Interference from HONO in the measurement of ambient air NO2 via photolytic conversion and quantification of NO

The reference method to quantify mixing ratios of the criteria air pollutant nitrogen dioxide (NO₂) is NO-O₃ chemiluminescence (CL), in which mixing ratios of nitric oxide (NO) are measured by sampling ambient air directly, and mixing ratios of NO_x (= sum of NO and NO₂) are measured by converting NO₂ to NO using, for example, heated molybdenum catalyst or, more selectively, photolytic conversion (P-CL). In this work, the nitrous acid (HONO) interference in the measurement of NO₂ by P-CL was investigated. Results with two photolytic NO₂ converters are presented. The first used radiation centered at 395 nm, a wavelength region commonly utilized in P-CL. The second used light at 415 nm, where the overlap with the HONO absorption spectrum and hence its photolysis rate are less. Mixing ratios of NO₂, NO_x and HONO entering and exiting the converters were quantified by Thermal Dissociation Cavity Ring-down Spectroscopy (TD-CRDS). Both converters exhibited high NO₂ conversion efficiency (CF_NO2; > 90%) and partial conversion of HONO. Plots of CF against flow rate were consistent with photolysis frequencies of 4.2 s^-1 and 2.9 s^-1 for NO₂ and 0.25 s^-1 and 0.10 s^?1 for HONO at 395 nm and 415 nm, respectively. CF_HONO was larger than predicted from the overlap of the emission and HONO absorption spectra. The results imply that measurements of NO₂ by P-CL marginally but systematically overestimate true NO₂ concentrations, and that this interference should be considered in environments with high HONO:NO₂ ratios such as the marine boundary layer or in biomass burning plumes.     

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Heterogeneous reactions of NO₂ on different surfaces play an important role in atmospheric NO_x removal and HONO formation, having profound impacts on photochemistry in polluted urban areas. Previous studies have suggested that the NO₂ uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during the daytime. However, the uptake behavior of NO₂ varies with different surfaces, and different uptake coefficients were used or derived in different studies. To obtain a more holistic picture of heterogeneous NO₂ uptake on different surfaces, a series of laboratory experiments using different flow tube reactors was conducted, and the NO₂ uptake coefficients (γ) were determined on inorganic particles, sea water and urban grime. The results showed that heterogeneous reactions on those surfaces were generally weak in dark conditions, with the measured γ varied from <10^?8 to 3.2 × 10^?7 under different humidity. A photo-enhanced uptake of NO₂ on urban grime was observed, with the obvious formation of HONO and NO from the heterogeneous reaction. The photo-enhanced γ was measured to be 1.9 × 10^?6 at 5% relative humidity (RH) and 5.8 × 10^?6 at 70% RH on urban grime, showing a positive RH dependence for both NO₂ uptake and HONO formation. The results demonstrate an important role of urban grime in the daytime NO₂-to-HONO conversion, and could be helpful to explain the unknown daytime HONO source in the polluted urban area.     

Significant influences of TiO2 crystal structures on NO2 and HONO emissions from the nitrates photolysis

The emissions of NO₂ and HONO from the KNO₃ photolysis in the presence of TiO₂ were measured using a round-shape reactor coupled to a NO_x analyzer. TiO₂ played important roles in the emission flux density of NO₂ (R_NO2) and HONO (R_HONO), depending on crystal structures and mass ratios of TiO₂. R_NO2 and R_HONO significantly decreased with increasing the rutile and anatase mass ratios from 0 to 8 and 0.5 wt.%, respectively. Nevertheless, with further increasing the anatase mass ratio to 8 wt.%, there was an increase in R_NO2 and R_HONO. R_NO2 on KNO₃/TiO₂/SiO₂ had positive correlation with the KNO₃ mass (1–20 wt.%), irradiation intensity (80–400 W/m²) and temperature (278–308 K), while it had the maximum value at the relative humidity (RH) of 55%. R_HONO on KNO₃/TiO₂/SiO₂ slightly varied with the KNO₃ mass and temperature, whereas it increased with the irradiation intensity and RH. In addition, the mechanism for NO₂ and HONO emissions from the nitrates photolysis and atmospheric implications were discussed.     

