Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone(O_(3))formation regime is a prerequisite in formulating an effective O_(3)pollution control strategy.Photochemical indicator is a simple and direct method in identifying O_(3)formation regimes.Most used indicators are derived from observations,whereas the role of atmospheric oxidation is not in consideration,which is the core driver of O_(3)formation.Thus,it may impact accuracy in signaling O_(3)formation regimes.In this study,an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O_(3)formation regimes during a long-lasting O_(3)exceedance event in September 2017 over the Pearl River Delta(PRD)of China.We discovered a clear relationship between atmospheric oxidative capacity and O_(3)formation regime.Over eastern PRD,O_(3)formation was mainly in a NO x-limited regime when HO_(2)/OH ratio was higher than 11,while in a VOC-limited regime when the ratio was lower than 9.5.Over central and western PRD,an HO_(2)/OH ratio higher than 5 and lower than 2 was indicative of NO x-limited and VOC-limited regime,respectively.Physical contribution,including horizontal transport and vertical transport,may pose uncertainties on the indication of O_(3)formation regime by HO_(2)/OH ratio.In comparison with other commonly used photochemical indicators,HO_(2)/OH ratio had the best performance in differentiating O_(3)formation regimes.This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O_(3)formation regime,and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O_(3)pollution over a photochemically active region.

Researchers Discover Quantum Switch for Regulating Photosynthesis

Photosynthesis is a crucial process that allows plants to convert carbon dioxide into organic compounds using solar energy.Light-harvesting complex II(LHCII)is a complex of pigment molecules bound to proteins.It switches between two main functions-dissipating harmful excess light energy as heat under high light intensity through nonphotochemical quenching,and transferring absorbed light to the reaction center with almost a unit efficiency under low light.

A Review of Atmospheric Chemistry Research in China:Photochemical Smog, Haze Pollution,and Gas-Aerosol Interactions

In this paper we present a review of atmospheric chemistry research in China over the period 2006-2010, focusing on tropospheric ozone, aerosol chemistry, and the interactions between trace gases and aerosols in the polluted areas of China. Over the past decade, China has suffered severe photochemical smog and haze pollution, especially in North China, the Yangtze River Delta, and the Pearl River Delta. Much scientific work on atmospheric chemistry and physics has been done to address this large-scale, complex environmental problem. Intensive field experiments, satellite data analyses, and model simulations have shown that air pollution is significantly changing the chemical and physical characters of the natural atmosphere over these parts of China. In addition to strong emissions of primary pollutants, photochemical and heterogeneous reactions play key roles in the formation of complex pollution. More in-depth research is recommended to reveal the formation mechanism of photochemical smog and haze pollution and their climatic effects at the urban, regional, and global scales.

Current technology development for CO2 utilization into solar fuels and chemicals:A review

The continuous consumption of fossil fuels causes two important impediments including emission of large concentrations of CO2 resulting in global warming and alarming utilization of energy assets.The conversion of greenhouse gas CO2 into solar fuels can be an expedient accomplishment for the solution of both problems,all together.CO2 reutilization into valuable fuels and chemicals is a great challenge of the current century.Owing to limitations in traditional approaches,there have been developed many novel technologies such as photochemical,biochemical,electrochemical,plasma-chemical and solar thermochemical.They are currently being used for CO2 capture,sequestration,and utilization to transform CO2 into valuable products such as syngas,methane,methanol,formic acid,as well as fossil fuel consumption reduction.This review summarizes different traditional and novel thermal technologies used in CO2 conversion with detailed information about their working principle,types,currently adopted methods,developments,conversion rates,products formed,catalysts and operating conditions.Moreover,a comparison of these novel technologies in terms of distinctive key features such as conversion rate,yield,use of earth metals,renewable energy,investment,and operating cost has been provided in order to have a useful review for future research direction.

