Exploring drivers of the aggravated surface O3 over North China Plain in summer of 2015-2019: Aerosols, precursors, and meteorology.

Continuous aggravated surface O3 over North China Plain (NCP) has attracted widely public concern. Herein, we evaluated the effects of changes in aerosols, precursor emissions, and meteorology on O3 in summer (June) of 2015-2019 over NCP via 8 scenarios with WRF-Chem model. The simulated mean MDA8 O3 in urban areas of 13 major cities in NCP increased by 17.1%∼34.8%, which matched well with the observations (10.8%∼33.1%). Meanwhile, the model could faithfully reproduce the changes in aerosol loads, precursors, and meteorological conditions. A relatively-even O3 increase (+1.2%∼+3.9% for 24-h O3 and +1.0%∼+3.8% for MDA8 O3) was induced by PM2.5 dropping, which was consistent with the geographic distribution of regional PM2.5 reduction. Meanwhile, the NO2 reduction coupled with a near-constant VOCs led to the elevated VOCs/NOx ratios, and then caused O3 rising in the areas under VOCs-limited regimes. Therein, the pronounced increases occurred in Handan, Xingtai, Shijiazhuang, Tangshan, and Langfang (+10.7%∼+13.6% for 24-h O3 and +10.2%∼+12.2% for MDA8 O3); while the increases in other cities were 5.7%∼10.5% for 24-h O3 and 4.9%∼9.2% for MDA8 O3. Besides, the meteorological fluctuations brought about the more noticeable O3 increases in northern parts (+12.5%∼+13.5% for 24-h O3 and +11.2%∼+12.4% for MDA8 O3) than those in southern and central parts (+3.2%∼+9.3% for 24-h O3 and +3.7%∼+8.8% for MDA8 O3). The sum of the impacts of the three drivers reached 16.7%∼21.9%, which were comparable to the changes of the observed O3. Therefore, exploring reasonable emissions-reduction strategies is essential for the ozone pollution mitigation over this region.

[Ozone Sensitivity Analysis and Control Strategy in Shijiazhuang City in July 2019].

The pollution characteristics of surface ozone and its response to meteorological factors were studied based on monitoring in July 2019 in Shijiazhuang City, China. Furthermore, the WRF-CMAQ model coupled with O3 isopleths (EKMA curves) were applied to explore the non-linear response relationship of O3 to precursors VOCs and NOx, aiming to identify a suitable precursor control strategy. The results showed that the days with the maximum daily 8-hour average ozone concentration (MDA8 O3) exceeded the standard by 70.9%. The nonattainment days were usually accompanied by higher temperature, lower relative humidity, and low winds, and the south and southeast winds occurred frequently. The O3 formation was in the strong VOC-limited regime in the urban area of Shijiazhuang, whereas it was in the NOx and VOCs transition regime in suburban areas. As for the urban area, under the condition of single NOx emission reduction, O3 pollution improved when continuous NOx emission reduction was higher than 50% during the nonattainment days. By contrast, during the non-polluted days, O3 concentrations would not rebound when the reduction ratio of NOx and VOCs was higher than 1. In conclusion, VOCs reduction should be the priority for emission reduction plans in urban areas, whereas all different NOx and VOCs ratios led to a decline in O3 concentration in the suburban areas, and a VOCs:NOx of 1:2 was recommended.

Exploring the causes for co-pollution of O3 and PM2.5 in summer over North China.

