Comparative study of reactive oxygen species and tetracycline degradation pathways in catalytic peroxodisulfate activation by asymmetric mesoporous TiO2 and the corresponding controlled-release materials.

The removal of trace amounts of antibiotics from water environments while simultaneously avoiding potential environmental hazards during the treatment is still a challenge. In this work, green, harmless, and novel asymmetric mesoporous TiO2 (A-mTiO2) was combined with peroxodisulfate (PDS) as active components in a controlled-release material (CRM) system for the degradation of tetracycline (TC) in the dark. The formation of reactive oxygen species (ROS) and the degradation pathways of TC during catalytic PDS activation by A-mTiO2 powder catalysts and the CRMs were thoroughly studied. Due to its asymmetric mesoporous structure, there were abundant Ti3+/Ti4+ couples and oxygen vacancies in A-mTiO2, resulting in excellent activity in the activation of PDS for TC degradation, with a mineralization rate of 78.6%. In CRMs, ROS could first form during PDS activation by A-mTiO2 and subsequently dissolve from the CRMs to degrade TC in groundwater. Due to the excellent performance and good stability of A-mTiO2, the resulting constructed CRMs could effectively degrade TC in simulated groundwater over a long period (more than 20 days). From electron paramagnetic resonance analysis and TC degradation experiments, it was interesting to find that the ROS formed during PDS activation by A-mTiO2 powder catalysts and CRMs were different, but the degradation pathways for TC were indeed similar in the two systems. In PDS activation by A-mTiO2, besides the free hydroxyl radical (·OH), singlet oxygen (1O2) worked as a major ROS participating in TC degradation. For CRMs, the immobilization of A-mTiO2 inside CRMs made it difficult to capture superoxide radicals (·O2-), and continuously generate 1O2. In addition, the formation of sulfate radicals (·SO4-), and ·OH during the release process of CRMs was consistent with PDS activation by the A-mTiO2 powder catalyst. The eco-friendly CRMs had a promising potential for practical application in the remediation of organic pollutants from groundwater.

Pulmonary Hypertension Induces Serotonin Hyperreactivity and Metabolic Reprogramming in Coronary Arteries via NOX1/4-TRPM2 Signaling Pathway.

BACKGROUND: Clinical evidence revealed abnormal prevalence of coronary artery (CA) disease in patients with pulmonary hypertension (PH). The mechanistic connection between PH and CA disease is unclear. Serotonin (5-hydroxytryptamine), reactive oxygen species, and Ca2+ signaling have been implicated in both PH and CA disease. Our recent study indicates that NOXs (NADPH [nicotinamide adenine dinucleotide phosphate] oxidases) and TRPM2 (transient receptor potential cation channel subfamily M member 2) are key components of their interplay. We hypothesize that activation of the NOX-TRPM2 pathway facilitates the remodeling of CA in PH. METHODS: Left and right CAs from chronic hypoxia and monocrotaline-induced PH rats were collected to study vascular reactivity, gene expression, metabolism, and mitochondrial function. Inhibitors or specific siRNA were used to examine the pathological functions of NOX1/4-TRPM2 in CA smooth muscle cells. RESULTS: Significant CA remodeling and 5-hydroxytryptamine hyperreactivity in the right CA were observed in PH rats. NOX1/4-mediated reactive oxygen species production coupled with TRPM2-mediated Ca2+ influx contributed to 5-hydroxytryptamine hyperresponsiveness. CA smooth muscle cells from chronic hypoxia-PH rats exhibited increased proliferation, migration, apoptosis, and metabolic reprogramming in an NOX1/4-TRPM2-dependent manner. Furthermore, the NOX1/4-TRPM2 pathway participated in mitochondrial dysfunction, involving mitochondrial DNA damage, reactive oxygen species production, elevated mitochondrial membrane potential, mitochondrial Ca2+ accumulation, and mitochondrial fission. In vivo knockdown of NOX1/4 alleviated PH and suppressed CA remodeling in chronic hypoxia rats. CONCLUSIONS: PH triggers an increase in 5-hydroxytryptamine reactivity in the right CA and provokes metabolic reprogramming and mitochondrial disruption in CA smooth muscle cells via NOX1/4-TRPM2 activation. This signaling pathway may play an important role in CA remodeling and CA disease in PH.

Comparative study of the performance of controlled release materials containing mesoporous MnOx in catalytic persulfate activation for the remediation of tetracycline contaminated groundwater.

