Molecular-Level Insights into the Relationship between Volatility of Organic Aerosol Constituents and PM2.5 Air Pollution Levels: A Study with Ultrahigh-Resolution Mass Spectrometry.

Volatility of organic aerosols (OAs) significantly influences new particle formation and the occurrence of particulate air pollution. However, the relationship between the volatility of OA and the level of particulate air pollution (i.e., particulate matter concentration) is not well understood. In this study, we compared the chemical composition (identified by an ultrahigh-resolution Orbitrap mass spectrometer) and volatility (estimated based on a predeveloped parametrization method) of OAs in urban PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 µm) samples from seven German and Chinese cities, where the PM2.5 concentration ranged from a light (14 µg m-3) to heavy (319 µg m-3) pollution level. A large fraction (71-98%) of compounds in PM2.5 samples were attributable to intermediate-volatility organic compounds (IVOCs) and semivolatile organic compounds (SVOCs). The fraction of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs) decreased from clean (28%) to heavily polluted urban regions (2%), while that of IVOCs increased from 34 to 62%. We found that the average peak area-weighted volatility of organic compounds in different cities showed a logarithmic correlation with the average PM2.5 concentration, indicating that the volatility of urban OAs increases with the increase of air pollution level. Our results provide new insights into the relationship between OA volatility and PM pollution levels and deepen the understanding of urban air pollutant evolution.

Trimethylamine from Subtropical Forests Rival Total Farmland Emissions in China.

Many types of living plants release gaseous trimethylamine (TMA), making it a potentially important contributor to new particle formation (NPF) in remote areas. However, a panoramic view of the importance of forest biogenic TMA at the regional scale is lacking. Here, we pioneered nationwide mobile measurements of TMA across a transect of contiguous farmland in eastern China and a transect of subtropical forests in southern China. In contrast to the farmland route, TMA concentrations measured during the subtropical forest route correlated significantly with isoprene, suggesting potential TMA emissions from leaves. Our high time-resolved concentrations obtained from a weak photo-oxidizing atmosphere reflected freshly emitted TMA, indicating the highest emission intensity from irrigated dryland (set as the baseline of 10), followed by paddy field (7.1), subtropical evergreen forests (5.9), and subtropical broadleaf and mixed forests (4.3). Extrapolating their proportions roughly to China, subtropical forests alone, which constitute half of the total forest area, account for nearly 70% of the TMA emissions from the nation's total farmland. Our estimates, despite the uncertainties, take the first step toward large-scale assessment of forest biogenic amines, highlighting the need for observational and modeling studies to consider this hitherto overlooked source of TMA.

Life-Course Health Risk Assessment of PM2.5 Elements in China: Exposure Disparities by Species, Source, Age, Gender, and Location.

Key stages in people's lives have particular relevance for their health; the life-course approach stresses the importance of these stages. Here, we applied a life-course approach to analyze the health risks associated with PM2.5-bound elements, which were measured at three sites with varying environmental conditions in eastern China. Road traffic was found to be the primary source of PM2.5-bound elements at all three locations, but coal combustion was identified as the most important factor to induce both cancer risk (CR) and noncancer risk (NCR) across all age groups due to the higher toxicity of elements such as As and Pb associated with coal. Nearly half of NCR and over 90% of CR occurred in childhood (1-6 years) and adulthood (>18 years), respectively, and females have slightly higher NCR and lower CR than males. Rural population is found to be subject to the highest health risks. Synthesizing previous relevant studies and nationwide PM2.5 concentration measurements, we reveal ubiquitous and large urban-rural environmental exposure disparities over China.

pH-Dependent Aqueous-Phase Brown Carbon Formation: Rate Constants and Implications for Solar Absorption and Atmospheric Photochemistry.

