Rapid hydrolysis of NO2 at High Ionic Strengths of Deliquesced Aerosol Particles.

Nitrogen dioxide (NO2) hydrolysis in deliquesced aerosol particles forms nitrous acid and nitrate and thus impacts air quality, climate, and the nitrogen cycle. Traditionally, it is considered to proceed far too slowly in the atmosphere. However, the significance of this process is highly uncertain because kinetic studies have only been made in dilute aqueous solutions but not under high ionic strength conditions of the aerosol particles. Here, we use laboratory experiments, air quality models, and field measurements to examine the effect of the ionic strength on the reaction kinetics of NO2 hydrolysis. We find that high ionic strengths (I) enhance the reaction rate constants (kI) by more than an order of magnitude compared to that at infinite dilution (kI=0), yielding log10(kI/kI=0) = 0.04I or rate enhancement factor = 100.04I. A state-of-the-art air quality model shows that the enhanced NO2 hydrolysis reduces the negative bias in the simulated concentrations of nitrous acid by 28% on average when compared to field observations over the North China Plain. Rapid NO2 hydrolysis also enhances the levels of nitrous acid in other polluted regions such as North India and further promotes atmospheric oxidation capacity. This study highlights the need to evaluate various reaction kinetics of atmospheric aerosols with high ionic strengths.

Atmospheric environment characteristic of severe dust storms and its impact on sulfate formation in downstream city.

This study comprehensively investigated the impact of dust storms (DSs) on downstream cities, by selecting representative DS events. In this paper, we discussed the characteristics of meteorological conditions, air pollutants, PM2.5 components, and their influence on sulfate formation mechanisms. During DSs, strong winds, reaching speeds of up to 10 m/s, led to significant increases in PM10 and PM2.5, with maximum concentrations of 2684.5 and 429 µg/m3, respectively. Primary gaseous pollutants experienced substantial reductions, with decline rates of 48.1, 34.9, 36.8, and 9.0 % for SO2, NO2, NH3, and CO, respectively. Despite a notable increase in PM2.5 concentrations, only 7.6 % of the total mass of PM2.5 was attributed to ionic and carbonaceous components, a much lower value than observed before the DSs (77.3 %). Concentrations of Fe, Ti, and Mn exhibited increases by factors of 6.5-14.1, 10.4-17.0, and 1.6-4.7, respectively. In contrast to the significant decrease of >76.2 % in nitrogen oxidation ratio (NOR), sulfur oxidation ratio (SOR) remained at a relatively high level, displaying a strong positive correlation with high concentrations of Fe, Mn, and Ti. Quantitative analysis revealed an average increase of 0.187 and 0.045 µg/m3 in sulfate from natural sources and heterogeneous generation, respectively. The heterogeneous reaction on mineral dust was closely linked to atmospheric humidity, radiation intensity, the form of metal existence, and concentrations of it. High concentrations of titanium dioxide and iron­manganese oxides in mineral dust promoted heterogeneous oxidation of SO2 through photocatalysis during the daytime and metal ion catalysis during the nighttime. This study establishes that the metal components in mineral dust promote heterogeneous sulfate formation, quantifies the yield of sulfate generated as a result, and provides possible mechanisms for heterogeneous sulfate formation.

QTL Detection and Candidate Gene Identification for Eating and Cooking Quality Traits in Rice (Oryza sativa L.) via a Genome-Wide Association Study.

The eating and cooking quality (ECQ) directly affects the taste of rice, being closely related to factors such as gelatinization temperature (GT), gel consistency (GC) and amylose content (AC). Mining the quantitative trait loci (QTLs), and gene loci controlling ECQ-related traits is vital. A genome-wide association study on ECQ-related traits was conducted, combining 1.2 million single nucleotide polymorphisms (SNPs) with the phenotypic data of 173 rice accessions. Two QTLs for GT, one for GC and five for AC were identified, of which two were found in previously reported genes, and six were newly found. There were 28 positional candidate genes in the region of qAC11. Based on a linkage disequilibrium (LD) analysis, three candidate genes were screened within the LD region associated with AC. There were significant differences between the haplotypes of LOC_Os11g10170, but no significant differences were found for the other two genes. The qRT-PCR results showed that the gene expression levels in the accessions with high ACs were significantly larger than those in the accessions with low ACs at 35d and 42d after flowering. Hap 2 and Hap 3 of LOC_Os11g10170 reduced the AC by 13.09% and 10.77%, respectively. These results provide a theoretical and material basis for improving the ECQ of rice.

Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity.

Hydroxymethanesulfonate (HMS) has been found to be an abundant organosulfur aerosol compound in the Beijing-Tianjin-Hebei (BTH) region with a measured maximum daily mean concentration of up to 10 µg per cubic meter in winter. However, the production medium of HMS in aerosols is controversial, and it is unknown whether chemical transport models are able to capture the variations of HMS during individual haze events. In this work, we modify the parametrization of HMS chemistry in the nested-grid GEOS-Chem chemical transport model, whose simulations provide a good account of the field measurements during winter haze episodes. We find the contribution of the aqueous aerosol pathway to total HMS is about 36% in winter in Beijing, due primarily to the enhancement effect of the ionic strength on the rate constants of the reaction between dissolved formaldehyde and sulfite. Our simulations suggest that the HMS-to-inorganic sulfate ratio will increase from the baseline of 7% to 13% in the near future, given the ambitious clean air and climate mitigation policies for the BTH region. The more rapid reductions in emissions of SO2 and NOx compared to NH3 alter the atmospheric acidity, which is a critical factor leading to the rising importance of HMS in particulate sulfur species.

Synthesizing evidence for the external cycling of NOx in high- to low-NOx atmospheres.

External cycling regenerating nitrogen oxides (NOx ≡ NO + NO2) from their oxidative reservoir, NOz, is proposed to reshape the temporal-spatial distribution of NOx and consequently hydroxyl radical (OH), the most important oxidant in the atmosphere. Here we verify the in situ external cycling of NOx in various environments with nitrous acid (HONO) as an intermediate based on synthesized field evidence collected onboard aircraft platform at daytime. External cycling helps to reconcile stubborn underestimation on observed ratios of HONO/NO2 and NO2/NOz by current chemical model schemes and rationalize atypical diurnal concentration profiles of HONO and NO2 lacking noontime valleys specially observed in low-NOx atmospheres. Perturbation on the budget of HONO and NOx by external cycling is also found to increase as NOx concentration decreases. Consequently, model underestimation of OH observations by up to 41% in low NOx atmospheres is attributed to the omission of external cycling in models.

Machine learning approaches reveal highly heterogeneous air quality co-benefits of the energy transition.

Estimating health benefits of reducing fossil fuel use from improved air quality provides important rationales for carbon emissions abatement. Simulating pollution concentration is a crucial step of the estimation, but traditional approaches often rely on complicated chemical transport models that require extensive expertise and computational resources. In this study, we develop a machine learning framework that is able to provide precise and robust annual average fine particle (PM2.5) concentration estimations directly from a high-resolution fossil energy use dataset. Applications of the framework with Chinese data reveal highly heterogeneous health benefits of avoiding premature mortality by reducing fossil fuel use in different sectors and regions in China with a mean of $19/tCO2 and a standard deviation of $38/tCO2. Reducing rural and residential coal use offers the highest co-benefits with a mean of $151/tCO2. Our findings prompt careful policy designs to maximize cost-effectiveness in the transition toward a carbon-neutral energy system.

Source apportionment of consumed volatile organic compounds in the atmosphere.

Conventional source apportionments of ambient volatile organic compounds (VOCs) have been based on observed and initial concentrations after photochemical correction. However, these results have not been related to ozone (O3) and secondary organic aerosol (SOA) formation. Thus, the apportioned contributions could not effectively support secondary pollution control development. Source apportionment of the VOCs consumed in forming O3 and SOA is needed. A consumed VOC source apportionment approach was developed and applied to hourly speciated VOCs data from June to August 2022 measured in Laoshan, Qingdao. Biogenic emissions (56.3%), vehicle emissions (17.2%), and gasoline evaporation (9.37%) were the main sources of consumed VOCs. High consumed VOCs from biogenic emissions mainly occurred during transport from parks to the southwest and northwest of study site. During the O3 pollution period, biogenic emissions (46.3%), vehicle emissions (24.2%), and gasoline evaporation (14.3%) provided the largest contributions to the consumed VOCs. However, biogenic emissions contribution increased to 57.1% during the non-O3 pollution period, and vehicle emissions and gasoline evaporation decreased to 16.5% and 9.01%, respectively. Biogenic emissions and the mixed source of combustion sources and solvent use contributed the most to O3 and SOA formation potentials during the O3 pollution period, respectively.

