Volatile organic compounds generation pathways and mechanisms from microplastics in water: Ultraviolet, chlorine and ultraviolet/chlorine disinfection.

Disinfection in water treatments induces microplastics (MPs) to produce various derivative products, among which the volatile organic compounds (VOCs) are still poorly understood. Ultraviolet (UV), chlorine and UV/chlorine disinfections were used to treat polypropylene (PP), polystyrene (PS) and polyvinylchloride (PVC) in this study. Modifications were observed on the MP surfaces, including melting, cracks, folds, and even forming oxygen-containing structures, resulting in the release of a diversity of VOCs. The polymer types of MPs influenced the VOCs characteristics. PP released alkanes, alkenes and aldehydes, while PVC released alkanes, alkenes and halogenated hydrocarbons. VOCs from PS were dominated by unique aromatic alkanes, alkenes and aldehydes. These derived VOCs are generated during different disinfections with distinct mechanisms. UV-C at 254 nm induced direct scission and radical oxidation on MPs. The derived VOCs were mainly bond-breaking fragments. Chlorination relied on HOCl/OCl- electrophilic reactions, resulting fewer VOCs since C-C skeleton MPs have strong resistance to electrophilic reactions. UV/chlorination promotes the generation of chlorine radicals and hydroxyl radicals, thereby causing oxidative damage. Various oxidized VOCs, such as benzaldehyde and acetophenone, were formed. The disinfection reactions can produce various VOCs from MPs, posing potential risks to the ecological environment and human beings.

[Chemical constituents from Pulsatillae Radix].

Chemical constituents of ethanol extract of Pulsatillae Radix were investigated. The n-butanol fraction of ethanol extract of Pulsatillae Radix was isolated and purified by macroporous resin and silica gel column chromatography and semi-preparative high performance liquid chromatography. The triterpenoid glycosides were identified by multiple spectral methods. Six compounds were obtained from the n-butanol fraction of ethanol extract of Pulsatillae Radix and identified as 23-aldehyde-cussosaponin C(1), cussosaponin C(2), anemoside B4(3), akebia saponin D(4), pulchinenoside E3(5), and hederacoside C(6). Among them, compound 1 was a new compound.

Ultrasonic-assisted extraction and adsorption separation: Large-scale preparation of trans-ε-Viniferin, suffruficosol B and trans-Gnetin H for the first time.

In this study, a Standard Operating Procedure (SOP) for the large-scale extraction, enrichment, and separation of suffruticosol B (SB), trans-ε-Viniferin (TV), trans-gnetin H (TG) from oil tree peony seeds shell (PSS) was successfully constructed. The ultrasonic-assisted extraction (UAE), macroporous adsorption resin (MAR), and column chromatography (CC) were employed to extract, enrich and separate SB, TV and TG from PSS, and the conditions were optimized. The results implied that SB (1.6937 g), TV (0.5884 g) and TG (3.8786 g) with the purity of 99.67 %, 99.32 % and 98.54 %, respectively, were obtained after the extraction, enrichment and separation. The total yields of the SB, TV and TG were 0.61 mg/g, 0.02 mg/g and 6.64 mg/g with the total extraction rates at 70.55 %, 69.77 % and 78.36 %, respectively. This is the first report on the large-scale extraction, enrichment and separation of oligostilbenes. The SOP in this paper could produce high purity SB, TV and TG, and provide a new idea for PSS as a new oligostilbene resource. The study expands the new development and research field of PSS and provides theoretical support for the green utilization of oil tree peony.

Multi-phase distribution and comprehensive ecological risk assessment of heavy metal pollutants in a river affected by acid mine drainage.