Construction and Characterization of an Atmospheric Simulation Smog Chamber

Currently, air pollution in Beijing has become a complex problem with two types of source pollutants： coal smoke and photochemical smog. Furthermore the maximum hourly mean concentration of O3 increases continuously, especially in the summer. In order to simulate the photochemical reaction, develop an air quality simulation model and further improve the air quality of Beijing, a precisely temperature-controlled, indoor, smog chamber facility was designed and constructed at Tsinghua University. Characterization experiments have been carried out to acquire the basic parameters of the smog chamber, such as the wall loss rates of NO2, NO, O3, C3H6 and particulate matter （PM）, the intensity of ultraviolet （UV） light in the chamber, the reactivity of the purified air and the reproducibility of the experimental results. The results indicate that the facility performs up to specifications, and can meet the demands required for simulating the photochemical reaction. The effect of high primary contaminated PM on the formation of ozone and secondary organic aerosol （SOA） is under investigation.

Photochemical pollution in Lanzhou, China - A case study

The photochemical air pollution in Xigu district of Lanshou city, Gansu Province was studied during a period of 1981-1984. The extremely high NMHC/NOx ratio and ozone level elevation after rain have been noticed. A series of outdoor and indoor reaction chamber simulation experiments conducted in order to understand the specific conditions. The ozone formation under NMHC/NOx condition and the possible reason for high ozone concentration after rain are discussed.

Photoassisted fenton oxidation of refractory organics in UASB-pretreated leachate

Nearly 91% of organic pollutants in Hong Kong leachate could be effectively removed by the UASB(upflow anaerobic sludge blanket) process followed by the fenton coagulation. The COD (chemical oxygen demand) of leachate was lowered from an average of 5620 mg/L to 1910 mg/L after the UASB treatment at 37℃, and was further lowered to 513 mg/L after fenton coagulation. The remaining refractory residues could be further removed by photochemical oxidation with the addition of H 2O 2. The BOD/COD ratio was greatly increased from 0.062 to 0.142, indicating the biodegradability of organic residues was improved. The photochemical oxidation for the fenton\|coagulation supernatant was most effective at pH 3\_4, with the addition of 800 mg/L of H 2O 2, and UV radiation time of 30 minutes. The final effluent contained only 148 mg/L of COD, 21 mg/L of BOD(biochemical oxygen demand) and 56 mg/L of TOC (total organic carbon).

Spatial and Temporal Distributions and Sources of Anthropogenic NMVOCs in the Atmosphere of China:A Review

As the key precursors of O_(3),anthropogenic non-methane volatile organic compounds(NMVOCs)have been studied intensively.This paper performed a meta-analysis on the spatial and temporal variations of NMVOCs,their roles in photochemical reactions,and their sources in China,based on published research.The results showed that both nonmethane hydrocarbons(NMHCs)and oxygenated VOCs(OVOCs)in China have higher mixing ratios in the eastern developed cities compared to those in the central and western areas.Alkanes are the most abundant NMHCs species in all reported sites while formaldehyde is the most abundant among the OVOCs.OVOCs have the highest mixing ratios in summer and the lowest in winter,which is opposite to NMHCs.Among all NMVOCs,the top eight species account for 50%−70%of the total ozone formation potential(OFP)with different compositions and contributions in different areas.In devolved regions,OFP-NMHCs are the highest in winter while OFP-OVOCs are the highest in summer.Based on positive matrix factorization(PMF)analysis,vehicle exhaust,industrial emissions,and solvent usage in China are the main sources for NMHCs.However,the emission trend analysis showed that solvent usage and industrial emissions will exceed vehicle exhaust and become the two major sources of NMVOCs in near future.Based on the meta-analysis conducted in this work,we believe that the spatio-temporal variations and oxidation mechanisms of atmospheric OVOCs,as well as generating a higher spatial resolution of emission inventories of NMVOCs represent an area for future studies on NMVOCs in China.

