Long-term exposure to nanoplastics reshapes the microbial interaction network of activated sludge.

Wastewater treatment plants have been identified as an important gathering spot for nanoplastics, possibly having unintended impacts on important biological nutrient removal processes. The underlying effects of long-term exposure of activated sludge to nanoplastics on nutrient removal and the mechanisms involved remain unclear. This study investigated the effect of polystyrene nanoplastics (Nano-PS) on the treatment performance and microbial community structure, and network in activated sludge. The results indicate that 1000 µg/L Nano-PS had chronic negative effects on the treatment performance in a continuous test over 140 days. Nano-PS had no significant impact in the earlier stages (0-50 days). However, as exposure time increased, the removal efficiencies of chemical oxygen demand, total phosphorous, and total nitrogen (TN) decreased by 2.7, 33.2, and 23.5%, respectively, in the later stages (87-132 days). These adverse impacts further manifested as a change in the topological characteristics, forming a smaller scale, lower complexity, and weaker transfer efficiency of the microbial network. Moreover, the scale and complexity of subnetwork-nitrogen removal bacteria and subnetwork-nitrifier were inhibited, leading to an increase in the effluent TN and NH4+-N. The decreased modules and connectors (keystone taxa) likely caused the deterioration of treatment performance and functional diversity, which was consistent with the change in PICRUSt results. Less competition, denser nodes, and more complex module structures were induced as a strategy to mediate the long-term stress of nano-PS. To our knowledge, this is the first attempt to explore the long-term effects of nano-PS on the microbial interaction network of activated sludge, laying an experimental foundation for reducing the risks associated with nanoplastics.

A novel fate and transport model for evaluating the presence and environmental risk of per-/poly-fluoroalkyl substances (PFASs) among multi-media in Lingang hybrid constructed wetland, Tianjin, China.

Accurately revealing and predicting the presence and risks of per-/poly-fluoroalkyl substances (PFASs) in constructed wetlands (CWs) is great significant for the construction and management of CWs, but very challenging. In this work, a novel fate and transport model was for the first time established to evaluate the spatially continuous distribution and environmental risks of PFASs among multi-media in Lingang hybrid CW fed by industry tailwater. 20 PFASs were detected from the Lingang CW, and the total concentration of the detected PFASs in water and sediments were in the range of 38.94-81.65 ng/L and 1.23-4.31 ng/g, respectively. PFOA, PFOS and PFBS were the main pollutants in water and sediments. A fate and transport model describing the distribution characteristics and fate of PFASs in Lingang hybrid CW was constructed, and its reliability was verified. The simulated results suggested that PFASs were mainly accumulated in sediments and long-chain PFASs were more easily adsorbed by sediments compared with short-chain PFASs. According to the principal component analysis-multiple linear regression (PCA-MLR), PFASs mainly came from the tailwater from the surrounding sewage treatment plants. Besides, the environmental risks were predicted by this novel model, suggesting that the risks still cannot be neglected due to the accumulation and continuous input of PFASs although the environmental risks of Lingang CW were low. This work provides a novel model for the understanding of presence and risks of PFASs among multi-media in CWs.

Presence of polycyclic aromatic hydrocarbons among multi-media in a typical constructed wetland located in the coastal industrial zone, Tianjin, China: Occurrence characteristics, source apportionment and model simulation.

In-depth understanding and accurately predicting the occurrence and fate of polycyclic aromatic hydrocarbons (PAHs) in constructed wetlands (CWs) is extremely crucial for optimizing the CWs construction and strengthening the risk control. However, few studies have focused on the PAHs among sediment-water-plant and model simulation in CWs. In this study, sediment, surface water and reed samples were gathered and analyzed from a typical CW. The concentrations of 16 PAHs (Σ16PAHs) in sediments, surface water and reeds ranged from 620 to 4277 µg/kg, 114 to 443 ng/L and 74.5 to 362 µg/kg, respectively. The coefficients of variation (CV) were calculated as 0.796, 0.431 and 0.473 for the above three media respectively, indicating that the spatial distribution variation was medium intensity. The fugacity fraction (ff) suggested that sediments might act as the secondary release source of most PAHs. According to the diagnostic ratios and principal component analysis-multiple linear regression (PCA-MLR), PAHs in this CW mainly come from fossil fuels combustion and petroleum leakage. PAHs in sediments showed high ecological risk at water inlet and moderate risk at the other functional zones, while low risks for surface water at all functional zones. Although the human health risk assessment indicated relatively low cancer risk, the health risk still cannot be ignored with the continuous input and accumulation of exogenous PAHs. A mathematical model covering the hydraulics parameters and composition characteristics of the wetland was established, and its reliability was verified. The simulated results obtained by the established model were basically consistent with the measured values. In addition, the total remove efficiency of PAHs in surface water was 40.2%, which calculated by the simulated model. This work provides helpful insight into the comprehension of occurrence and fate of PAHs among multi-media in CWs.