To date, there is a lack of a comprehensive research on heavy metals detection and ecological risk assessment in river water, sediments, pore water (PW) and suspended solids (SS). Here, the concentrations of heavy metals, including Cu, Zn, Mn, Cd, Pb and As, and their distribution between the four phases was studied. Samples for analysis were taken from twelve sites of the Hengshi River, Guangdong Province, China, during the rainy and dry seasons. A new comprehensive ecological risk index (CERI) based on considering metal contents, pollution indices, toxicity coefficients and water categories is offered for prediction of potential risk on aquatic organisms. The results of comprehensive analysis showed that the highest concentrations of Cu, Zn and Mn of 6.42, 87.17 and 98.74mg/L, respectively, in PW were comparable with those in water, while concentrations of Cd, Pb and As of 609.5, 2757 and 96.38µg/L, respectively, were 2-5 times higher. The sum of the exchangeable and carbonate fractions of target metals in sediments followed the order of Cd > Mn > Zn > Pb > Cu > As. The distribution of heavy metals in phases followed the order of sediment > SS > water > PW, having the sum content in water and PW lower than 2% of total. The elevated ecological risk for a single metal and the phase were 34,585 for Cd and 1160 for water, respectively, implied Cd as a priority pollutant in the considered area. According to the CERI, the maximum risk value of 769.3 was smaller than 1160 in water, but higher than those in other phases. Out of considering the water categories and contribution coefficients, the CERI was proved to be more reliable for assessing the pollution of rivers with heavy metals. These results imply that the CERI has a potential of adequate assessment of multi-phase composite metals pollution.

Distribution, partition and removal of polycyclic aromatic hydrocarbons (PAHs) during coking wastewater treatment processes.

In this study, we report the performance of a full-scale conventional activated sludge (A-O1-O2) treatment in eliminating polycyclic aromatic hydrocarbons (PAHs). Both aqueous and solid phases along with the coking wastewater treatment processes were analyzed for the presence of 18 PAHs. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent and sludge samples. In the coking wastewater treatment system, 4-5 ring PAHs were the dominant compounds, while 4 rings PAHs predominated in the sludge samples. Over 98% of the PAH removal was achieved in the coking wastewater treatment plant (WWTP), with the total concentration of PAHs being 21.3 ± 1.9 µg L(-1) in the final effluent. During the coking wastewater treatment processes, the association of the lower molecular weight PAH with suspended solids was generally less than 60%, while the association of higher molecular weight PAHs was greater than 90%. High distribution efficiencies (Kdp and Kds) were found, suggesting that adsorption was the potential removal pathway of PAHs. Finally, the mass balances of PAHs in various stages of the coking WWTP were obtained, and the results indicated that adsorption to sludge was the main removal pathway for PAHs in the coking wastewater treatment processes.

Degradation of polycyclic aromatic hydrocarbons in a coking wastewater treatment plant residual by an O3/ultraviolet fluidized bed reactor.

Coking wastewater treatment plant (CWWTP) represents a typical point source of polycyclic aromatic hydrocarbons (PAHs) to the water environment and threatens the safety of drinking water in downstream regions. To enhance the removal of residual PAHs from bio-treated coking wastewater, a pilot-scale O3/ultraviolet (UV) fluidized bed reactor (O3/UV FBR) was designed and different operating factors including UV irradiation intensity, pH, initial concentration, contact time, and hydraulic retention time (HRT) were investigated at an ozone level of 240 g h(-1) and 25 ± 3 °C. A health risk evaluation and cost analysis were also carried out under the continuous-flow mode. As far as we know, this is the first time an O3/UV FBR has been explored for PAHs treatment. The results indicated that between 41 and 75 % of 18 target PAHs were removed in O3/UV FBR due to synergistic effects of UV irradiation. Both increased reaction time and increased pH were beneficial for the removal of PAHs. The degradation of the target PAHs within 8 h can be well fitted by the pseudo-first-order kinetics (R (2) > 0.920). The reaction rate was also positively correlated with the initial concentrations of PAHs. The health risk assessment showed that the total amount of carcinogenic substance exposure to surface water was reduced by 0.432 g day(-1). The economic analysis showed that the O3/UV FBR was able to remove 18 target PAHs at a cost of US$0.34 m(-3). These results suggest that O3/UV FBR is efficient in removing residuals from CWWTP, thus reducing the accumulation of persistent pollutant released to surface water.

The occurrence and fate of phenolic compounds in a coking wastewater treatment plant.

