Ozone Chemistry on Greasy Glass Surfaces Affects the Levels of Volatile Organic Compounds in Indoor Environments.

The chemistry of ozone (O3) on indoor surfaces leads to secondary pollution, aggravating the air quality in indoor environments. Here, we assess the heterogeneous chemistry of gaseous O3 with glass plates after being 1 month in two different kitchens where Chinese and Western styles of cooking were applied, respectively. The uptake coefficients of O3 on the authentic glass plates were measured in the dark and under UV light irradiation typical for indoor environments (320 nm < λ < 400 nm) at different relative humidities. The gas-phase product compounds formed upon reactions of O3 with the glass plates were evaluated in real time by a proton-transfer-reaction quadrupole-interface time-of-flight mass spectrometer. We observed typical aldehydes formed by the O3 reactions with the unsaturated fatty acid constituents of cooking oils. The formation of decanal, 6-methyl-5-hepten-2-one (6-MHO), and 4-oxopentanal (4-OPA) was also observed. The employed dynamic mass balance model shows that the estimated mixing ratios of hexanal, octanal, nonanal, decanal, undecanal, 6-MHO, and 4-OPA due to O3 chemistry with authentic grime-coated kitchen glass surfaces are higher in the kitchen where Chinese food was cooked compared to that where Western food was cooked. These results show that O3 chemistry on greasy glass surfaces leads to enhanced VOC levels in indoor environments.

[Chemical Speciation, Influencing Factors, and Regression Model of Heavy Metals in Farmland of Typical Carbonate Area with High Geological Background, Southwest China].

The speciation of heavy metals in soil is an important factor determining their bioavailability and toxicity, and it is crucial for the scientific assessment of ecological risks posed by heavy metals in soils of typical carbonate areas with high geological background in southwest China. In order to investigate the distribution of speciation of heavy metals in soils of carbonate rock with high geological background, we selected a typical carbonate rock distribution area in Guizhou Province and used the second national soil survey plots as sampling units. A total of 309 topsoil samples were collected from farmland. The improved Tessier seven-step sequential extraction method was used to analyze the seven chemical forms of heavy metals:water-soluble (F1); exchangeable (F2); carbonate-bound (F3); weakly organic-bound (F4); iron-manganese oxide-bound (F5); strongly organic-bound (F6); and residual (F7) forms of arsenic (As), cadmium (Cd), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb), and zinc (Zn). The study found that the residual forms of heavy metals As, Cu, Hg, Ni, Pb, and Zn in the soil accounted for more than 50%, the effective components (F1-F3) accounted for less than 5%, and the potential biological effective components (F4-F6) were less than 45%, indicating low reactivity and low ecological risk. The effective and potentially bioavailable components of Cd accounted for 55.49% and 29.37%, respectively, which were much higher than those of other heavy metals. The ecological risk based on the speciation of heavy metals in the soil was much lower than that based on the total content of heavy metals. The stepwise regression equations could effectively establish the relationship between the bioavailable and potentially bioavailable fractions of Cd, Cu, and Pb and their influencing factors. Total heavy metal contents and pH value were important factors influencing the speciation of heavy metals in soils of carbonate rock with high geological background areas. The enrichment of heavy metal elements in the residual fraction was influenced by long-term zinc smelting activities and the weathering of carbonate rocks into soil. Soil organic matter (OM) and oxide content had a relatively small influence on the speciation of heavy metals in the soil.

Heterogeneous chemistry of ozone with floor cleaning agent: Implications of secondary VOCs in the indoor environment.

Human daily activities such as cooking, and cleaning can affect the indoor air quality by releasing primary emitted volatile organic compounds (VOCs), as well as by the secondary product compounds formed through reactions with ozone (O3) and hydroxyl radicals (OH). However, our knowledge about the formation processes of the secondary VOCs is still incomplete. We performed real-time measurements of primary VOCs released by commercial floor-cleaning detergent and the secondary product compounds formed by heterogeneous reaction of O3 with the constituents of the cleaning agent by use of high-resolution mass spectrometry. We measured the uptake coefficients of O3 on the cleaning detergent at different relative humidities in dark and under different light intensities (320 nm < λ < 400 nm) relevant for the indoor environment. On the basis of the detected compounds we developed tentative reaction mechanisms describing the formation of the secondary VOCs. Intriguingly, under light irradiation the formation of valeraldehyde was observed based on the photosensitized chemistry of acetophenone which is a constituent of the cleaning agent. Finally, we modeled the observed mixing ratios of three aldehydes, glyoxal, methylglyoxal, and 4-oxopentanal with respect to real-life indoor environment. The results suggest that secondary VOCs initiated by ozone chemistry can additionally impact the indoor air pollution.

