Correlation analysis between the in vivo bioavailability and in vitro bioaccessibility of nitro PAHs in soil: Application of simplified FOREhST in vitro methods based on the Chinese pharmacopoeia.

In this study, the relative bioavailability (RBA) of nitrated polycyclic aromatic hydrocarbons (NPAHs) in soil samples (n = 30) was assessed using an in vivo mouse model. Based on the correlation between the bioaccessibility data obtained from the Tenax improved traditional Fed ORganic Estimation human Simulation Test (FOREhST) in vitro method (TITF) and the bioavailability data obtained from in vivo experiments, the TITF method was further optimized and simplified by referring to the "Pharmacopoeia of the People's Republic of China: Volume IV, 2020" to adjust the formulation and parameters of the gastrointestinal fluid (GIF) in order to establish a simpler and lower cost in vitro method for the determination of the bioaccessibilities of NPAHs. The dose-accumulation relationship of the in vivo experiment showed that the linear dose-response was better in adipose tissue (R2 = 0.77-0.93), and the accumulation of NPAHs in adipose tissue was higher than that in kidney or liver tissue. Depending on the mouse adipose model, the NPAHs-RBA ranged from 1.88 % to 73.92 %, and a strongly significant negative relationship (R2 = 0.94, p < 0.05) was found between the NPAHs-RBA and Log Kow. The simplified experiment of the TITF showed that the composition of the GIF medium had a significant effect on the bioaccessibilities of NPAHs. The NPAH bioaccessibilities measured by the Tenax improved simplified FOREhST method (TISF) (9.0-36.5 %) were higher than that of the traditional FOREhST method (6.8-22.8 %) but significantly lower than that of the TITF method (16.8-55.2 %). With an increase in the bile concentration in the GIF (from 6 to 10 g/L), the bioaccessibilities of NPAHs increased from 9.0 to 36.5 % to 12.9-42.4 %. The accuracies of the four in vitro methods for predicting the bioavailabilities of NPAHs was in the following order: Tenax improved simplified FOREhST method with increased bile concentration (TITF-IB) (R2 = 0.54-0.87) ≈ TITF (R2 = 0.55-0.85) > TISF (R2 = 0.41-0.77) > FOREhST (R2 = 0.02-0.68). These results indicated that the simple in vitro method could also effectively predict the bioavailabilities of NPAHs.

Bioaccessibility and bioavailability of NPAHs in soils using in vitro-in vivo assays: Comparison of laboratory and outdoor environmental aging effect.

Aging process is one of the most important factors that markedly reduces bioaccessibility and bioavailability (bioac-bioav) of organic contaminants. However, only few data on comparison of the effects of laboratory artificial aging (LAA) and outdoor environmental aging (OEA) processes on nitrated polycyclic aromatic hydrocarbons (NPAHs) bioac-bioav are available. In the current study, oral bioac-bioav of NPAHs in LAA and OEA soils (aging time intervals: 0, 45, 90, 120 and 150 d) were measured by in vitro traditional Fed ORganic Estimation human Simulation Test (FOREhST) and Tenax improved FOREhST (TI-FOREhST) methods, and in vivo mouse model. Tenax significantly increased the bioaccessibility of NPAHs in freshly spiked and aging soils from 0.3-40.9 % to 15.6-95.3 %, and 0.3-40.9 % to 1.0-84.5 %, respectively. Aging significantly reduced the NPAHs bioaccessibility (from 36.5 % to 10.7 %, and 12.1 % to 5.1 % as measured by FOREhST and TI-FOREhST, respectively) and bioavailability (from 27.7 % to 9.9 %, as measured by mouse model). The changes in bioac-bioav were mainly observed within the first 120 d of aging. The statistical analyses of NPAHs bioac-bioav showed no significant difference (p > 0.05) among the aging time intervals in LAA and OEA soils, which demonstrated that the LAA can relatively represent the OEA. Determination of TOC content in LAA and OEA soil can intuitively reflect whether the difference of NPAHs bioac-bioav between two aging treatment groups is significant. The mean bioaccessibility of NPAHs in soil measured by TI-FOREhST (mean 20.6 %) is closer to the bioavailability measured by mouse model (mean 19.4 %), indicating that Tenax improved in vitro method is more reliable than traditional methods, to predict the bioavailability of NPAHs.

[Degradation mechanisms of dimethyl phthalate in the UV-H2O2 system].

To investigate the photodegradation process of dimethyl phthalate (DMP) in the ultraviolet light (UV)-H2O2 system, mass spectrometer was used to identify degradation products and further more, to speculate the possible mechanisms of degradation process. Experimental results showed that the degradation efficiency of 10 mg x L(-1) DMP reached 92.3% in 90 minutes in the UV-H2O2 system, and the more H2O2 was added, the faster DMP decomposed. The pH of DMP solution decreased from the initial 6.5 to 4.98, because of the generating of organic phenolic acids and small acid molecules generated by the degradation of DMP. By the GC/MS as well as LC/MS analysis, degradation products of the DMP in the UV-H2O2 system were thought to comprise six categories, from which we could infer that hydrolysis occurs simultaneously on the two side chains of the DMP, generating phthalic acid that can quickly change to the more stable terephthalic acid. In addition, DMP could also occur benzene ring replacement as well as the ring condensed of the side chains. Finally, by the role of *OH, DMP and its aromatic intermediates occurred ring-opening reaction, and benzene ring was destroyed and generated organic acids of small molecular, which was further mineralized to CO2 and water.

Feasibility of a two-stage reduction/subsequent oxidation for treating Tetrabromobisphenol A in aqueous solutions.