Effects of 4f Electron Characteristics and Alternation Valence of Rare Earths on Photosynthesis: Regulating Distribution of Energy and Activities of Spinach Chloroplast

Chloroplasts were isolated from spinach treated with taCl3, CeCl3, and NdCl3. Because of owning 4f electron characteristics and alternation valence, Ce treatment presented the highest enhancement in light absorption, energy transfer from LHC Ⅱ to PS Ⅱ, excitation energy distribution from PS Ⅰ to PS Ⅱ, and fluorescence quantum yield around 680 nm. Compared with Ce treatment, Nd treatment resulted in relatively lower enhancement in these physiological indices, as Nd did not have alternation valence. La treatment presented the lowest enhancement, as La did not have either 4f electron or alternation valence. The increase in activities of whole chain electron transport, PS ⅡDCPIP photoreduction, and oxygen evolution of chloroplasts was of the following order： Ce〉Nd 〉La〉 control. However, the photoreduction activities of spinach PS I almost did not change with La, Ce, or Nd treatments. The results suggested that 4f electron characteristics and alternation valence of rare earths had a close relationship with photosynthesis improvement.

Hypoglycaemic effect of Berberis vulgaris L.in normal and streptozotocin-induced diabetic rats

Objective:To achieve a primary pharmacological screening contained in the aqueous extract of Berberis vulgaris(B.vulgaris) and to examine the hypoglycaemic effect and biochemical parameters of aqueous and saponins extract on groups of rats rendered diabetic by injection of streptozotocin.Methods:The phytochemicol tests to detect the presence of different compounds were based on the visual observation of color change or formation of precipitate after the addition of specific reagents.Diabetes was induced in rats by intraperitoneal(i.p.) injection of streptozotocin(STZ) at a dose of 65 mg/kg bw.The fasting blood glucose levels were estimated by glucose oxidase-peroxidase reactive strips(Dextrostix,Bayer Diagnostics).Blood samples were taken by cutting the tip of the tail.Serum cholesterol and serum triglycerides were estimated by enzymatic DHBS colorimetric method.Results:Administration of 62.5 and 2S.0 mg/kg of saponins and aqueous extract respectively in normal rats group shows a significant hypoglycemic activity(32.33%and 40.17%respectively) during the first week.However,diabetic group treated with saponin extract produced a maximum fall of 73.1%and 76.03%at day 1 and day 21 compared to the diabetics control.Also,blood glucose levels of the diabetic rats treated with aqueous extract showed decrease of 78.79%on the first day and the effect remains roughly constant during 3 week. Both extracts also declined significantly biochemical parameters(20.77%-49.00%).The control in the loss of body weight was observed in treated diabetic rats as compared to diabetic controls. Conclusions:These results demonstrated significant antidiabetic effects and showed that serum cholesterol and serum triglycerides levels were decreased,significantly,consequently this plant might be of value in diabetes treatment.

The Photochemical Study of HSA and BSA with Resonance Light Scattering and Fluorescence Spectra

The resonance light-scattering (RLS) of human serum albumin (HSA) and bovine serum albumin (BSA) is reported for the first time, and applied to study photochemical reaction of HSA and BSA. The fact of photocrosslinking self-association effect in HSA and BSA solutions is identified by the enhancement of RLS. The fluorescence quenching at about 350 nm and 700 nm proves that tryptophan (Trp) residues are one of the photochemical activity sites in HSA and BSA molecules. The Rayleigh scattering (RS) spectra of HSA and BSA that were neglected in fluorescence spectra before are found at about 296 nm, 592 nm and 888 nm for the first time, and are of adventageous to studying the aggregation of HSA or BSA. The possible photochemical reaction mechanism is also proposed.

Assessment of Photochemical Reflectance Index as a Tool for Evaluation of Chlorophyll Fluorescence Parameters in Cotton and Peanut Cultivars Under Water Stress Condition

The relationships between photochemical reflectance index （PRI） and the chlorophyll fluorescence parameters were examined to assess suitability of PRI as a remote-sensing tool for the chlorophyll fluorescence parameters. A greenhouse experiment was conducted using cotton and peanut crops under water stress condition. Five cotton and six peanut cultivars were grown using Andosole soil in pots maintained at two water levels; the control and water stress treatment （WS） of 100 and 50% of the daily transpiration, respectively. Higher non-photochemical quenching （NPQ） was exhibited by peanut than that of cotton by the water stress. On the other hand, the decreases of the actual quantum yield of photosystem II （△F/F＇m） and PRI by the water stress in cotton were larger than those in peanut. There were positively significant correlation coefficients between PRI and △F/F＇m in cotton at noon and in the afternoon including the control and WS. The correlations of PRI with NPQ were negatively significant at noon and in the afternoon for cotton, and in the afternoon for peanut. No clear relationship was found among these parameters in the morning probably due to the diurnal increase in global solar radiation. It was concluded that there would be a possibility to detect the effects of water stress on △F/F＇m and NPQ by PRI with some exceptions, although PRI could not note varietals differences in △F/F＇m and NPQ for each treatment.