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide (SO₂) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO₃) combined with NO₂ and acetic acid to investigate their effects on the heterogeneous reaction of SO₂ on CaCO₃ particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO₂ or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO₂ and SO₂ that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO₂ that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO₂ with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.     

Measurement of HONO flux using the aerodynamic gradient method over an agricultural field in the Huaihe River Basin, China

To investigate nitrous acid(HONO) levels and potential HONO sources above crop rotation fields. The HONO fluxes were measured by the aerodynamic gradient(AG) method from 14 December 2019 to 2 January 2020 over an agricultural field in the Huaihe River Basin. The ambient HONO levels were measured at two different heights(0.15 and 1.5 m), showing a typical diurnal cycle with low daytime levels and high nighttime levels. The upward HONO fluxes were mostly observed during the day, whereas deposition...     

Observations of N2O5 and NO3 at a suburban environment in Yangtze river delta in China: Estimating heterogeneous N2O5 uptake coefficients

The nitrate radical(NO₃) and dinitrogen pentoxide(N_2.5) play an important role in the nocturnal atmosphere chemistry.Observations of N03 radicals and N₂ O₅ were performed in a semirural ground site at Tai’Zhou in polluted southern China using cavity ring down spectroscopy(CRDS) from 23 May to 15 June 2018.The observed N03 and N₂ O₅ concentrations were relatively low,with 1 min average value of 4.4±2.2 and 26.0±35.7 pptV,respective...     

Effectiveness evaluation of water-sprinkling in controlling urban fugitive road dust based on TRAKER method: A case study in Baoding, China

Fugitive road dust (FRD) contributes a great deal to urban rainwater and air pollution and is commonly controlled by water-sprinkling in most Chinese cities. However, there is a lack of information on its effectiveness. We used the Testing Re-entrained Aerosol Kinetic Emissions from Roads (TRAKER) method to monitor different types of roads in Baoding city before and within 1 hr after water-sprinkling and obtained the road dirtiness index (a) and PM concentration in the road environment ($T_{\mathrm{T}}^{*}$), to evaluate the removal efficiency for PM deposited on the road surface (${\eta }_a$) and the reduction efficiency for the PM concentration in the road environment (${\eta }_{\text{PM}}$). The results give that the ${\eta }_a$ for three types of roads is ranked: branch road (87%-–100%) > major arterial road (80%-83%) > minor arterial road (68%-77%), and the ${\eta }_{\text{PM}}$ ranked: minor arterial road (70%) > branch road (46%-58%) > major arterial road (37%-53%). The ${\eta }_a$ and ${\eta }_{\text{PM}}$ varied non-linearly with time and presented a quadratic curve. The average effective control time (${\eta }_{\mathit{a}}$> 0) was 62 min on the major and minor arterial roads, and much longer than 1 hr on branch roads. The ${\eta }_{\text{PM}}$ values diminished completely by 72 min on average from the end of sprinkling for the three types of roads. Water-sprinkling can remove PM₁₀ particles from the road surface and reduce their concentration in the road environment more thoroughly than PM_2.5. Our findings could be helpful for controlling urban FRD emissions more efficiently and precisely.     

Turnover of dissolved organic carbon fuels nocturnal CO2 emissions from a headwater catchment reservoir, Southeastern China: Effects of ecosystem metabolism on source partitioning of CO2 emissions