A "two-stage reduction/subsequent oxidation" (T-SRO) process consists of Fe-Ag reduction and Fenton-like oxidation under ultrasound (US) radiation. Due to the refractory oxidation of brominated flame retardant, T-SRO was employed to remove Tetrabromobisphenol A (TBBPA) by the combination of first debromination and succeeding oxidation. It indicated that the T-SRO process resulted in a complete decrease in TBBPA concentration and a 99.2% decrease in BPA concentration. The T-SRO process for the removal of TBBPA is much effective than Fenton-like oxidation of TBBPA alone. The result showed that US radiation improved the Fenton-like oxidation rate of BPA solutions. The addition of dissolved iron into the Fenton-like oxidation system could accelerate the first 2 min reaction, but had little effect on the following process. The main intermediate products resulting from TBBPA reduction and BPA oxidation were identified by GC-MS and LC-MS/MS. On the basis of this analysis, reactions with •OH radical were identified as the major chemical pathways during BPA oxidation.

[Sorption and desorption behavior of the herbicide mefenacet on soils].

The sorption-desorption experiments of the herbicide mefenacet on five soils with different physicochemical properties were conducted using bath equilibrium methods, and the effects of soil organic matter and pH value on sorption of this herbicide were also investigated. The results showed that the sorption and desorption behaviors of mefenacet on soils could be well described by both the linear model and Freundlich model. Sorption distribution coefficients K(oc) for five tested soil are between 849.5 L x kg(-1) and 1 818.8 L x kg(-1), which shows that mefenacet can be well adsorbed on soils. It is found that the sorption coefficients, K(d), K(f), and K(f) (1/n) had good correlation with organic matter content (OM) in soils. It is obviously suggested that organic matter was the dominant factor affecting the sorption of mefenacet on soils. For the same soil, the sorption amount of mefenacet decreased with the increase of pH value. The desorption hysteresis of mefenacet was revealed in the single-cycle sorption and desorption experiments, which indicated a weak transferability of this herbicide in soils.

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin.

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied. Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time, the analysis of the extracts from the soil was carried out using gas chromatography (GC). The photodegradation of pyrethroids in water system was conducted under UV irradiation. The effect of Cu2+ on the pesticides degradation was measured with half life (t0.5) of degradation. It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed. But Cu2+ could accelerate photodegradation of the pyrethroids in water. The t0.5 for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil. As for photodegradation, t0.5 for cyhalothrin reduced from 173.3 to 115.5 min and for cypermethrin from 115.5 to 99.0 min. The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms. However, it had catalyst tendency for photodegradation in water system. The difference for the degradation efficiency of pyrethroid isomers in soil was also observed. Copper could obviously accelerate the degradation of some special isomers.

[Microwave assisted photocatalytic degradation of phenol in aqueous solution].

Experimental study on microwave assisted photocatalytic degradation of phenol in aqueous solution was carried out with modified domestic microwave oven, electrodeless discharge lamps (EDLs) and TiO2 catalyst. Results showed that the removal rate of phenol in the MAPC process was 92% after 30 min reaction. Loss of total organic carbon (TOC) was 84% . The optimal conditions for the MAPC method were 10 mg/L phenol, 900 W MW output energy, 50 mL solution volume, EDLs-3, 1-4 g/l. catalyst dosage and 15 mL/min of flowing velocity in the circulating mode. The MAPC process was promising in treating phenolic waste water.

Photocatalytic degradation of methylene blue in TiO2 aqueous suspensions using microwave powered electrodeless discharge lamps.

Photocatalytic degradation of methylene blue (MB) in TiO(2) aqueous suspensions using microwave (MW) powered electrodeless discharge lamps (EDLs) was studied. MB of initial concentration 100 mg/l was mainly decomposed in the process of photocatalytic degradation using EDLs (PCD/EDLs) after 15 min of irradiation. The corresponding mineralization efficiency was 45%. The influence of factors as EDLs, solution volume and TiO(2) catalyst dosage on the decomposition of MB in the PCD/EDLs process was also investigated. The optimal decomposition efficiency was observed when EDLs-4 (four 10 mm x 50 mm EDLs), solution volume of 50 ml and TiO(2) catalyst dosage of 1-4 g/l were used in the study. The PCD/EDLs process was promising in treating MB polluted water.

Enhanced photocatalytic activity of nanotube-like titania by sulfuric acid treatment.

The TiO2 nanotube sample was prepared via a NaOH solution in a Teflon vessel at 150 degrees C. The as-prepared nanotubes were then treated with H2 SO4 solutions. The TiO2 nanotube has a crystalline structure with open-ended and multiwall morphologies. The TiO2 nanotubes before and after surface acid treatment were characterized by X-ray diffraction (XRD), scanning electron microscopy(SEM), transmission electron microscopy (TEM) and UV-VIS dispersive energy spectrophotometry (DRS). The photocatalytic activity of the samples was evaluated by photocatalytic degradation of acid orange II in aqueous solutions. It was found that the order of photocatalytic activity was as follows: TiO2 nanotubes treated with 1.0 mol/L H2SO4 solution (TiO2 (1.0M H2SO4) snanotubes) > TiO2 nanotubes treated with 0.2 mol/L H2SO4 solution (TiO2 (0.2M H2O4) nanotubes) > TiO2 nanotubes > TiO2 powder. This was attributed to the fact that TiO2 nanotubes treated with H2SO4 was composed of smaller particles and had higher specific surface areas. Furthermore, the smaller TiO2 particles were beneficial to the transfer and separation of photo-generated electrons and holes in the inner of and on the surface of TiO2 particles and reduced the recombination of photo-generated electrons and holes. Acid treatment was particularly effective for TiO2 nanotubes, this increase in activity was correlated with the concentration of H2 SO4 solution.