The Effect of Human Occupancy on Indoor Air Quality through Real-Time Measurements of Key Pollutants.

The primarily emitted compounds by human presence, e.g., skin and volatile organic compounds (VOCs) in breath, can react with typical indoor air oxidants, ozone (O3), and hydroxyl radicals (OH), leading to secondary organic compounds. Nevertheless, our understanding about the formation processes of the compounds through reactions of indoor air oxidants with primary emitted pollutants is still incomplete. In this study we performed real-time measurements of nitrous acid (HONO), nitrogen oxides (NOx = NO + NO2), O3, and VOCs to investigate the contribution of human presence and human activity, e.g., mopping the floor, to secondary organic compounds. During human occupancy a significant increase was observed of 1-butene, isoprene, and d-limonene exhaled by the four adults in the room and an increase of methyl vinyl ketone/methacrolein, methylglyoxal, and 3-methylfuran, formed as secondary compounds through reactions of OH radicals with isoprene. Intriguingly, the level of some compounds (e.g., m/z 126, 6-methyl-5-hepten-2-one, m/z 152, dihydrocarvone, and m/z 194, geranyl acetone) formed through reactions of O3 with the primary compounds was higher in the presence of four adults than during the period of mopping the floor with commercial detergent. These results indicate that human presence can additionally degrade the indoor air quality.

Daytime SO2 chemistry on ubiquitous urban surfaces as a source of organic sulfur compounds in ambient air.

The reactions of sulfur dioxide (SO2) with surface-bound compounds on atmospheric aerosols lead to the formation of organic sulfur (OS) compounds, thereby affecting the air quality and climate. Here, we show that the heterogeneous reaction of SO2 with authentic urban grime under near-ultraviolet sunlight irradiation leads to a large suite of various organic compounds including OS released in the gas phase. Calculations indicate that at the core area of Guangzhou, building surface uptake of SO2 is 15 times larger than uptake of SO2 on aerosol surfaces, yielding ~20 ng m-3 of OS that represents an important fraction of the observed OS compounds (60 to 200 ng m-3) in ambient aerosols of Chinese megacities. This chemical pathway occurring during daytime can contribute to the observed fraction of OS compounds in aerosols and improve the understanding of haze formation and urban air pollution.

Unveiling the pH-Dependent Yields of H2O2 and OH by Aqueous-Phase Ozonolysis of m-Cresol in the Atmosphere.

Hydrogen peroxide (H2O2) and hydroxyl radical (OH) are important oxidants in the atmospheric aqueous phase such as cloud droplets and deliquescent aerosol particles, playing a significant role in the chemical transformation of organic and inorganic pollutants in the atmosphere. Atmospheric aqueous-phase chemistry has been considered to be a source of H2O2 and OH. However, our understanding of the mechanisms of their formation in atmospheric waters is still incomplete. Here, we show that the aqueous-phase reaction of dissolved ozone (O3) with substituted phenols such as m-cresol represents an important source of H2O2 and OH exhibiting pH-dependent yields. Intriguingly, the formation of H2O2 through the ring-opening mechanism is strongly promoted under lower pH conditions (pH 2.5-3.5), while higher pH favors the ring-retaining pathways yielding OH. The rate constant of the reaction of O3 with m-cresol increases with increasing pH. The reaction products formed during the ozonolysis of m-cresol are analyzed by an Orbitrap mass spectrometer, and reaction pathways are suggested based on the identified product compounds. This study indicates that aqueous-phase ozonolysis of phenolic compounds might be an alternative source of H2O2 and OH in the cloud, rain, and liquid water of aerosol particles; thus, it should be considered in future model studies.