Dam reservoirs in headwater catchments, as critical zones for their proximity to terrestrial sources, play important roles in dissolved organic carbon (DOC) cycling. However, the effects of ecosystem metabolism (EM) on DOC cycling are not well known. Here, in-situ diurnal and monthly observations were conducted to measure EM (including gross primary production (GPP), ecosystem respiration (ER) and heterotrophic respiration (HR)), DOC turnover and CO₂ emissions in a headwater catchment reservoir in Southeastern China in 2020. Our study showed the nocturnal CO₂ emission rate was about twice as high as in daytime, and was strongly driven by EM. The values for DOC turnover velocity ranged from 0.10 to 1.59 m/day, and the average DOC turnover rate was 0.13 day⁻¹, with the average removal efficiency of 12%. The contribution of respired DOC to daily CO₂ emissions ranged from 17% to 61%. The accumulated efficiencies were estimated to be 13% for the selected 15 reservoirs throughout the Changjiang River network, corresponding to about 0.34 Tg C/year of the respired DOC. The modified CO₂ flux was 0.75 Tg C/year, and respired DOC accounted for about 45% of total emitted CO₂ from the 15 larger reservoirs. Our research emphasizes the necessity of incorporating the effects of EM into studies of reservoir DOC removal and CO₂ emissions.     

Cross-boundary transport and source apportionment for PM2.5 in a typical industrial city in the Hebei Province, China: A modeling study

Cross-boundary transport of air pollution is a difficult issue in pollution control for the North China Plain. In this study, an industrial district (Shahe City) with a large glass manufacturing sector was investigated to clarify the relative contribution of fine particulate matter (PM_2.5) to the city's high levels of pollution. The Nest Air Quality Prediction Model System (NAQPMS), paired with Weather Research and Forecasting (WRF), was adopted and applied with a spatial resolution of 5 km. During the study period, the mean mass concentrations of PM_2.5, SO₂, and NO₂ were observed to be 132.0, 76.1, and 55.5 μg/m³, respectively. The model reproduced the variations in pollutant concentrations in Shahe at an acceptable level. The simulation of online source-tagging revealed that pollutants emitted within a 50-km radius of downtown Shahe contributed 63.4% of the city's total PM_2.5 concentration. This contribution increased to 73.9±21.2% when unfavorable meteorological conditions (high relative humidity, weak wind, and low planetary boundary layer height) were present; such conditions are more frequently associated with severe pollution (PM_2.5 ≥ 250 μg/m³). The contribution from Shahe was 52.3±21.6%. The source apportionment results showed that industry (47%), transportation (10%), power (17%), and residential (26%) sectors were the most important sources of PM_2.5 in Shahe. The glass factories (where chimney stack heights were normally < 70 m) in Shahe contributed 32.1% of the total PM_2.5 concentration in Shahe. With an increase in PM_2.5 concentration, the emissions from glass factories accumulated vertically and narrowed horizontally. At times when pollution levels were severe, the horizontally influenced area mainly covered Shahe. Furthermore, sensitivity tests indicated that reducing emissions by 20%, 40%, and 60% could lead to a decrease in the mass concentration of PM_2.5 of of 12.0%, 23.8%, and 35.5%, respectively.     

Effect of potential HONO sources on peroxyacetyl nitrate (PAN) formation in eastern China in winter

As an important secondary photochemical pollutant, peroxyacetyl nitrate (PAN) has been studied over decades, yet its simulations usually underestimate the corresponding observations, especially in polluted areas. Recent observations in north China found unusually high concentrations of PAN during wintertime heavy haze events, but the current model still cannot reproduce the observations, and researchers speculated that nitrous acid (HONO) played a key role in PAN formation. For the first time we systematically assessed the impact of potential HONO sources on PAN formation mechanisms in eastern China using the Weather Research and Forecasting/Chemistry (WRF-Chem) model in February of 2017. The results showed that the potential HONO sources significantly improved the PAN simulations, remarkably accelerated the RO_x (sum of hydroxyl, hydroperoxyl, and organic peroxy radicals) cycles, and resulted in 80%–150% enhancements of PAN near the ground in the coastal areas of eastern China and 10%–50% enhancements in the areas around 35–40°N within 3 km during a heavy haze period. The direct precursors of PAN were aldehyde and methylglyoxal, and the primary precursors of PAN were alkenes with C > 3, xylenes, propene and toluene. The above results suggest that the potential HONO sources should be considered in regional and global chemical transport models when conducting PAN studies.     