Co-pollution of surface O3 and PM2.5 has become the most predominant type of air pollutions in Beijing-Tianjin-Hebei region in the hot season since 2017, particularly in May-July. Analysis based on observational data showed that co-pollution was always accompanied by high temperature, moderate relative humidity, extremely high SO2, and higher NO2. We also found that the meteorology and precursor dependence of O3 was similar between co-pollution and O3- single pollution. While PM2.5 in co-pollution was more related to temperature, relative humidity, and precursors, that in PM2.5-singe pollution were more related to small winds. These results indicate that co-pollution seemed to be more affected by atmospheric chemistry. According to the PM2.5 components, secondary inorganic aerosols (SIA) composed 44.3-48.7% of PM2.5 in co-pollution, while those accounting for 42.1-46.5% and 41.2-44.3%, respectively, in O3- and PM2.5-single pollution, which further confirmed the relatively stronger atmospheric chemistry processes in co-pollution. And the high proportion of SIA in co-pollution was mainly attributed to SO42-, which was observed to rapidly boom in non-refractory submicron aerosol (NR-PM1) on the condition of high level of O3 at daytime. Additionally, we further explored the interactions of O3 and PM2.5 in co-pollution. It was found that most (~61.9%) co-pollution episodes were initiated by high O3 at daytime; while for other episodes, high PM2.5 firstly occurred under the more stable meteorological conditions, and then accumulation of precursors further induced high O3. A higher SIA concentration was observed in O3-initiated co-pollution, indicating that the atmospheric oxidation in co-pollution caused by chemical processes was stronger than that by physical processes, which was further approved by the higher values of SOR and NOR in O3-initiated co-pollution. This observational study revealed that controlling O3 and precursor SO2 is the key to abating co-pollution in the hot season.

[Applying Photochemical Indicators to Analyze Ozone Sensitivity in Handan].

Ozone pollution in Handan has become severe in recent years and in the summer of 2018, the average maximum daily 8-hour average ozone concentration in Handan was 175 µg·m-3 with a maximum of 257 µg·m-3. Ozone concentrations exceeded the National Air Quality Grade Ⅱ Standard in 59% of cases. In this study, the H2O2/HNO3 indicator was applied to analyze summertime ozone sensitivity in Handan using the WRF-CMAQ modeling system. The results showed that H2O2/HNO3 was more appropriate than other ozone indicators, both theoretically and based on simulation outputs. The good simulation effect of CMAQ on H2O2 and HNO3 was attributed to fine emission inventory and grid resolution. The H2O2/HNO3 simulation results showed that the relative importance of a VOCs-limited regime decreased month by month; a VOCs-NOx-mixed-limited regime was dominant in June; and a NOx-limited regime was more dominant in July and August than in June. The remarkable spatial difference in VOCs and NOx emission ratios among the counties of Handan led to differences in ozone sensitivity. The VOCs-limited regime was concentrated in counties where VOCs/NOx emission ratios were lower than 1.7. Southern counties had a NOx-limited regime, where VOCs/NOx emission ratios were higher than 6.9. Counties with VOCs/NOx emission ratios varying from 1.7 to 6.9 were more susceptible to both VOCs and NOx. According to these results, the transition range of HCHO/NO2, O3/HNO3, and O3/NOx ratios were adjusted to 0.35-0.6, 20-35, and 10-25 respectively. Adjusting the transition range of H2O2/(O3+NO2) was not effective, indicating that this indicator may not be applicable to Handan.

Understanding the selective-sensing mechanism of lysine by fluorescent nanosensors based on graphene quantum dots.

The selectivity of single-amino acid nanosensors is still not well understood. Herein, the factors that govern graphene-based nanomaterials for the selective detection of lysine are reported to guide the design of single-amino acid nanosensors. Graphene quantum dots (GQDs), nitrogen-doped GQDs (N-GQDs), and nitrogen/sulfur co-doped GQDs (N,S-GQDs) were used to sense lysine. The interaction mode and mechanism adjusted selectivity of the zero-dimensional graphene-based quantum dots to lysine ascribe to the solution behavior, molecular size, number of atoms as electron donors in graphene, and driving force. Being a basic amino acid, lysine is protonated with a positive charge below solution pH of 9. It adsorbed on the graphene-based quantum dots via electrostatic attraction, which blocked the internal charge transfer pathway inducing fluorescence enhancement at 420 nm. The protonated ɛ-amine side of lysine is responsible for the course. The small diameter of the lysine of ɛ-amine (<0.35 nm) favored its approach to the quantum dots, resulting in a fluorescence change, which could not be achieved with the larger arginine. The activated sites for interaction with lysine located at the edges of the layers of graphene to reach high selectivity. The N-GQDs and N,S-GQDs are much more sensitive to lysine than the GQDs because they contain nitrogen atoms as electron donors. They had similar linear detection ranges and detection limits, which suggested that the contribution of sulfur for lysine detection was minor. The results of this study provide new insights into the design of GQDs-based single-analyte nanosensors with high selectivity.