HKUST-1-derived highly ordered Cu nanosheets with enriched edge sites, stepped (211) surfaces and (200) facets for effective electrochemical CO2 reduction.

A novel electrode composed of Cu nanosheets constructed from nanoparticles was synthesized by in situ electrochemical derivation from the metal-organic framework (MOF) HKUST-1. The prepared derivative electrode (HE-Cu) exhibited higher Faradaic efficiency (FE, 56.0%) of electrochemical CO2 reduction (CO2R) compared with that of pristine Cu foil (p-Cu, 32.3%) at an overpotential of -1.03 V vs. a reversible hydrogen electrode (RHE). HE-Cu also exhibited lower onset potential of CO2R as well as inhibiting the H2 evolution reaction. Electrochemical measurements revealed that HE-Cu exhibited higher CO2 adsorption (1.58-fold) and a larger electrochemical active surface area (1.24-fold) compared with p-Cu. Physicochemical characterization and Tafel analysis showed that stepped Cu (211) surfaces, (200) facets and Cu edge atoms on HE-Cu contributed significantly to the enhanced CO2R activity and/or HCOOH and/or C2 product selectivity. The FEs of HCOOH and C2 products for HE-Cu increased 1.57-fold and 10.6-fold at an overpotential of -1.19 V vs. RHE compared with p-Cu. Although CH4 was produced on p-Cu, its formation was totally suppressed on HE-Cu due to the increase of edge sites and (200) facets. Our study demonstrates that electroreduction of MOFs is a promising method to prepare novel and stable electrochemical catalysts with unique surface structures. The fabricated derivative electrode not only promoted electrochemical CO2R activity but also exhibited high C2 product selectivity.

Clinical Observation and Prognostic Analysis of Patients With Klebsiella pneumoniae Bloodstream Infection.

Background and purpose: The clinical prognosis of Klebsiella pneumoniae(K. pneumoniae) bloodstream infection is poor, and the prevalence of drug-resistant bacteria makes clinical anti-infective treatment more challenging. This retrospective study evaluated the epidemiological characteristics of patients with K. pneumoniae, the risk factors for drug-resistant bacterial infection and death, and analyzed treatment options. Methods: Clinical data of 297 patients diagnosed with K. pneumoniae bacteremia between June 2014 and June 2019 were collected. Results: Intensive care unit hospitalization history, operation history, recent antibiotic use history, mechanical ventilation, and number of days hospitalized before bloodstream infection were found to be independent risk factors for drug-resistant bacterial infection. The risk of death for carbapenem-resistant K. pneumoniae infection was 2.942 times higher than that for carbapenem-sensitive K. pneumoniae infection. For extensively drug-resistant K. pneumoniae bacteremia patients, the mortality rate of combined anti-infective therapy was lower. Conclusions: Clinicians should pay attention to patients with high-risk drug-resistant bacteria infection and administer timely anti-infection treatment. The findings of this study may provide some suggestions for early identification and standardized treatment of patients with K. pneumoniae bacteremia.

TiO2 quantum dots loaded sulfonated graphene aerogel for effective adsorption-photocatalysis of PFOA.

With the pollution of perfluoroalkyl substances (PFASs) became increasingly serious, the researches focused on removal of PFASs by adsorption-photocatalysis method has attracted considerable attention. To make the catalyst TiO2 disperse uniformly as quantum dots onto hydrophobic surface which was liable to attract perfluorooctanoic acid (PFOA), the surfactant sodium dodecyl sulfate (SDS) were used in this work, which not only connected the hydrophilic TiCl3 to the hydrophobic sulfonated graphene (SG) nanosheets, but also behaved as the molecular template for controlled nucleation and growth of the nanostructured TiO2. After 3D SG-TiO2 QD nanosheets were fabricated, a series of 3D SG-TiO2 QD aerogels were self-assembled by ice-template. TiO2 uniformly distributed on the surface of SG aerogel at QD size level (2-3 nm) and the size of TiO2 could be effectively regulated by concentration of SDS. Compared with aggregated TiO2 material, 3D SG-TiO2 QD aerogels owned higher adsorption and photocatalytic performance. Benefiting from the hydrophobic surface of 3D SG as well as dispersed TiO2 QDs, 3D SG-TiO2 QD could enrich PFOA instantaneously (0.0381/s) and photocatalytic decomposed them effectively (1.898 E-4/s). PFOA degradation by hole and hydroxyl radicals proceeded via a stepwise mechanism. The column made of 3D SG-TiO2 QD could remove PFOA persistently in cycles of permeation. 3D SG-TiO2 QD possessed powerful adsorption-photocatalytic decomposition capability of PFOA and steady reusability performance. The present work highlights the individual roles and synergistic effect of TiO2 QD and 3D SG for effectively removing PFOA.