Controlled release materials (CRMs) are an emerging oxidant delivery technique for in-situ chemical oxidation (ISCO) that solve the problems of contaminant rebound, backflow and wake during groundwater remediation. CRMs were fabricated using ordered mesoporous manganese oxide (O-MnOx) and sodium persulfate (Na2S2O8) as active components, for the removal of antibiotic pollutants from groundwater. In both static and dynamic groundwater environments, persulfate can first be activated by O-MnOx within CRMs to form sulfate radicals and hydroxyl radicals, with these radicals subsequently dissolving out from the CRMs and degrading tetracycline (TC). Due to their excellent persulfate activation performance and good stability, the constructed CRMs could effectively degrade TC in both static and dynamic simulated groundwater systems over a long period (>21 days). The TC removal rate reached >80 %. Changing the added content of O-MnOx and persulfate could effectively regulate the performance of the CRMs during TC degradation in groundwater. The process and products of TC degradation in the dynamic groundwater system were the same as in the static groundwater system. Due to the strong oxidizing properties of sulfate radicals and hydroxyl radicals, TC molecules were completely mineralized within the groundwater systems, resulting in only trace levels of degradation products being detectable, with low- or non-toxicity. Therefore, the CRMs constructed in this study exhibited good potential for practical application in the remediation of organic pollutants from both static and dynamic groundwater environments.

[Effects of clay minerals on the transport of perfluorooctanoic acid in saturated porous media]. / é»åœŸçŸ¿ç‰©å¯¹å ¨æ°Ÿè¾›é ¸åœ¨é¥±å’Œå¤šå­”ä»‹è´¨ä¸­è¿ç§»è¡Œä¸ºçš„å½±å“.

We examined the effects of representative clay minerals, montmorillonite (M) and kaolin (K), on perfluorooctanoic acid (PFOA) transport under saturated conditions. Results showed that low amounts of M or K addition increased and high addition amounts reduced PFOA retardation in quartz sand during the transport. With increasing addition of clay minerals (0-50%, weight ratio), the retardation factor of the M-added system increased from 1.03±0.00 to 1.31±0.03 and then decreased to 0.72±0.06, while that of the K-added system increased to 1.30±0.02 and then decreased to 0.49±0.11. Results of the tracer experiment showed that low amount of M or K addition did not produce preferential flow, while high amount addition induced obvious preferential flow, which resulted in the decrease in PFOA retardation. In addition, due to limitations of the highly negative-charged surface of the M or K modified sand and the solid-liquid ratio of column experiment, the modified M or K sand had low adsorption capacity of PFOA and thus almost did not affect PFOA retention. However, the adsorption and desorption of PFOA by clay minerals might still be responsible for the increases in PFOA retardation with low amount of M or K addition. The results are of great significance for accurately assessing the transport process and eco-environmental risks of PFOA in soil-groundwater systems.

Characterizing property and treatability of dissolved effluent organic matter using size exclusion chromatography with an array of absorbance, fluorescence, organic nitrogen and organic carbon detectors.

In this study, size exclusion chromatography with an array of absorbance, fluorescence, organic nitrogen and organic carbon detectors was used for characterizing property and treatability of effluent organic matter (EfOM) from 12 wastewater treatment plants. According to their apparent molecular weight (AMW), EfOM fractions were assigned to biopolymers (>20 kDa), humic substances that comprise sub-fractions of humic-like acids (HA-I & HA-II, 2.3-7.0 kDa) and fulvic-like acids (FA, 1.5-2.3 kDa), building blocks (0.55-1.5 kDa) and low molecular weight neutral substances (<550 Da). The fractions of biopolymers and low molecular weight neutral substances didn't show humic-like fluorescence, while the fractions of HA-II, FA and building blocks usually had signatures of both humic-like and protein-like fluorescence. Humic substances generally contributed the largest proportion of dissolved organic carbon and nitrogen (DOC & DON) in effluents. Coagulation removed EfOM fractions following the order of biopolymers > HA subfraction > FA subfraction > building blocks, while little removal of protein-like fluorescence in HA-II and FA subfractions was detected. Anion exchange treatment could effectively reduce DOC and DON concentrations; the sequence of the treatment efficiency was humic substances > biopolymers > building blocks. Increasing O3 doses caused DOC and DON of EfOM to be gradually transformed from large AMW fractions into small AMW fractions, while chromophores and fluorophores in HA subfractions were relatively more refractory than those in the other fractions. Size exclusion chromatography with multiple detectors are suggested to be an informative technique for estimating treatability of EfOM by advanced wastewater treatment processes.