[Pollution Characteristics and Sensitivity of Surface Ozone in a Typical Heavy-Industry City of the North China Plain in Summer].

The pollution characteristics of surface ozone and its response to meteorological factors and precursors were studied based on monitoring and Model-3/CMAQ modeling from May to August 2018 in Handan City, China. The monitoring results showed that the maximum daily 8-hour average ozone concentration (MDA8 O3) ranged from 38.0-238.0 µg·m-3, and the nonattainment for ozone reached 44.7% during the studied period, indicating the more severe photochemical pollution in summer in Handan City. The ozone concentration was positively correlated with temperature (R=0.74 on nonattainment days and 0.42 on attainment days), but negatively correlated with relative humidity (R=-0.63 on nonattainment days and -0.58 on attainment days), demonstrating the role of photochemistry in the surface ozone of Handan City. Moreover, the highest ozone level occurred at wind speeds higher than 2.25 m·s-1 or lower than 1.00 m·s-1 during ozone nonattainment days, which indicated that regional transport and local accumulation can both cause serious ozone pollution in the city. Regarding the response of ozone to its precursors (VOCs and NOx), model simulation results based on the brute force method showed the stronger positive sensitivity to VOCs, but a weak negative sensitivity to NOx. Therefore, reduction of anthropogenic VOCs emissions is the key to improving ozone pollution in Handan City. We used the propylene-equivalent method to identify the importance of alkene and aromatic species for ozone pollution during ozone nonattainment days.

A graphene oxide-based fluorescent sensor for recognition of glutamate in aqueous solutions and bovine serum.

A novel fluorescence probe based on graphene-aminofluorescein (GAF) for sensing glutamate is prepared by modifying graphene oxide (GO) with 5-aminofluorescein (AF), and shows high sensitivity and selectivity. The strong fluorescence of the GAF probe is quenched in the presence of glutamate, and the quenching exhibits a good linear relationship with the glutamate concentration within the range of 1-45 mg/L. In bovine serum, the accurate quantitation of glutamate is possible within the range of 6 mg/L to 30 mg/L. At the pH of 3.32 (close to the isoelectric point of glutamate), GAF can selectively detect glutamate in preference to other amino acids. The high sensitivity and specificity of this sensor enable a new method for the detection of glutamate in aqueous solutions and serums.

Synthesis and adsorption performance of dithiocarbamate-modified glycidyl methacrylate starch.

The design of chelating polymers with fast complexation of the metal ions is particularly interest. In this work, the dithiocarbamate-modified glycidyl methacrylate starch was synthesized and characterized by FT-IR, (13)C NMR and XRD spectra. Its sorption performance for heavy metals fixation was studied. It was found that the removal process of metal ions involved a fast increase stage followed by a slower stage. There was a higher match between the pseudo-second-order equation and the experimental data. The sorption rate constants were related to the substitution rates of hydrated metal ions in aqueous solutions, showing typical chemisorption. The Langmuir isotherm gave satisfying fits to equilibrium data of metals adsorption. And the capacities followed the sequence Cu(2+)>Cd(2+)>Co(2+)>Zn(2+)>Ni(2+)>Mn(2+), which could be well demonstrated with chelating interaction caused by sulfur atoms. Such understanding provides new insights as how to synthesize and use the dithiocarbamate-based polysaccharides.

Optical turn-on sensor based on graphene oxide for selective detection of D-glucosamine.