Biochemical and genetic toxicity of dinotefuran on earthworms (Eisenia fetida).

Dinotefuran is a third-generation neonicotinoid insecticide, that is considered promising due to its excellent properties. In the present work, the biochemical and genetic toxicity of dinotefuran on earthworms were evaluated at a series of environmental background concentrations. Meanwhile, the effective concentrations of dinotefuran in artificial soil during the entire exposure period were monitored. The present results showed that dinotefuran was stable in artificial soil, and its concentrations changed no more than 20% during the 28-d exposure. At 1.0 mg/kg and 2.0 mg/kg, dinotefuran induced excess generation of ROS, resulting in significant changes in antioxidant enzyme activities and functional gene expression. Moreover, lipids, proteins and nucleic acids were oxidized and damaged by the excess ROS induced by dinotefuran, resulting in serious destruction of the structure and function of cells. Additionally, the toxicity of dinotefuran showed obvious dose- and time-dependent effects. Therefore, we consider that dinotefuran may be a high-risk pollutant for earthworms.

Residue analysis and risk assessment of tebuconazole in jujube (Ziziphus jujuba Mill).

In this study, a sensitive and reliable analytical method, based on a modified Quick, Easy, Cheap, Effective, Rugged and Safe procedure, was established for determination of tebuconazole in jujube. After extraction with acetonitrile, the samples were cleaned up by dispersive solid-phase extraction with primary secondary amine, and determined by high-performance liquid chromatography tandem mass spectrometry. At fortification levels of 0.01, 0.1 and 2.0 mg kg-1 , the average recoveries of tebuconazole in jujube were in the range 97.6-101.9%, with relative standard deviations of 1.5-3.5%. The dissipation and residual levels of tebuconazole in jujube under field conditions were investigated. Tebuconazole dissipated relatively slowly in jujube, with a half-life of 33.0 days. The terminal residue experiments of tebuconazole in jujube were conducted in four locations in China and the risk was evaluated using risk quotients (RQ). RQ values were found to be significantly lower than RQ = 1, indicating that the risk to human health of using the recommended doses of tebuconazole in jujube was not significant. This study could provide guidance for the safe and reasonable use of tebuconazole in jujube and serve as a reference for the establishment of limit of maximum residue in China.

Dissipation and residues of myclobutanil in tobacco and soil under field conditions.

Field experiments were conducted in two different locations to determine the dissipation pattern and residue levels of myclobutanil in tobacco leaves and soil. Myclobutanil 12.5 % microemulsion (ME) formulation was sprayed once at 3.0 mL/ha, and the residues in green tobacco leaves dissipated to more than 50 % of the initial deposits 5 days after application and up to above 90 % after 21 days. The dissipation rate of myclobutanil in soil was lower than that in green tobacco leaves. The residues dissipated above 50 % of the initial deposits 7 days after treatment and dissipated about 90 % after 42 days. The calculated half-life values (T (1/2)) were found to be 4.89-6.77 days in green tobacco leaves and 12.88-19.20 days in soil, respectively. The ultimate residues of myclobutanil in flue-cured tobacco leaves and soil were determined after the third and fourth applications at levels of 2.0 and 3.0 mL/ha. Myclobutanil residues in cured tobacco leaves 21 days after the last treatment ranged from 0.85 to 3.27 mg/kg. Meanwhile, the residues detected in soil reached below 0.045 mg/kg 21 days after the last treatment.

Disruption of the gene encoding ß-1, 3-glucanase in marine-derived Williopsis saturnus WC91-2 enhances its killer toxin activity.