The occurrence of 14 phenolic compounds (PCs) was assessed in the raw, treated wastewater, dewatered sludge and gas samples from a coking wastewater treatment plant (WWTP) in China. It was found that 3-cresol was the dominant compound in the raw coking wastewater with a concentration of 183 mg L(-1), and that chlorophenols and nitrophenols were in the level of µg L(-1). Phenol was the dominant compound in the gas samples, while 2,4,6-trichlorophenol predominated in the dewatered sludge sample. The anaerobic and aerobic tanks played key roles in the elimination of chlorophenols and phenols, respectively. Analysis of daily mass flows of PCs in WWTP showed that 89-98% of phenols and 83-89% of nitrophenols were biodegraded, and that 44-69% of chlorophenols were adsorbed to sludge, indicating that the fate of PCs was highly influenced by their biodegradability and physical-chemical property.

Identification and removal of polycyclic aromatic hydrocarbons in wastewater treatment processes from coke production plants.

Identification and removal of polycyclic aromatic hydrocarbons (PAHs) were investigated at two coke plants located in Shaoguan, Guangdong Province of China. Samples of raw coking wastewaters and wastewaters from subunits of a coke production plant were analyzed using gas chromatography-mass spectrometry (GC/MS) to provide a detailed chemical characterization of PAHs. The identification and characterization of PAH isomers was based on a positive match of mass spectral data of sample peaks with those for PAH isomers in mass spectra databases with electron impact ionization mass spectra and retention times of internal reference compounds. In total, 270 PAH compounds including numerous nitrogen, oxygen, and sulfur heteroatomic derivatives were positively identified for the first time. Quantitative analysis of target PAHs revealed that total PAH concentrations in coking wastewaters were in the range of 98.5 ± 8.9 to 216 ± 20.2 µg/L, with 3-4-ring PAHs as dominant compounds. Calculation of daily PAH output from four plant subunits indicated that PAHs in the coking wastewater came mainly from ammonia stripping wastewater. Coking wastewater treatment processes played an important role in removing PAHs in coking wastewater, successfully removing 92 % of the target compounds. However, 69 weakly polar compounds, including PAH isomers, were still discharged in the final effluent, producing 8.8 ± 2.7 to 31.9 ± 6.8 g/day of PAHs with potential toxicity to environmental waters. The study of coking wastewater herein proposed can be used to better predict improvement of coke production facilities and treatment conditions according to the identification and removal of PAHs in the coke plant as well as to assess risks associated with continuous discharge of these contaminants to receiving waters.

Identification and characterization of polycyclic aromatic hydrocarbons in coking wastewater sludge.

GC-MS analysis was performed on the coking sludge from a coking wastewater treatment plant (WWTP) to allow detailed chemical characterization of polycyclic aromatic hydrocarbons (PAHs). The identification and characterization of the isomers of PAHs was based on a positive match of mass spectral data of their isomers with mass spectra databases or based on a comparison of electron impact ionization mass spectra and retention times of target compounds with those reference compounds. In total, 160 PAH compounds including numerous N-, O-, S-, OH-, and Cl-containing derivatives were positively identified for the first time. Quantitative analysis of target compounds was performed in the selected ion-monitoring mode using the internal standard method. The total concentrations of selected compounds in the coking sludge samples from the anaerobic tank, aerobic tank, hydrolytic tank, and secondary clarifier of the WWTP ranged from 1690 ± 585 to 6690 ± 522 mg/kg, which were much higher than those in other industrial and municipal sludges. PAHs with four and five rings were found to be the dominant compounds, and diagnostic ratios of these compounds suggested that they had the characteristics of coal combustion and pyrolysis.

Coking wastewater treatment plant as a source of polycyclic aromatic hydrocarbons (PAHs) to the atmosphere and health-risk assessment for workers.