Changes in source apportioned VOCs during high O3 periods using initial VOC-concentration-dispersion normalized PMF.

Ambient volatile organic compounds (VOCs) concentrations are affected by emissions, dispersion, and chemistry. This work developed an initial concentration-dispersion normalized PMF (ICDN-PMF) to reflect the changes in source emissions. The effects of photochemical losses for VOC species were corrected by estimating the initial data, and then applying dispersion normalization to reduce the impacts of atmospheric dispersion. Hourly speciated VOC data measured in Qingdao from March to May 2020 were utilized to test the method and had assessed its effectiveness. Underestimated solvent use and biogenic emissions contributions due to photochemical losses during the O3 pollution (OP) period reached 4.4 and 3.8 times the non-O3 pollution (NOP) period values, respectively. Increased solvent use contribution due to air dispersion during the OP period was 4.6 times the change in the NOP period. The influence of chemical conversion and air dispersion on the gasoline and diesel vehicle emissions was not apparent during either period. The ICDN-PMF results suggested that biogenic emissions (23.1 %), solvent use (23.0 %), motor-vehicle emissions (17.1 %), and natural gas and diesel evaporation (15.8 %) contributed most to ambient VOCs during the OP period. Biogenic emissions and solvent use contributions during the OP period increased by 187 % and 135 % compared with the NOP period, respectively, whereas that of liquefied petroleum gas substantially decreased during the OP period. Controlling solvent use and motor-vehicles could be effective in controlling VOCs in the OP period.

Drivers of High Concentrations of Secondary Organic Aerosols in Northern China during the COVID-19 Lockdowns.

During the COVID-19 lockdown in early 2020, observations in Beijing indicate that secondary organic aerosol (SOA) concentrations increased despite substantial emission reduction, but the reasons are not fully explained. Here, we integrate the two-dimensional volatility basis set into a state-of-the-art chemical transport model, which unprecedentedly reproduces organic aerosol (OA) components resolved by the positive matrix factorization based on aerosol mass spectrometer observations. The model shows that, for Beijing, the emission reduction during the lockdown lowered primary organic aerosol (POA)/SOA concentrations by 50%/18%, while deteriorated meteorological conditions increased them by 30%/119%, resulting in a net decrease in the POA concentration and a net increase in the SOA concentration. Emission reduction and meteorological changes both led to an increased OH concentration, which accounts for their distinct effects on POA and SOA. SOA from anthropogenic volatile organic compounds and organics with lower volatility contributed 28 and 62%, respectively, to the net SOA increase. Different from Beijing, the SOA concentration decreased in southern Hebei during the lockdown because of more favorable meteorology. Our findings confirm the effectiveness of organic emission reductions and meanwhile reveal the challenge in controlling SOA pollution that calls for large organic precursor emission reductions to rival the adverse impact of OH increase.

Observed changes in China's methane emissions linked to policy drivers.

China is set to actively reduce its methane emissions in the coming decade. A comprehensive evaluation of the current situation can provide a reference point for tracking the country's future progress. Here, using satellite and surface observations, we quantify China's methane emissions during 2010-2017. Including newly available data from a surface network across China greatly improves our ability to constrain emissions at subnational and sectoral levels. Our results show that recent changes in China's methane emissions are linked to energy, agricultural, and environmental policies. We find contrasting methane emission trends in different regions attributed to coal mining, reflecting region-dependent responses to China's energy policy of closing small coal mines (decreases in Southwest) and consolidating large coal mines (increases in North). Coordinated production of coalbed methane and coal in southern Shanxi effectively decreases methane emissions, despite increased coal production there. We also detect unexpected increases from rice cultivation over East and Central China, which is contributed by enhanced rates of crop-residue application, a factor not accounted for in current inventories. Our work identifies policy drivers of recent changes in China's methane emissions, providing input to formulating methane policy toward its climate goal.