Potential Oxidative Stress in the Bodies of Electric Arc Welding Operators: Effect of Photochemical Smog

Objective To investigate whether photochemical smog emitted during the process of electric arc welding might cause oxidative stress and potential oxidative damage in the bodies of welding operators. Methods Seventy electric arc welding operators (WOs) and 70 healthy volunteers (HVs) were enrolled in a randomized controlled study design, in which the levels of vitamin C (VC) and vitamin E (VE) in plasma as well as the activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX), and the level of lipoperoxide (LPO) in erythrocytes were determined by spectrophotometry. Results Compared with the average values of the above experimental parameters in the HVs group, the average values of VC and VE in plasma as well as those of SOD, CAT and GPX in erythrocytes in the WOs group were significantly decreased (P<0.005-0.0001), while the average value of LPO in erythrocytes in the WOs group was significantly increased (P<0.0001). The findings from the partial correlation analysis on the controlling of age suggested that with a prolonged duration of exposure to photochemical smog the values of VC, VE, SOD, and GPX, except for CAT, in the WOs were decreased gradually (P<0.05-0.005), the value of LPO in the WOs was increased gradually (P<0.001), and that with the ozone dose increased in the air in each worksite VC, VE, SOD, CAT and GPX decreased (P<0.005-0.001), but LPO increased (P<0.001). The findings from the reliability analysis for the VC, VE, SOD, CAT, GPX, and LPO values which were used to reflect oxidative stress and potential oxidative damage in the WOs showed that the reliability coefficients?alpha (6 items) was 0.8021, P<0.0001, and that the standardized item alpha was 0.9577, P<0.0001. Conclusion Findings in the present study suggest that there exists an oxidative stress induced by long-term exposure to photochemical smog in the bodies of WOs, thereby causing potential oxidative and lipoperoxidative damages in their bodies.

Traffic emission and its impact on air quality in Guangzhou area

A comprehensive field measurement was set up in Guangzhou City of China and the key was placed on NO\-x and O\-3 pollution. The results indicated that the average driving speed of vehicle was only 14 km/h in downtown with high frequency of idle and acceleration. Upward fluxes of CO and NO were observed in Dongfeng Street. NO\-x annual mean concentration in urban area increased year by year, and NO\-x was identified as the most important pollutant since 1995. Photochemical smog pollution was serious in general, spatial and seasonal distribution of O\-3 was observed. O\-3 concentration was kept in a high level in autumn, and its formation was restrained in summer due to frequent thunderstorm and high humidity. The numerical simulation showed the average concentration and maximum concentration of O\-3 would increase 60%—100% if vehicular emission increased 100% in Guangzhou.

Sonochemical Synthesis of Core/Shell Structured CdS/TiO_2 Nanocrystals Composites

A simple sonochemical route for the surface coating of titanium dioxide on cadmium sulfide nanocrystal was reported. After 2 h ultrasonic irradiation treatment, the mixture of CdS nanocrystals and tetrabutyl titanate in an aqueous medium yielded CdS/TiO2 nanocrystals composites with core/shell structure. The thickness of TiO2 layer with smooth interface could be easily controlled via changing the concentration of the precursors and the time of irradiation. The core/shell nanocrysrals were characterized by X-ray diffraction, transmission electron microscope and UV-vis spectrometry techniques. The prepared semiconductor composites with particular band structure present appealing properties especially in photochemical activity.