PAHs were identified and some of them were determined in the air around a coking wastewater treatment plant (WWTP) using passive air samplers. Seventy seven PAHs were found in the emissions from the degreasing tanks, the aeration tanks and the secondary clarifiers. ∑PAH concentrations within the plant (373.3±27.3-12959.5±685.9 ng/m(3)) were 3-41 times higher compared to the reference sites (315.7±50.2-363.4±77.5 ng/m(3)). The identification of numerous PAHs and high concentrations of these selected ones in the air of the studied sites indicated that the coking WWTP was a new source of atmospheric PAHs. Variations in the PAH pattern were observed in air within the coking WWTP. For example, Flu and Pyr accounted for 35-46% of the total contents at the degreasing tanks, but less than 10% at the hydrolytic tanks. The calculation of the diagnostic ratios suggested that PAHs in the emissions had the source characters of coal combustion. Furthermore, highly elevated PAH concentrations were determined at the degreasing tanks compared to the other tanks (i.e., aeration tanks and secondary clarifiers) and likely associated with their high concentrations in the coking wastewater and increased volatilization at high water temperature. Health risk assessments were carried out by evaluating the inhalation PAH exposure data. The resultant inhalation exposure levels due to TEQ(BaP) for workers ranged from 1.6±0.6 to 71.2±8.2 ng/m(3), and the estimated lung cancer risks were between 0.1×10(-3)±0.1×10(-4) and 5.2×10(-3)±0.5×10(-3), indicating PAHs in the air around the degreasing tanks and the aerobic tanks would have potential lung cancer risk for the operating workers.

The behaviors and fate of polycyclic aromatic hydrocarbons (PAHs) in a coking wastewater treatment plant.

The occurrence, behaviors and fate of 18 PAHs were investigated in a coking wastewater treatment plant in Songshan coking plant, located in Shaoguan, Guangdong Province of China. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent, sludge and gas samples. In raw coking wastewater, high molecular weight (MW) PAHs were the dominant compounds, while 3-6 ring PAHs predominated in the final effluent. The dominant compounds in gas samples were phenathrene, fluoranthene and pyrene, while they were fluoranthene, pyrene, chrysene and benzo[k]fluoranthene for sludge. The process achieved over 97% removal for all the PAHs, 47-92% of eliminations of these target compounds in liquid phase were achieved in biological stage. Different behaviors of PAHs were observed in the primary tank, anaerobic tank, aerobic tank, hydrolytic tank and coagulation tank units, while heavier and lower ones were mainly removed in anaerobic tank and aerobic tanks, respectively. Regarding the fate of PAHs, calculated fractions of mass losses for low MW PAHs due to transformation and adsorption to sludge accounted for 15-50% and 24-49%, respectively, while the rest was less than 1%. For high MW PAHs, the mass losses were mainly due to adsorption to sludge and separation with tar (contributing 56-76% and 22-39%, respectively), and the removal through transformation was less.

Distribution and health-risk of polycyclic aromatic hydrocarbons in soils at a coking plant.

Nineteen soil samples were collected in and around Songshan coking plant in Guangdong province of China and analyzed for eighteen polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-mass spectrometry (GC-MS). The total concentration of PAHs ranged from 2.36 to 1146.39 mg kg(-1) dry weight, varying significantly among the sampling sites, most individual PAHs were correlated with each other. A cluster analysis was performed to examine the correlation of PAH distribution, five groups were observed with sample types in the coking plant. 2-3 ring PAHs were predominant in group I and II, while 4-5 ring PAHs showed great abundance in group III, IV and V, which contributed to the distance from the emission sources in the coking plant and the behaviors of particle-bound and gaseous PAHs. The ratios of Flu : (Flu + Pyr), BaA : (BaA + Chr), InP : (InP + BgP) and Ant : (Ant + Phen) ratios were 0.51-0.87, 0.16-0.89, 0.47-0.68 and 0.03-0.60, respectively. The total index of all studied soils was > 6, indicating that the source of the PAHs in coking plant soils were from the pyrolysis processes. Health risk assessments were carried out by dermal PAH exposure data to quantify cancer risk. The resultant lifetime exposure levels due to TEQ(BaP) desorbed onto skin for workers ranged from 2.25 × 10(-7) to 7.86 × 10(-5) mg kg(-1) per day, and the estimated cancer risks were between 8.45 × 10(-6) and 2.94 × 10(-3), indicating that the dermal exposures of PAHs to coking workers might be acceptable in most soil sites.

Type-3 ryanodine receptors mediate hypoxia-, but not neurotransmitter-induced calcium release and contraction in pulmonary artery smooth muscle cells.