QTL mapping and identification of candidate genes using a genome-wide association study for heat tolerance at anthesis in rice (Oryza sativa L.).

Heat tolerance (HT) of rice at anthesis is a key trait that ensures high and stable yields under heat stress. Finding the quantitative trait loci (QTLs) and gene loci controlling HT is crucial. We used relative spikelet fertility (RSF) as a measure of HT. The phenotypic values of RSF in 173 rice accessions were investigated in two environments and showed abundant variations. We performed a genome-wide association study on RSF using 1.2 million single nucleotide polymorphisms (SNPs). Five QTLs were significantly associated with RSF were identified, four were found in previously reported QTLs/genes, and one was novel. The novel QTL qRSF9.2 was mapped into the 22,059,984-22,259,984 bp region, which had 38 positional candidate genes. By combining the linkage disequilibrium analysis, the QTL region was narrowed to 22,110,508-22,187,677 bp, which contained 16 candidate genes. Among them, only gene LOC_Os09g38500 contained nonsynonymous SNPs that were significantly associated with RSF. In addition, accessions with large and small RSF values had corresponding respective high and low gene expression levels. Furthermore, the RSF of the CC allele was significantly higher than that of the TT allele. Hap 2 and Hap 3 can increase heat tolerance by 7.9 and 11.3%, respectively. Our results provide useful information that recommends further cloning of qRSF9.2 and breeding heat-tolerant rice varieties by marker-assisted selection.

Vertically Resolved Aerosol Chemistry in the Low Boundary Layer of Beijing in Summer.

Air quality in Beijing has been improved significantly in recent years; however, our knowledge of the vertically resolved aerosol chemistry in summer remains poor. Here, we carried out comprehensive measurements of aerosol composition, gaseous species, and aerosol optical properties on a meteorological tower in Beijing in summer and compared with those measured in winter. Our results showed that aerosol liquid water (ALW) contributing approximately 50% of the total mass with higher values aloft played a crucial role in aerosol formation. Particularly, the higher nitrate concentration in city aloft than at the ground level during daytime was mainly due to the enhanced gas-particle partitioning driven by ALW and particle acidity. The vertical profiles of organic aerosol (OA) factors varied more differently in the urban boundary layer. Although the ubiquitous decreases in primary OA with the increase in height were mainly due to the influences of local emissions and vertical convection, the vertical differences in oxygenated OA between summer and winter may be related to the photochemical processing of different biogenic and anthropogenic volatile organic compounds. The single-scattering albedo, brown carbon, and absorption Ångstrom exponent of aerosol particles also presented different vertical profiles between day and night due to the vertical changes in aerosol chemistry.

Deep decarbonization of the Indian economy: 2050 prospects for wind, solar, and green hydrogen.

The paper explores options for a 2050 carbon free energy future for India. Onshore wind and solar sources are projected as the dominant primary contributions to this objective. The analysis envisages an important role for so-called green hydrogen produced by electrolysis fueled by these carbon free energy sources. This hydrogen source can be used to accommodate for the intrinsic variability of wind and solar complementing opportunities for storage of power by batteries and pumped hydro. The green source of hydrogen can be used also to supplant current industrial uses of gray hydrogen produced in the Indian context largely from natural gas with important related emissions of CO2. The paper explores further options for use of green hydrogen to lower emissions from otherwise difficult to abate sectors of both industry and transport. The analysis is applied to identify the least cost options to meet India's zero carbon future.

Ammonium Chloride Associated Aerosol Liquid Water Enhances Haze in Delhi, India.

