0). Meanwhile, DOM at a low level promoted the sorption capacity of sediment toward 2,3,7,8-TCDT, while the high concentration of DOM inhibited this effect. In addition, the values of logKoc were obtained using high-performance liquid chromatography (HPLC) and did not show any significant correlation with organic carbon (OC) contents, thereby indicating that the partition effect was the dominating influencing factor for the sorption of 2,3,7,8-TCDT both on sediments and soil. This work provides useful data to understand the sorption behavior of 2,3,7,8-TCDT on sediments and soil and assess its potential environmental risk.
Asunto(s)
Contaminantes del Suelo , Suelo , Adsorción , Carbono/química , Sedimentos Geológicos/química , Lagos , Suelo/química , Contaminantes del Suelo/análisisRESUMEN
Polychlorinated diphenyl sulfides (PCDPSs) represent an emerging group of constituents that are persistent, bioaccumulative and toxic (PBT) substances of great concern in terms of human health and ecological integrity. However, little is known about the occurrence, environmental behaviour and ecological risks of PCDPSs in lake environments. In this study, the concentrations of 21 PCDPSs were determined in surface water, suspended particulate matter (SPM), sediments, and 8 fish species from Chaohu Lake, China. Eighteen PCDPS congeners were prevalently detected in the samples, with concentrations ranging from 0.272-1.69 ng/L (water), 0.477-2.03 ng/g d.w. (SPM), 0.719-4.07 ng/g d.w. (sediment) and 0-0.131 ng/g w.w. (fish), respectively. Medium- and high-chlorinated PCDPSs in SPM and sediment were significantly higher than those in water samples. Increased PCDPS concentrations were found in higher trophic level fishes and those with a demersal habitat preference, indicating their bioaccumulation and biomagnification potential. The logBCFs, BSSAFs, and BSAFs of PCDPS congeners in fishes were determined to be 3.91-5.18, 0.0500-2.33, and 0.0360-4.94 L/kg, respectively. The organic carbon normalized partition coefficients (logKoc) of PCDPSs in surface water-SPM (4.61-5.54 L/g) and surface water-sediment (4.38-5.69 L/g) systems were determined, and it was found that highly chlorinated PCDPSs were more prone to migrate from water to sediment and SPM. The toxic equivalent (TEQ) values of PCDPSs in the samples (lower than 10-1 pg/g or pg/L) and daily intake via fish consumption (0.180-0.340 µg/kg/day) were estimated for humans, and cumulative risk quotients (RQs) after correction at ten sampling sites (0.065-0.66) were calculated for green algae. The findings elucidated the environmental behaviour of PCDPSs in Chaohu Lake.