An integrated migration and transformation model to evaluate the occurrence characteristics and environmental risks of Nitrogen and phosphorus in constructed wetland.

In this study, an integrated migration and transformation (IMT) model based on microbial action, plant absorption, sediment release and substrate adsorption was firstly established to evaluate the temporal-spatial distribution of N and P in Lingang hybrid constructed wetland (CW), Tianjin. Compared to the conventional transformation model that only considers the microbial action, the IMT model could accurately predict the occurrence characteristics of N and P. In Lingang CW, NO3--N (0.56-3.63 mg/L) was the most important form of N, and the TP was at a relatively low concentration level (0.04-0.07 mg/L). The spatial distribution results showed that a certain amount of N and P could be removed by CW. Form the temporal perspective, the N and P concentrations were greatly affected by the dissolved oxygen (DO). The simulated values obtained by IMT model indicated that the distribution of N and P was more affected by the temporality compared with the spatiality, which was consistent with measured values. Besides, the PCA indicated that TN, NO3--N and DO were important factors, which affected the water quality of CW. The Nemerow pollution index method based on the simulated values indicated that Lingang CW was overall moderately polluted, and the subsurface area was the main functional unit of pollutants removal in CW. This work provides a new model for accurately predicting the occurrence characteristics of N and P pollutants in CW, which is of great significance for identifying its environmental risks and optimizing the construction of wetlands.

The valence and Rydberg excited states of CH2: a theoretical exploration.

Using the completed active space second-order perturbation (CASPT2) method, valence and Rydberg excited states of CH(2) molecule are probed with the large atomic natural orbital (ANO-L) basis set. Five states are optimized and the geometric parameters are in good agreement with the available data in literatures, furthermore, the state of 2(1)B(1) is obtained for the first time. Valence and Rydberg excited states of CH(2) are also calculated for the vertical transitions with the ANO-L+ basis set that is constructed by adding a set of 1s1p1d Rydberg orbitals into the ANO-L basis set. Two Rydberg states of the p(~3)A(2) and r(~3) B(1) at 9.88 and 10.50 eV are obtained for the first time, and the 3a(1) → 3d(yz) nature of the state p(~3)A(2) and the 3a(1) → d(x2-y2) nature of the state r(~3)B(1) are confirmed.

A theoretical investigation of the excited states of OCLO radical, cation, and anion using the CASSCF/CASPT2 method.

Using the complete active space self-consistent field method with a large atomic natural orbital basis set, 10, 13, and 9 electronic states of the OClO radical, OClO(+) cation, and OClO(-) anion were calculated, respectively. Taking the further correlation effects into account, the second-order perturbation (CASPT2) calculations were carried out for the energetic calibration. The photoelectron spectroscopy of the OClO radical and OClO(-) anion were extensively studied in the both case of the adiabatic and vertical ionization energies. The calculated results presented the relatively complete assignment of the photoelectron bands of the experiments for OClO and its anion. Furthermore, the Rydberg states of the OClO radical were investigated by using multiconfigurational CASPT2 (MS-CASPT2) theory under the basis set of large atomic natural orbital functions augmented with an adapted 1s1p1d Rydberg functions that have specially been built for this study. Sixteen Rydberg states were obtained and the results were consistent with the experimental results.

Theoretical studies on the low-lying electronic states of the HSO neutral radical and its cation.

Using the complete active space self-consistent field (CASSCF) method with large atomic natural orbital (ANO-L) basis set, four electronic states of the HSO neutral radical are optimized. The vertical transitions of the HSO neutral radical are investigated by using the same method under the basis set of ANO-L functions augmented with a series of adapted 1s1p1d Rydberg functions, through which eight valence states and eight Rydberg states are probed. Ionic states of the HSO neutral radical are extensively studied in both cases of the adiabatic and vertical ionization, from which the relatively complete understanding of ionization energies is given. To include further correlation effects, the second-order perturbation method (CASPT2) is implemented, and the comparison between CASSCF and CASPT2 methods is performed.