In this study we examined the expression of RyR subtypes and the role of RyRs in neurotransmitter- and hypoxia-induced Ca2+ release and contraction in pulmonary artery smooth muscle cells (PASMCs). Under perforated patch clamp conditions, maximal activation of RyRs with caffeine or inositol triphosphate receptors (IP3Rs) with noradrenaline induced equivalent increases in [Ca2+]i and Ca2+-activated Cl- currents in freshly isolated rat PASMCs. Following maximal IP3-induced Ca2+ release, neither caffeine nor chloro-m-cresol induced a response, whereas prior application of caffeine or chloro-m-cresol blocked IP3-induced Ca2+ release. In cultured human PASMCs, which lack functional expression of RyRs, caffeine failed to affect ATP-induced increases in [Ca2+]i in the presence and absence of extracellular Ca2+. The RyR antagonists ruthenium red, ryanodine, tetracaine, and dantrolene greatly inhibited submaximal noradrenaline- and hypoxia-induced Ca2+ release and contraction in freshly isolated rat PASMCs, but did not affect ATP-induced Ca2+ release in cultured human PASMCs. Real-time quantitative RT-PCR and immunofluorescence staining indicated similar expression of all three RyR subtypes (RyR1, RyR2, and RyR3) in freshly isolated rat PASMCs. In freshly isolated PASMCs from RyR3 knockout (RyR3-/-) mice, hypoxia-induced, but not submaximal noradrenaline-induced, Ca2+ release and contraction were significantly reduced. Ruthenium red and tetracaine can further inhibit hypoxic increase in [Ca2+]i in RyR3-/- mouse PASMCs. Collectively, our data suggest that (a) RyRs play an important role in submaximal noradrenaline- and hypoxia-induced Ca2+ release and contraction; (b) all three subtype RyRs are expressed; and (c) RyR3 gene knockout significantly inhibits hypoxia-, but not submaximal noradrenaline-induced Ca2+ and contractile responses in PASMCs.

Mouse dispatched mutants fail to distribute hedgehog proteins and are defective in hedgehog signaling.

Hedgehog (Hh) signaling plays a major role in multiple aspects of embryonic development, which involves both short- and long-range signaling from localized Hh sources. One unusual aspect of Hh signaling is the autoproteolytic processing of Hh followed by lipid modification. As a consequence, the N-terminal fragment of Hh becomes membrane anchored on the cell surface of Hh-producing cells. A key issue in Hh signaling is to understand the molecular mechanisms by which lipid-modified Hh protein is transported from its sites of synthesis and subsequently moves through the morphogenetic field. The dispatched gene, which encodes a putative multipass membrane protein, was initially identified in Drosophila and is required in Hh-producing cells, where it facilitates the transport of cholesterol-modified Hh. We report the identification of the mouse dispatched (Disp) gene and a phenotypic analysis of Disp mutant mice. Disp-null mice phenocopy mice deficient in the smoothened gene, an essential component for Hh reception, suggesting that Disp is essential for Hh signaling. This conclusion was further supported by a detailed molecular analysis of Disp knockout mice, which exhibit defects characteristic of loss of Hh signaling. We also provide evidence that Disp is not required for Hh protein synthesis or processing, but rather for the movement of Hh protein from its sites of synthesis in mice. Taken together, our results reveal a conserved mechanism of Hh protein movement in Hh-producing cells that is essential for proper Hh signaling.

[LIM protein KyoT2 interacts with human tight junction protein ZO-2-i3].

It was reported that LIM protein KyoT2 negatively regulated transcription by association with the RBP-J DNA-binding protein. Using yeast two-hybrid system with LIM protein KyoT2 as a bait, we have isolated an alternatively spliced form of human tight junction protein 2--ZO-2-i3. Sequence analysis indicated that ZO-2-i3 is composed of 19 exons, and selected usage of exons led to an alteration in the region following the kinase domain as compared with the published sequence. To identify the interaction between LIM protein KyoT2 and ZO-2-i3, yeast two-hybrid system, purification of KyoT2 protein, and GST pull-down assay were performed in the experiments. After KyoT2 and ZO-2-i3 changed vectors, positive two-hybrid yeast was obtained. Using KyoT2 protein and antibody in GST pull-down assay positive result was also obtained. Therefore we conformed KyoT2 interacted ZO-2-i3 in vitro. Furthermore it was identified in yeast that KyoT2 associated with ZO-2-i3 through its LIM2 domain.