The interaction between water vapor and atmospheric aerosol leads to enhancement in aerosol water content, which facilitates haze development, but its concentrations, sources, and impacts remain largely unknown in polluted urban environments. Here, we show that the Indian capital, Delhi, which tops the list of polluted capital cities, also experiences the highest aerosol water yet reported worldwide. This high aerosol water promotes secondary formation of aerosols and worsens air pollution. We report that severe pollution events are commonly associated with high aerosol water which enhances light scattering and reduces visibility by 70%. Strong light scattering also suppresses the boundary layer height on winter mornings in Delhi, inhibiting dispersal of pollutants and further exacerbating morning pollution peaks. We provide evidence that ammonium chloride is the largest contributor to aerosol water in Delhi, making up 40% on average, and we highlight that regulation of chlorine-containing precursors should be considered in mitigation strategies.

The importance of hydroxymethanesulfonate (HMS) in winter haze episodes in North China Plain.

Hydroxymethanesulfonate (HMS), a key marker species of aqueous-phase processing, plays a significant role in sulfur budget in atmosphere. Here we have a comprehensive characterization of HMS at urban and rural sites in North China Plain (NCP) by using the real-time measurements from a high-resolution aerosol mass spectrometer (AMS) and a single-particle AMS together with offline filter analysis. Our results showed much higher winter concentration of HMS at the rural site (average±1σ: 2.58 ± 2.56 µg m-3) than that (1.70 ± 2.68 µg m-3) in Beijing due to the more frequent fog events, low particle acidity and high concentration of precursors. The HMS on average contributed 6.3% and 5.2% to organic aerosol (OA), and 16% and 12% to the total particulate sulfur, at the rural and urban sites, respectively. HMS was highly correlated with aqueous-phase secondary OA and sulfate, and its contribution to the total particulate sulfur increased significantly as a function of relative humidity demonstrating the effective HMS production from aqueous-phase processing. Single-particle analysis showed that HMS-containing particles were mainly mixed with amine-related compounds. In addition, we found that organosulfur compounds (OS) estimated from sulfur-containing fragments of AMS correlated well with HMS at both urban and rural sites. While OS at the rural site was dominated by HMS, other types of OS were also important in urban area. The high HMS also affected the estimation of particle acidity using the AMS measured and predicted ammonium, particularly during severe haze episodes. Overall, our results demonstrated the importance of HMS in winter in NCP, and it could be more important in total particulate sulfur budget as the continuous decrease in sulfate in the future.

Residential building materials: An important source of ambient formaldehyde in mainland China.

This study investigates the contribution of formaldehyde from residential building materials to ambient air in mainland China. Based on 265 indoor field tests in 9 provinces, we estimate that indoor residential sources are responsible for 6.66% of the total anthropogenic formaldehyde in China's ambient air (range for 31 provinces: 1.88-18.79%). Residential building materials rank 6th among 81 anthropogenic sources (range: 2nd-10th for 31 provinces). Emission intensities show large spatial variability between and within regions due to different residential densities, emission characteristics of building materials, and indoor thermal conditions. Our findings indicate that formaldehyde from the indoor environment is a significant source of ambient formaldehyde, especially in urban areas. This study will help to more accurately evaluate exposure to ambient formaldehyde and its related pollutants, and will assist in formulating policies to protect air quality and public health.

Production of hydrogen from offshore wind in China and cost-competitive supply to Japan.

The Japanese government has announced a commitment to net-zero greenhouse gas emissions by 2050. It envisages an important role for hydrogen in the nation's future energy economy. This paper explores the possibility that a significant source for this hydrogen could be produced by electrolysis fueled by power generated from offshore wind in China. Hydrogen could be delivered to Japan either as liquid, or bound to a chemical carrier such as toluene, or as a component of ammonia. The paper presents an analysis of factors determining the ultimate cost for this hydrogen, including expenses for production, storage, conversion, transport, and treatment at the destination. It concludes that the Chinese source could be delivered at a volume and cost consistent with Japan's idealized future projections.

An Unambiguous Synchronization Scheme for GNSS BOC Signals Based on Reconstructed Correlation Function.