Characterization of precipitation in the background of atmospheric pollutants reduction in Guilin: Temporal variation and source apportionment

Rainfall samples were collected from three observation sites in Guilin from 2013 to 2017, and the chemical composition characteristics of precipitation and the contribution made by different ion sources were analyzed when atmospheric pollutants levels were reduced. The results showed that acid gas emissions and atmospheric pollutant concentrations continued to decline during the study period. However, the change in the volume-weighted mean p H at the three sites suggested that acid rain pollutio...     

Seasonal variation and sources of atmospheric polycyclic aromatic hydrocarbons in a background site on the Tibetan Plateau

The study of atmospheric polycyclic aromatic hydrocarbons (PAHs) in northeastern Tibetan Plateau with fragile ecological environment and complex atmospheric circulation system is blank. To understand the characteristics and sources of persistent organic pollutants in the atmosphere of the northeastern Tibetan Plateau, we monitored levels in the central Qilian Mountain. From 2016 to 2017, we collected 45-pair (particle + gas) samples using active air samplers to investigate the sources, transport paths, and their influencing factors. Sources of PAHs were analysed with a source diagnostic model, and atmospheric transport paths were calculated. The concentration range for ∑₁₅PAHs was 439–4666 pg/m³, and the average was 2015 pg/m³. The PAHs in central Qilian Mountain are mainly low molecular weight (LMW) PAHs. Winter concentrations of PAHs were higher than those in summer. The transport of PAHs is mainly affected by westerlies, and there are seasonal differences. Source analysis showed that PAHs mainly came from coal and biomass combustion and vehicle emissions, with seasonal differences. This study clarifies the concentration and seasonal variation of PAHs in the northern Tibetan Plateau, which is conducive to understanding the atmospheric transport process and fate of pollutants. The background site of Qilian Mountains located in the Silk Road economic belt has the value and significance of long-term observation of pollutants.     

A preliminary study on pollution characteristics of surfactant substances in fine particles in the Beibu Gulf Region of China

The pollution characteristics of surfactant substances in fine particles (PM_2.5) in spring were studied in the Beibu Gulf Region of China, 68 samples of PM_2.5 were collected at Weizhou Island in Beihai City from March 12 to April 17, 2015. The Anionic Surfactant Substances (ASS) and Cationic Surfactant Substances (CSS) in the samples were analyzed using Byethyl Violet Spectrophotometry and Disulfide Blue Spectrophotometry, respectively. Combined with the data from backward trajectory simulation, the effects of air pollutants from remote transport on the pollution characteristics of surfactant substances in PM_2.5 in the Beibu Gulf Region were analyzed and discussed. The results showed that the daily mean concentrations of ASS and CSS in spring in the Beibu Gulf Region were 165.20 pmol/m³ and 8.05pmol/m³, and the variation ranges were 23.21–452.55 pmol/m³ and 0.65–31.31 pmol/m³, accounting for 1.82‰ ± 1.65‰ and 0.12‰ ± 0.11‰ of the mass concentration of PM_2.5, respectively. These concentrations were lower than those in comparable regions around the world. There was no clear correlation between the concentrations of ASS and CSS in PM_2.5 and the mass concentrations of PM_2.5. Tourism and air transport had a positive contribution on the concentrations of ASS. The concentration of surfactant substances in PM_2.5 was significantly impacted by wind speed and wind direction. Atmospheric temperature, air pressure and precipitation had little effect on the concentrations of surfactant substances. Surfactant substances in PM_2.5 significantly impacted visibility. Results also showed that the main sources of surfactant substances were from the southern China and Southeast Asia.     