Developing surrogate indicators for predicting suppression of halophenols formation potential and abatement of estrogenic activity during ozonation of water and wastewater.

This study focused on developing surrogate indicators for predicting oxidation of phenolic groups in dissolved organic matter (DOM), suppression of halophenols' formation potential and abatement of estrogenic activity during ozonation of water and wastewater. The evolution of pH-dependent differential absorbance spectra suggests that O3 preferentially reacts with the DOM phenolic moieties and less so with the aromatic carboxylic groups with increasing O3/DOC (dissolved organic carbon) ratios and changes of UV absorbance and fluorescence. When ozonation used as pretreatment, the formation of halophenols in subsequent chlorination decreased linearly with increasing O3 doses or changes of UV absorbance until it reached 85% suppression of the halophenols' formation from unaltered DOM. The thresholds of decreases of UVA254, UVA280 and humic-like fluorescence corresponding to 85% suppression of halophenols' formation were in the range of 25%-30%, 30%-35% and 30%-45%, respectively. Pre-ozonation also showed a moderate suppression of haloacetic acids (HAAs) formation potentials, ≤26.5% for reverse osmosis isolate of Suwannee River natural organic matter and ≤31.5% for Yangtze River at applied O3 doses. Measurement of changes of estrogenic activity during ozonation of water and wastewater showed that to attain a >90% abatement of estrogenic activity, the corresponding thresholds of decreases of UVA254, UVA280 and humic-like fluorescence were ∼30%, ∼40%, and ∼70%, respectively. Bromate formation was also suppressed to below 10 µg/L before these thresholds. This study suggests that optimal ozonation conditions and a balance between control of disinfection byproducts (halophenols, HAAs and bromate) and elimination of estrogenic activity can be reached based on online data.

Applying UV absorbance and fluorescence indices to estimate inactivation of bacteria and formation of bromate during ozonation of water and wastewater effluent.

Ozone is an effective oxidant and disinfectant commonly used for elimination of micropollutants and inactivation of resistant microbes. However, undesirable oxidation/disinfection byproducts such as bromate might form during ozonation. In this study, the UV absorbance and fluorescence indices were applied as surrogate indicators for predicting the inactivation of bacteria and formation of bromate during ozonation of water and wastewater effluents. The inactivation efficiencies of lab-cultured Escherichia coli (E. coli) and autochthonous bacteria were measured by plating (for E. coli only) and flow cytometry with fluorescence staining. During ozonation of E. coli spiked into wastewater effluents (∼106 cell/mL), the priority of inactivation efficiency determined by different cell viability methods were in the order of CFU > membrane damage > DNA damage. Approximately, 99% membrane damage and/or 90% DNA damage are conservatively supposed as an indicator for sufficient bacterial inactivation as well as degradation of antibiotic resistance genes. The related required O3 dosing thresholds for sufficient inactivation of E. coli and autochthonous bacteria refer to ∼0.6 O3/DOC (g/g), ∼50% decrease of UVA254, ∼60% decrease of UVA280, or ∼80% decrease of humic-like fluorescence. Within the range of 106-108 cell/mL, the bacterial concentration did not have significant effects on the required thresholds of the specific O3 doses or spectroscopic indicators required for bacterial inactivation. The addition of 50 mM tert-BuOH as ·OH scavenger increased the required specific ozone doses but decreased the losses of spectroscopic indicators necessary for sufficient bacterial inactivation, and also suggested that the membrane/DNA damages for bacterial inactivation were mainly attributed to the direct O3 attacks. The bromate concentration was determined using ion chromatography with MS/MS detection. The results showed that when O3 was dosed at the required thresholds for sufficient bacterial inactivation, bromate formation could usually be suppressed below 10 µg/L. The present work supports that it is possible to reach a balance between bacterial inactivation and bromate formation.

A new 5(6→7)abeo-sterol from Podocarpus fleuryi.

A new 5(6→7)abeo-sterol, podosterol (1), together with 20 known compounds, were isolated from the leaves of Podocarpus fleuryi. Their structures were elucidated by means of extensive spectroscopic analysis. Podosterol was assessed for its cytotoxicity against five human tumor cell lines (HL-60, SMMC-7721, A-549, MCF-7, and SW-480), and the result showed that it had no activity.

[Laboratory Investigation of DNAPL Migration Behavior and Distribution at Varying Flow Velocities Based on Light Transmission Method].