By incorporating the well-known fluorophore 8-aminoquinoline into graphene oxide, we have successfully prepared a turn-on fluorescent sensor capable of specific detection of D-glucosamine with a high selectivity and sensitivity. This methodology provides a new concept for the design and development of highly selective and sensitive turn-on optical sensors for selective detection of aminosaccharides and many other biomolecules.

Equilibrium and molecular mechanism of anionic dyes adsorption onto copper(II) complex of dithiocarbamate-modified starch.

The assembly of dyes molecules on metal-polymer complexes is of interest due to their potential applications in photovoltaic cell, separation, and wastewater treatment. In the present work, the interaction of anionic dyes (acid orange 7, acid orange 10, acid green 25, and acid red 18) with the copper(II) complex of dithiocarbamate-modified starch (DTCSCu) was investigated. The sorption studies showed that the interaction mechanism was based on chelating adsorption. The equilibrium data fitted well with Langmuir-Freundlich isotherm, and the capacities followed the order AO7 > AG25 > AR18 > AO10. It was affected by the structure of the dye. The sulfonate groups located on benzene rings favored efficient adsorption. Despite the difference in capacity, the molar n(dye):n(Cu) ratios for acid orange 10, acid red 18, and acid green 25 were approximately 1:2 when the maximum capacities for the dyes were achieved at the optimal pH of 4. It suggested that one dye molecule bound to one dinuclear copper center on DTCSCu. The molar n(dye):n(Cu) ratio for the smallest dye, acid orange 7 (AO7), approached 1:1, demonstrating two AO7 molecules binding to two copper ions of the dinuclear core. The dyes adsorption related to the dinuclear copper core available on the polymer was further verified by electron spin resonance studies. Such interaction resulted in the formation of a ternary dye-metal-polymer complex. The ternary complexes were more stable than DTCSCu, which favored the adsorptions.

Ethylenediamine modified starch as biosorbent for acid dyes.

This work investigated the sorption performance of the ethylenediamine modified starch (CAS) for the removal of acid dyes from aqueous solutions. The influence of pH on adsorption of acid orange 10 (AO10), acid green 25 (AG25) and amido black 10B (AB10B) was evaluated. The sorption kinetics, equilibrium uptake and desorption of the loaded dyes in sodium sulfate solution were studied. It was found that the interaction mechanism was based on electrostatic attraction and hydrogen bonding. The adsorption of AG25 and AB10B followed pseudo-second-order model, whereas AO10 followed both pseudo-first-order and pseudo-second-order models. The best isotherm was Langmuir equation and the capacities followed the sequence AB10B>AG25>AO10. The different behaviors of individual dyes adsorption on CAS were largely dependent on the number of hydrophilic functional groups, which had strong tendency to form hydrogen bonds with the biosorbent. Dye release in sodium sulfate solutions was determined by the salt concentration and nature of dyes.

A sugar-quinoline fluorescent chemosensor for selective detection of Hg2+ ion in natural water.

A selective and sensitive fluorescent sensor for detection of Hg2+ in natural water was achieved by incorporating the well-known fluorophore quinoline group and a water-soluble D-glucosamine group within one molecule.

Chromium(III) complexes of D-glucosaminic acid and their effect on decreasing blood sugar in vivo.

Two chromium(III) complexes of glucosaminic acid were synthesized by neutralization and exchange reaction. The formation of 1 : 1 and 2 : 3 (Cr : glucosaminate) complexes was confirmed by elemental analyses and spectroscopic studies. The effect of the complexes on decreasing blood sugar was investigated on type-2 diabetes model rats induced by tetraoxypyrimidine. The results indicated that the effect on decreasing blood sugar was comparable to that of picolinate chromium complex (Cr(pic)(3)) currently used world wide.

Naked-eye detection of fluoride ion in water: a remarkably selective easy-to-prepare test paper.

A test paper for high-selectivity detecting fluoride ion in natural aqueous environments without any spectroscopic instrumentation was achieved by using Ru-bipy based quinonehydrazone as a chromo- and fluorogenic hybrid chemosensor.