Concentrations and distribution of novel brominated flame retardants in the atmosphere and soil of Ny-Ålesund and London Island, Svalbard, Arctic

Novel brominated flame retardants (NBFRs) were investigated in Arctic air and soil samples collected from Ny-Ålesund and London Island, Svalbard, during Chinese scientific research expeditions to the Arctic during 2014–2015. The concentrations of Σ₉NBFRs in the Arctic air and soil were 4.9–8.7 pg/m³ (average 6.8 pg/m³) and 101–201 pg/g dw (average 150 pg/g dw), respectively. The atmospheric concentration of hexabromobenzene (HBB) was significantly correlated with that of pentabromotoluene (PBT) and pentabromobenzene (PBBz), suggesting similar source and environmental fate in the Arctic air. No significant spatial difference was observed among the different sampling sites, both for air and soil samples, indicating that the effects of the scientific research stations on the occurrence of NBFRs in the Arctic were minor. The fugacities from soil to air of pentabromoethylbenzene (PBEB), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE), and decabromodiphenylethane 1,2-bis (pentabromophenyl) ethane (DBDPE) were lower than the equilibrium value, indicating a nonequilibrium state of these compounds between air and soil, the dominant impact of deposition and the net transport from air to soil. The correlation analysis between the measured and predicted soil-atmosphere coefficients based on the absorption model showed that the impact of the soil organic matter on the distribution of NBFRs in the Arctic region was minor. To the best of our knowledge, this work is one of the limited reports on atmospheric NBFRs in the Arctic and the first study to investigate the occurrence and fate of NBFRs in the Arctic soil.     

A critical review on the technique and mechanism of microwave-based denitrification in flue gas

Microwave radiation has received extensive attention due to its significant thermal and non-thermal effects, and the development of MW-based denitrification in flue gas has become one of the most promising methods to avoid the defects of ammonia escape, high temperature and cost in traditional SCR. This review introduces the thermal and non-thermal effects of microwaves and divides MW-based denitrification methods into MW reduction and oxidation denitrification, systematically summarizes these denitrification methods, including MW discharge reduction, MW-induced catalytic reduction using active carbon, molecular sieves, metal oxides (transition metals, perovskites, etc.), MW-induced oxidation denitrification with and without additional oxidant, and discusses their removal pathway and mechanism. Finally, several research prospects and directions regarding the development of microwave-based denitrification methods are provided.     

Effects of natural organic matter on cadmium mobility in paddy soil: A review

Cadmium (Cd) contamination in paddy soil has caused public concern. The uptake of Cd by rice plants depends on soil Cd mobility, which is in turn substantially influenced by organic matter (OM). In this review, we first summarize the fate of Cd in soil and the role of OM. We then focus on the effects of OM on Cd mobility in paddy soil and the factors influencing the remedial effectiveness of OM amendments. We further discuss the performance of straw incorporation in the remediation of Cd-contaminated paddy soils reported in laboratory and field studies. Considering the huge production of organic materials (such as straw) in agriculture, the use of natural OM for soil remediation has obvious appeal due to the environmental benefits and low cost. Although there have been successful application cases, the properties of OM amendments and soil can significantly affect the remedial performance of the OM amendments. Importantly, straw incorporation alone does not often decrease the mobility of Cd in soil or the Cd content in rice grains. Careful evaluation is required when considering natural OM amendments, and the factors and mechanisms that influence their remedial effectiveness need further investigation in paddy soil with realistic Cd concentrations.     

Impact of pre-oxidation on the formation of byproducts in algae-laden water disinfection: Insights from fluorescent and molecular weight