As the ß-1, 3-glucanase produced by the marine-derived Williopsis saturnus WC91-2 could inhibit the activity of the killer toxin produced by the same yeast, the WsEXG1 gene encoding exo-ß-1, 3-glucanase in W. saturnus WC91-2 was disrupted. The disruptant WC91-2-2 only produced a trace amount of ß-1, 3-glucanase but had much higher activity of killer toxin than W. saturnus WC91-2. After the disruption of the WsEXG1 gene, the expression of the gene was significantly decreased from 100% in the cells of W. saturnus WC91-2 to 27% in the cells of the disruptant WC91-2-2 while the expression of the killer toxin gene in W. saturnus WC91-2 and the disruptant WC91-2-2 was almost the same. During 2-l fermentation, the disruptant WC91-2-2 could produce the highest amount of killer toxin (the size of the inhibition zone was 22 ± 0.7 mm) within 36 h when the cell growth reached the middle of the log phase.

Dissolved organic nitrogen (DON) profile during backwashing cycle of drinking water biofiltration.

A comprehensive investigation was made in this study on the variation of dissolved organic nitrogen (DON) during a whole backwashing cycle of the biofiltration for drinking water treatment. In such a cycle, the normalized DON concentration (C(effluent)/C(influent)) was decreased from 0.98 to 0.90 in the first 1.5h, and then gradually increased to about 1.5 in the following 8h. Finally, it remained stable until the end of this 24-hour cycle. This clearly 3-stage profile of DON could be explained by three aspects as follows: (1) the impact of the backwashing on the biomass and the microbial activity; (2) the release of soluble microbial products (SMPs) during the biofiltration; (3) the competition between heterotrophic bacteria and nitrifying bacteria. All the facts supported that more DON was generated during later part of the backwashing cycle. The significance of the conclusion is that the shorter backwashing intervals between backwashing for the drinking water biofilter should further decrease the DON concentration in effluent of biofilter.

Enhanced ß-galactosidase production from whey powder by a mutant of the psychrotolerant yeast Guehomyces pullulans 17-1 for hydrolysis of lactose.

In order to isolate ß-galactosidase overproducers of the psychrotolerant yeast Guehomyces pullulans 17-1, its cells were mutated by using nitrosoguanidine (NTG). One mutant (NTG-133) with enhanced ß-galactosidase production was obtained. The mutant grown in the production medium with 30.0 g/l lactose and 2.0 g/l glucose could produce more ß-galactosidase than the same mutant grown in the production medium with only 30.0 g/l lactose while ß-galactosidase production by its wild type was sensitive to the presence of glucose in the medium. It was found that 40.0 g/l of the whey powder was the most suitable for ß-galactosidase production by the mutant. After optimization of the medium and cultivation conditions, the mutant could produce 29.2 U/ml of total ß-galactosidase activity within 132 h at the flask level while the mutant could produce 48.1 U/ml of total ß-galactosidase activity within 144 h in 2-l fermentor. Over 77.1% of lactose in the whey powder (5.0% w/v) was hydrolyzed in the presence of the ß-galactosidase activity of 280 U/g of lactose within 9 h while over 77.0% of lactose in the whey was hydrolyzed in the presence of ß-galactosidase activity of 280 U/g of lactose within 6 h. This was the first time to show that the ß-galactosidase produced by the psychrotolerant yeast could be used for hydrolysis of lactose in the whey powder and whey.

Removal of dichloroacetic acid from drinking water by using adsorptive ozonation.

Chloroacetic acids, formed during the disinfection process in potable water production, are considered to pose a potential risk to human health. This article deals with dichloroacetic acid (DCAA) removal from drinking water by using a process of bentonite based adsorptive ozonation. This process is formed by combined addition of ozone, bentonite and Fe(3+). During the reaction, DCAA is removed by the joint effect of adsorption, ozonation and catalytic oxidation. In addition, under the effect of the adsorption, natural organic matters (NOM) can be adsorbed onto the bentonite surface, resulting in a reduced scavenging effect toward HO· radicals, and hence eliminate the negative effect of NOM on DCAA removal. At the initial stage of the reaction, Fe(3+) is rapidly hydrolyzed to polycations and adsorbed onto the bentonite surface or into its structural layers. This positively charges the surface of the bentonite and increases its surface area, resulting in a strong adsorption of HA or DCAA. Furthermore, Fe(3+) catalyzes ozone decomposition to form HO· thus further improving the efficiency. The adsorptive ozonation has been shown to be potentially advantageous in destruction of toxic, dissolved pollutants in drinking water, and appears to have great potential for a wide range of treatment applications.