The migration and distribution of dense non-aqueous phase liquid (DNAFL) in subsurtace are attectea ny many factors. We selected PCE as the substitute contaminant, and performed several well-controlled two-dimensional sandbox experiments to investigate the effect of flow velocity on DNAPL infiltration and redistribution. Light transmission method (LTM) was used to monitor the transport process of DNAPL in the sandbox and quantitatively measure DNAPL saturation. The spatial moments based on measured DNAPL saturation were used to describe the average spatial behavior of DNAPL plume at various times. Experimental results showed a strong correlation between results obtained by LTM and the known amounts of DNAPL added into the sandbox (R2 >0.98). The LTM accurately reflected the infiltration and redistribution processes. The results of DNAPL saturation and first moment (mass center) showed that the increased velocity promoted not only lateral but also vertical migration, leading to an inclined percolation path. Also vertical migration reacted more sensitive to flow velocity. The second moment (spread variance) showed that the increased velocity promoted lateral and vertical spread, increasing the pollution scope. The histogram of DNAPL saturation showed a unimodal distribution at low flow velocity, but showed a bimodal distribution at lager flow velocity, and the distance between two peaks became higher with the increasing flow velocity.

[Models for quantification of fluid saturation in two-phase flow system by light transmission method and its application].

Based on light transmission method in quantification of liquid saturation and its application in two-phase flow system, two groups of sandbox experiments were set up to study the migration of gas or Dense Non-Aqueous Phase Liquids (DNAPLs) in water saturated porous media. The migration of gas or DNAPL was monitored in the study. Two modified Light Intensity-Saturation (LIS) models for water/gas two-phase system were applied and verified by the experiment data. Moreover two new LIS models for NAPL/water system were developed and applied to simulate the DNAPL infiltration experiment data. The gas injection experiment showed that gas moved upward to the top of the sandbox in the form of 'fingering' and finally formed continuous distribution. The results of DNAPL infiltration experiment showed that TCE mainly moved downward as the result of its gravity, eventually formed irregular plume and accumulated at the bottom of the sandbox. The outcomes of two LIS models for water/gas system (WG-A and WG-B) were consistent to the measured data. The results of two LIS models for NAPL/water system (NW-A and NW-B) fit well with the observations, and Model NW-A based on assumption of individual drainage gave better results. It could be a useful reference for quantification of NAPL/water saturation in porous media system.

[An integrated assessment method of ecological quality status in coastal waters: taking Tong'an Bay as a case].

Based on the integrated assessment methods of ecological quality status (EcoQS) in coastal waters abroad as well as the domestic related research status, 11 indices were selected from the biotic and physicochemical elements of water and sediment to built an integrated EcoQS assessment index system, and, with the comprehensive consideration of domestic and international evaluation standards, 5 levels of EcoQS classified as "high, good, moderate, poor, and bad" were determined. Then, an integrated assessment method of EcoQS in coastal waters was established by using analytic hierarchy process (AHP) and fuzzy mathematics method, and tested by the analysis of the correlations between the EcoQS grade and the major anthropogenic disturbances and pollutant concentrations of Tong' an Bay. The EcoQS of Tong' an Bay was assessed as moderate, i.e., the Bay was moderately disturbed and in transitional to poor status. The established integrated assessment method could not only reflect the major anthropogenic environmental pressure and risk factors, but also give an early warning of the pollutants satisfied by law in the study area.

[Study on the influence of bioclogging on permeability of saturated porous media by experiments and models].

This paper studied on the influence of bioclogging on permeability of saturated porous media. Laboratory hydraulic tests were conducted in a two-dimensional C190 sand-filled cell (55 cm wide x 45 cm high x 1.28 cm thick) to investigate growth of the mixed microorganisms (KB-1) and influence of biofilm on permeability of saturated porous media under condition of rich nutrition. Biomass distributions in the water and on the sand in the cell were measured by protein analysis. The biofilm distribution on the sand was observed by confocal laser scanning microscopy. Permeability was measured by hydraulic tests. The biomass levels measured in water and on the sand increased with time, and were highest at the bottom of the cell. The biofilm on the sand at the bottom of the cell was thicker. The results of the hydraulic tests demonstrated that the permeability due to biofilm growth was estimated to be average 12% of the initial value. To investigate the spatial distribution of permeability in the two dimensional cell, three models (Taylor, Seki, and Clement) were used to calculate permeability of porous media with biofilm growth. The results of Taylor's model showed reduction in permeability of 2-5 orders magnitude. The Clement's model predicted 3%-98% of the initial value. Seki's model could not be applied in this study. Conclusively, biofilm growth could obviously decrease the permeability of two dimensional saturated porous media, however, the reduction was much less than that estimated in one dimensional condition. Additionally, under condition of two dimensional saturated porous media with rich nutrition, Seki's model could not be applied, Taylor's model predicted bigger reductions, and the results of Clement's model were closest to the result of hydraulic test.