Photochemical degradation of environmentally persistent perfluorooctanoic acid (PFOA) in the presence of Fe(Ⅲ)

Environmentally persistent and bioaccumulative perfluorooctanic acid （PFOA） was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol/L Fe（Ⅲ）, 80% of PFOA with initial concentration of 48μmol/L （20 mg/L） was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe（Ⅲ） initiated degradation of PFOA irradiated with 254 nm UV light.

Environmental chamber study of the photochemical reaction of ethyl methyl sulfide and NO_x

A series of experiments were conducted in a self-made smog chamber at （300 ＋ 1） K and 1.01 × 10^5 Pa to simulate the photochemical reaction of ethyl methyl sulfide （EMS） and NOx. The results showed that the higher the initial concentration of EMS, the more ozone was generated in the simulative reactions. It was found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d（Oa-NO） and IR （incremental reactivity） were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this article for the five simulative reactions were 1.55 × 10^-2, 0.99 × 10^-2, 1.36 × 10^-2, 2.47 × 10^-2, and 1.65 × 10^-2, respectively. A comparison between the results we obtained here and the results we obtained previously for di-tert-butyl peroxide and acetylene showed that the potential reactivity of EMS on ozone formation was at a relatively low level.

A New Index Developed for Fast Diagnosis of Meteorological Roles in Ground-Level Ozone Variations

China experienced worsening ground-level ozone(O_(2)) pollution from 2013 to 2019. In this study, meteorological parameters, including surface temperature(T_(2)), solar radiation(SW), and wind speed(WS), were classified into two aspects,(1) Photochemical Reaction Condition(PRC = T_(2)× SW) and(2) Physical Dispersion Capacity(PDC = WS). In this way, a Meteorology Synthetic Index(MSI = PRC/PDC) was developed for the quantification of meteorology-induced ground-level O_(2)pollution. The positive linear relationship between the 90 th percentile of MDA8(maximum daily 8-h average) O_(2)concentration and MSI determined that the contribution of meteorological changes to ground-level O-3 varied on a latitudinal gradient, decreasing from ~40% in southern China to 10%–20% in northern China. Favorable photochemical reaction conditions were more important for ground-level O_(2)pollution. This study proposes a universally applicable index for fast diagnosis of meteorological roles in ground-level O_(2)variability, which enables the assessment of the observed effects of precursor emissions reductions that can be used for designing future control policies.

RO_(x) Budgets and O_(3) Formation during Summertime at Xianghe Suburban Site in the North China Plain

Photochemical smog characterized by high concentrations of ozone(O_(3)) is a serious air pollution issue in the North China Plain(NCP)region,especially in summer and autumn.For this study,measurements of O_(3),nitrogen oxides(NO_(x)),volatile organic compounds(VOCs),carbon monoxide(CO),nitrous acid(HONO),and a number of key physical parameters were taken at a suburban site,Xianghe,in the NCP region during the summer of 2018 in order to better understand the photochemical processes leading to O_(3)formation and find an optimal way to control O_(3)pollution.Here,the radical chemistry and O_(3)photochemical budget based on measurement data from 1−23 July using a chemical box model is investigated.The daytime(0600−1800 LST)average production rate of the primary radicals referred to as RO_(x)(OH+HO2+RO2)is 3.9 ppbv h−1.HONO photolysis is the largest primary RO_(x)source(41%).Reaction of NO2+OH is the largest contributor to radical termination(41%),followed by reactions of RO2+NO2(26%).The average diurnal maximum O_(3)production and loss rates are 32.9 ppbv h−1 and 4.3 ppbv h−1,respectively.Sensitivity tests without the HONO constraint lead to decreases in daytime average primary RO_(x)production by 55%and O_(3)photochemical production by 42%,highlighting the importance of accurate HONO measurements when quantifying the RO_(x)budget and O_(3)photochemical production.Considering heterogeneous reactions of trace gases and radicals on aerosols,aerosol uptake of HO2 contributes 11%to RO_(x)sink,and the daytime average O_(3)photochemical production decreases by 14%.The O_(3)-NO_(x)-VOCs sensitivity shows that the O_(3)production at Xianghe during the investigation period is mainly controlled by VOCs.

Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai,Shandong Province

Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.