A GH57 family amylopullulanase from deep-sea Thermococcus siculi: expression of the gene and characterization of the recombinant enzyme.

The gene encoding a new extracellular amylopullulanase (type II pullulanase) was cloned from an extremely thermophilic anaerobic archaeon Thermococcus siculi strain HJ21 isolated previously from a deep-sea hydrothermal vent. The functional hydrolytic domain of the amylopullulanase (TsiApuN) and its MalE fusion protein (MTsiApuN) were expressed heterologously. The complete amylopullulanase (TsiApu) was also purified from fermentation broth of the strain. The pullulanase and amylase activities of the three enzymes were characterized. TsiApu had optimum temperature of 95°C for the both activities, while MTsiApuN and TsiApuN had a higher optimum temperature of 100°C. The residual total activities of MTsiApuN and TsiApuN were both 89% after incubation at 100°C for 1 h, while that of TsiApu was 70%. For all the three enzymes the optimum pHs for amylase and pullulanase activities were 5.0 and 6.0, respectively. By analyzing enzymatic properties of the three enzymes, this study suggests that the carboxy terminal region of TsiApu might interfere with the thermoactivity. The acidic thermoactive amylopullulanases MTsiApuN and TsiApuN could be further employed for industrial saccharification of starch.

Hymenobacter daecheongensis sp. nov., isolated from stream sediment.

A Gram-negative, strictly aerobic, non-spore-forming, rod-shaped, red-pink bacterium, designated strain Dae14(T), was isolated from stream sediment collected near Daecheong Dam, South Korea, and its taxonomic position was investigated by using a polyphasic approach. Phylogenetic analysis of 16S rRNA gene sequences showed that strain Dae14(T) belonged to the genus Hymenobacter. Sequence similarities between strain Dae14(T) and the type strains of Hymenobacter species with validly published names ranged from 91.3 to 94.3 %. The predominant cellular fatty acids of strain Dae14(T) were iso-C(15 : 0), C(16 : 1)omega5c, summed feature 5 (iso-C(17 : 1) I and/or anteiso-C(17 : 1) B) and iso-C(16 : 0). The DNA G+C content was 62.2 mol%. Results of phylogenetic, chemotaxonomic and phenotypic characterization indicated that strain Dae14(T) can be distinguished from all known Hymenobacter species and represents a novel species, for which the name Hymenobacter daecheongensis sp. nov. is proposed, with Dae14(T) (=KCTC 22258(T)=LMG 24498(T)) as the type strain.

Spirosoma panaciterrae sp. nov., isolated from soil.

A Gram-negative, yellowish bacterial strain, designated Gsoil 1519(T), was isolated from soil of a ginseng field in Pocheon province (South Korea) and characterized using a polyphasic approach to determine its taxonomic position. Comparative 16S rRNA gene sequence analysis showed that strain Gsoil 1519(T) belongs to the family 'Flexibacteraceae' and is related to Spirosoma rigui KCTC 12531(T) (91.8 % similarity) and Spirosoma linguale LMG 10896(T) (91.5 % similarity). Phylogenetic distances from any other recognized species within the family 'Flexibacteraceae' were greater than 14.7 %. The G+C content of the genomic DNA of strain Gsoil 1519(T) was 50.1 %. The detection of MK-7 as the predominant menaquinone and a fatty acid profile with C(16 : 1)omega5c, summed feature 4 (C(16 : 1)omega7c and/or iso-C(15 : 0) 2-OH), iso-C(15 : 0) and C(16 : 0) as the major acids supported the affiliation of strain Gsoil 1519(T) to the genus Spirosoma. On the basis of its phenotypic properties and phylogenetic distinctiveness, strain Gsoil 1519(T) should be classified in the genus Spirosoma as a representative of a novel species, for which the name Spirosoma panaciterrae sp. nov. is proposed. The type strain is Gsoil 1519(T) (=KCTC 22263(T)=DSM 21099(T)).