[Biological responses of maize seedlings to single and combined stress of cadmium and phenanthrene].

Maize (Zea mays L.) pot-culture experiments were conducted in this study for exploring the biological responses of maize seedlings to single and joint stress of Cadmium (Cd) and phenanthrene. The results showed that single-Cd treatment with Cd concentration ranging from 0 to 50 mg/kg had no significant influences on the above-ground biomass, root biomass, and the soluble protein of maize seedlings; with the increase of Cd concentrations, the maize leaf SOD activities appeared as an increasing-decreasing trend, while the POD, CAT, APX activities increased persistently. The APX is very sensitive to Cd stress, which increased 38% than control treatment at lower Cd treatment (1 mg/kg). The accumulation of O2-* is one of the main cause of single-Cd toxicity. Under the Cd-phenanthren combined stress, the SOD activity increased at lower Cd concentration (1 mg/kg) , which can reached to 1.66 times of control treatment, and decreased when Cd concentration becomes high. The SOD activity is a sensitive index in response to the Cd-phenanthren combined pollution. Unlike SOD activity, the activities of POD, CAT and APX were obviously induced by combined pollution of Cd and phenanthren; but these enzyme activities decreased when compared with the single-Cd stress, which suggested that the combined toxicity of Cd and phenanthrene is stronger than the single-Cd stress. And the accumulation of O2-* and *OH is one of the main cause of Cd-phenanthrene combined toxicity.

[Three-dimensional fluid attenuated inversion recovery imaging at 3T MRI in sudden deafness: its findings and relationship with the prognosis].

OBJECTIVE: To investigate inner ear of patients with sudden deafness with three-dimensional fluid attenuated inversion recovery (3D FLAIR) MRI, and the relationship between the results of 3D FLAIR and the prognosis. METHODS: Twenty-three patients with sudden deafness received 3D FLAIR at 3T MRI, and the signals of inner ear were recorded. Hearing levels were evaluated at initial visit and after treatment. The relationship between 3D FLAIR findings and hearing prognosis was evaluated. RESULTS: Eight patients with sudden deafness showed high signals in the affected cochlea on 3D FLAIR, the others of affected cochlea and all of contralateral cochlea showed no signal on 3D FLAIR. The age, sex, affected side, period to initial visit and initial audiogram had no difference between cochlea no signal group and high signal group. The average auditory threshold (x±s) in cochlea high signal group (90±21) dB HL was significant higher than that in cochlea no signal group (60±28) dB HL, P<0.05 at patients' discharge. After treatment, in cochlea no signal group, two cases' hearing was complete recovered, remarkable improvement in five cases, slight improvement in two cases and no change in six cases. In cochlea high signal group, hearing was slight improvement in one case and no change in seven cases. The prognosis was significant difference between two groups. Five of seven patients with vertigo and sudden deafness showed high signal in affected side vestibule on 3D FLAIR, and the hearing of whom had no change after treatment. CONCLUSION: 3D FLAIR can show high signal in affected inner ear in sudden deafness patients, and which is related to a poor hearing prognosis.

[Study on the start-up of an innovative polyethylene carrier biotrickling filter treating waste gas containing hydrogen sulphide].

Start-up of an innovative biotrickling bed packed with high density polyethylene carrier was studied. Two biofilm formation methods, continuous liquid stream (CLS) and gas-liquid phase joint (GLJ) biofilm formation, were studied for a quick start-up of biotrickling bed reactor treating gaseous hydrogen sulfide. Results show that the start-up time of the former is shorter, i. e. about 7 d at temperature 20- 28 degrees C . More steady performance was found in the reactor with CLS biofilm formation when sudden changes of GRT and inlet sulfide concentration happened. The removal efficiency of the former kept above 95% when inlet hydrogen sulphide concentration below 343 mg/m(3). Furthermore, the removal efficiency of S2- from the liquid used as the monitoring parameter of biofilm formation is suggested. After start-up period accomplished, no notable influence observed on removal efficiency when reducing supply of carbon source in trickling liquid through two different methods. The results show that the elimination of hydrogen sulphide in waste gas mainly attributed to autotrophic bacteria.