Binary offset carrier (BOC) modulation is a new modulation method that has been gradually applied to the Global Satellite Navigation System (GNSS) in recent years. However, due to the multi-peaks in its auto-correlation function (ACF), it will incur a false lock and generate synchronization ambiguous potentially. In this paper, an unambiguous synchronization method based on a reconstructed correlation function is proposed to solve the ambiguity problem. First, through the shape code vector constructed in this paper, the general cross-correlation function (CCF) expression of the BOC modulated signal will be obtained. Based on the features of the signal correlation function, it is decomposed into a matrix form of trigonometric functions. Then, it generates two local signal waves using a specific method, then the proposed method is implemented to obtain a no-side-peak correlation function by reconstructing the cross-correlation between the received signal and the two local signals. Simulations showed that it fully eliminates the side-peak threat and significantly removes the ambiguity during the synchronization of the BOC signals. This paper also gives the improved structure of acquisition and tracking. The detailed theoretical deduction of detection probability and code tracking error is demonstrated, and the corresponding phase discrimination function is given. In terms of de-blurring ability and detection probability performance, the proposed method outperformed other conventional approaches. The tracking performance was superior to the comparison methods and the phase discrimination curve only had a zero-crossing, which successfully removed the false lock points. In addition, in multipath mitigation, it outperformed the ACF of the BOC signal, and performs as well as the autocorrelation side-peak cancellation technique (ASPeCT) for BOC(kn,n) signals.

Ozone pollution in the North China Plain spreading into the late-winter haze season.

Surface ozone is a severe air pollution problem in the North China Plain, which is home to 300 million people. Ozone concentrations are highest in summer, driven by fast photochemical production of hydrogen oxide radicals (HOx) that can overcome the radical titration caused by high emissions of nitrogen oxides (NOx) from fuel combustion. Ozone has been very low during winter haze (particulate) pollution episodes. However, the abrupt decrease of NOx emissions following the COVID-19 lockdown in January 2020 reveals a switch to fast ozone production during winter haze episodes with maximum daily 8-h average (MDA8) ozone concentrations of 60 to 70 parts per billion. We reproduce this switch with the GEOS-Chem model, where the fast production of ozone is driven by HOx radicals from photolysis of formaldehyde, overcoming radical titration from the decreased NOx emissions. Formaldehyde is produced by oxidation of reactive volatile organic compounds (VOCs), which have very high emissions in the North China Plain. This remarkable switch to an ozone-producing regime in January-February following the lockdown illustrates a more general tendency from 2013 to 2019 of increasing winter-spring ozone in the North China Plain and increasing association of high ozone with winter haze events, as pollution control efforts have targeted NOx emissions (30% decrease) while VOC emissions have remained constant. Decreasing VOC emissions would avoid further spreading of severe ozone pollution events into the winter-spring season.

[Evaluation of Different ISORROPIA-â ¡ Modes and the Influencing Factors of Aerosol pH Based on Tianjin Online Data].

Aerosol acidity is closely related to particle properties and the explosive growth of secondary particles. Aerosol pH is difficult to measure directly but can be estimated indirectly by thermodynamic equilibrium modeling. ISORROPIA-Ⅱ is one of the most commonly used thermodynamic models and includes different modes (forward and reverse) and aerosol states (stable and metastable). Studies have shown that the calculated pH results vary with the selected mode and phase state. In addition to the selection of modes and phases, there are also other factors that influence the modeling results. In order to explore the appropriate mode and phase selection of ISORROPIA-Ⅱ as well as the factors influencing the model results under the air pollution characteristics of typical Chinese cities, the simulation results of different modes and aerosol states were analyzed by using online hourly data for Tianjin. The results showed that the pH calculations using the forward mode and metastable state were satisfactory at a higher RH. With increased temperature, the pH, aerosol water content, and concentration proportion in the aerosol phase of semi-volatile components all decreased. RH affected aerosol pH by influencing the aerosol water content and concentration of semi-volatile components. An increased cation concentration led to an increased pH and NH3 concentration but a decreased HNO3 concentration, whereas an increased anion concentration had the opposite effect. Ca2+, SO42-, NO3-, and NH4+ had a great influence on pH. Compared with SO42-, NO3- had less effect on pH. Sensitive areas exist in the influence of NH4+ on pH, and a high NH4+ concentration did not cause a continuous pH increase. This study can improve the understanding of aerosol pH simulation using ISORROPIA-Ⅱ, and provides reference for research on the pH-related secondary generation mechanism, semi-volatile component gas-particle distribution, and pollution control measures.