Pre-oxidation has been reported to be an effective way to remove algal cells in water, but the released algal organic matter (AOM) could be oxidized and lead to the increment in disinfection by-product (DBP) formation. The relationship between pre-oxidation and AOM-derived DBP formation needs to be approached more precisely. This study compared the impact of four pre-oxidants, ozone (O₃), chlorine dioxide (ClO₂), potassium permanganate (KMnO₄) and sodium hypochlorite (NaClO), on the formation of nitrogenous (N-) and carbonaceous (C-) DBPs in AOM chlorination. The characterization (fluorescent properties, molecular weight distribution and amino acids concentration) on AOM samples showed that the characterization properties variations after pre-oxidation were highly dependent on the oxidizing ability of oxidants. The disinfection experiments showed that O₃ increased DBP formation most significantly, which was consistent with the result of characterization properties variations. Then canonical correspondent analysis (CCA) and Pearson's correlation analysis were conducted based on the characterization data and DBP formation. CCA indicated that C-DBPs formation was highly dependent on fluorescent data. The formation of haloacetic acids (HAAs) had a positive correlation with aromatic protein-like component while trichloromethane (TCM) had a positive correlation with fulvic acid-like component. Pearson's correlation analysis showed that low molecular weight fractions were favorable to form N-DBPs. Therefore, characterization data could provide the advantages in the control of DBP formation, which further revealed that KMnO₄ and ClO₂ were better options for removing algal cells as well as limiting DBP formation.     

Evidence of aircraft activity impact on local air quality: A study in the context of uncommon airport operation

Wuhan Tianhe International Airport (WUH) was suspended to contain the spread of COVID-19, while Shanghai Hongqiao International Airport (SHA) saw a tremendous flight reduction. Closure of a major international airport is extremely rare and thus represents a unique opportunity to straightforwardly observe the impact of airport emissions on local air quality. In this study, a series of statistical tools were applied to analyze the variations in air pollutant levels in the vicinity of WUH and SHA. The results of bivariate polar plots show that airport SHA and WUH are a major source of nitrogen oxides. NO_x, NO₂ and NO diminished by 55.8%, 44.1%, 76.9%, and 40.4%, 33.3% and 59.4% during the COVID-19 lockdown compared to those in the same period of 2018 and 2019, under a reduction in aircraft activities by 58.6% and 61.4%. The concentration of NO₂, SO₂ and PM_2.5 decreased by 77.3%, 8.2%, 29.5%, right after the closure of airport WUH on 23 January 2020. The average concentrations of NO, NO₂ and NO_x scatter plots at downwind of SHA after the lockdown were 78.0%, 47.9%, 57.4% and 62.3%, 34.8%, 41.8% lower than those during the same period in 2018 and 2019. However, a significant increase in O₃ levels by 50.0% and 25.9% at WUH and SHA was observed, respectively. These results evidently show decreased nitrogen oxides concentrations in the airport vicinity due to reduced aircraft activities, while amplified O₃ pollution due to a lower titration by NO under strong reduction in NO_x emissions.     

A review of atmospheric benzene homologues in China: Characterization, health risk assessment, source identification and countermeasures

Benzene homologues are important chemical precursors to the formation of ground-level ozone and secondary organic aerosol(SOA) in the atmosphere,in addition,some toxic species are harmful to human health.Strict countermeasures have been taken to fight air pollution since 2013,and total amount control of volatile organic compounds is being promoted in China at present.Therefore,it is important to understand the pollution situation and the control status of ambient benzene homologues in China.This...     

Influence of urban morphological parameters on the distribution and diffusion of air pollutants: A case study in China

Air pollution has a serious fallout on human health, and the influences of the different urban morphological characteristics on air pollutants cannot be ignored. In this study, the relationship between urban morphology and air quality (wind speed, CO, and PM_2.5) in residential neighborhoods at the meso-microscale was investigated. The changes in the microclimate and pollutant diffusion distribution in the neighborhood under diverse weather conditions were simulated by Computational Fluid Dynamics (CFD). This study identified five key urban morphological parameters (Building Density, Average Building Height, Standard Deviation of Building Height, Mean Building Volume, and Degree of Enclosure) which significantly impacted the diffusion and distribution of pollutants in the neighborhood. The findings of this study suggested that three specific strategies (e.g. volume of a single building should be reduced, DE should be increased) and one comprehensive strategy (the width and height of the single building should be reduced while the number of single buildings should be increased) could be illustrated as an optimized approach of urban planning to relief the air pollution. The result of the combined effects could provide a reference for mitigating air pollution in sustainable urban environments.