Aqueous-phase reactions of α-dicarbonyls with amines or ammonium have been identified as important sources of secondary brown carbon (BrC). However, the kinetics of BrC formation and the effects of pH are still not very clear. In this study, the kinetics of BrC formation by aqueous reactions of α-dicarbonyls (glyoxal and methylglyoxal) with ammonium, amino acids, or alkylamines in bulk solution at different pH values are investigated. Our results reveal pH-parameterized BrC production rate constants, kBrCII (m-1 [M]-2 s-1), based on the light absorption between 300 and 500 nm: log10(kBrCII) = (1.0 ± 0.1) × pH - (7.4 ± 1.0) for reactions with glyoxal and log10(kBrCII) = (1.0 ± 0.1) × pH - (6.3 ± 0.9) for reactions with methylglyoxal. The linear slopes closing to 1.0 indicate that BrC formation is governed by the nitrogen nucleophilic addition pathway. Consequently, the absorptivities of the produced BrC increase exponentially with the increase of pH. BrC from reactions with methylglyoxal at higher pH (≥6.5) exhibits optical properties comparable to BrC from biomass burning or coal combustion, categorized as the "weakly" absorbing BrC, while BrC from reactions with methylglyoxal at lower pH (<6.0) or reactions with glyoxal (pH 5.0-7.0) falls into the "very weakly" absorbing BrC. The pH-dependent BrC feature significantly affects the solar absorption ability of the produced BrC and thus the atmospheric photochemical processes, e.g., BrC produced at pH 7.0 absorbs 14-16 times more solar power compared to that at pH 5.0, which in turn could lead to a decrease of 1 order of magnitude in the photolysis rate constants of O3 and NO2.

Methylsiloxanes from Vehicle Emissions Detected in Aerosol Particles.

Methylsiloxanes have gained growing attention as emerging pollutants due to their toxicity to organisms. As man-made chemicals with no natural source, most research to date has focused on volatile methylsiloxanes from personal care or household products and industrial processes. Here, we show that methylsiloxanes can be found in primary aerosol particles emitted by vehicles based on aerosol samples collected in two tunnels in São Paulo, Brazil. The aerosol samples were analyzed with thermal desorption-proton transfer reaction-mass spectrometry (TD-PTR-MS), and methylsiloxanes were identified and quantified in the mass spectra based on the natural abundance of silicon isotopes. Various methylsiloxanes and derivatives were found in aerosol particles from both tunnels. The concentrations of methylsiloxanes and derivatives ranged 37.7-377 ng m-3, and the relative fractions in organic aerosols were 0.78-1.9%. The concentrations of methylsiloxanes exhibited a significant correlation with both unburned lubricating oils and organic aerosol mass. The emission factors of methylsiloxanes averaged 1.16 ± 0.59 mg kg-1 of burned fuel for light-duty vehicles and 1.53 ± 0.37 mg kg-1 for heavy-duty vehicles. Global annual emissions of methylsiloxanes in vehicle-emitted aerosols were estimated to range from 0.0035 to 0.0060 Tg, underscoring the significant yet largely unknown potential for health and climate impacts.

Transmission Line Voltage Measurement Utilizing a Calibrated Suspension Grounding Voltage Sensor.

The accurate voltage measurement of distribution networks is of great significance in power dispatching and fault diagnosis. Voltage sensors based on the spatial electric field effect do not require grounding, which provides the possibility for the distributed measurement of transmission line voltages. However, the divider ratio of suspension grounding voltage sensors is affected by the height between the sensor and the ground, as well as the distance between the sensor and the telegraph pole. In this paper, a self-calibration method based on internal capacitance transformation is proposed to realize the on-line calibration of suspension grounding voltage sensors. The calibration is accomplished by switching different parameters in the conditioning circuit, and the calibration process does not require power failure or known input excitation. In addition, the impact of electric fields in the other two phases of three-phase transmission lines on measurement through simulation research is quantified in this paper. In order to reduce the impact of interference electric fields, an equipotential shielding structure is designed. The circuit topology and probe prototype have been developed and testing has been conducted in laboratory conditions; the experimental results show that the maximum relative error of voltage amplitude is 1.65%, and the phase relative error is 0.94%. The measurement accuracy is not limited by the height to ground or the distance to the telegraph pole. In addition, in the application of an equipotential shielding probe, the maximum deviation of measured voltage is 0.7% with and without interference electric fields.

New Insights into the Brown Carbon Chromophores and Formation Pathways for Aqueous Reactions of α-Dicarbonyls with Amines and Ammonium.

Aqueous-phase reactions of α-dicarbonyls with ammonium or amines have been identified as important sources of secondary brown carbon (BrC). However, the identities of most chromophores in these reactions and the effects of pH remain largely unknown. In this study, the chemical structures, formation pathways, and optical properties of individual BrC chromophores formed through aqueous reactions of α-dicarbonyls (glyoxal and methylglyoxal) with ammonium, amino acids, or methylamine at different pH's were characterized in detail by liquid chromatography-photodiode array-high resolution tandem mass spectrometry. In total, 180 chromophores are identified, accounting for 29-79% of the light absorption of bulk BrC for different reactions. Thereinto, 155 newly identified chromophores, including 76 imidazoles, 57 pyrroles, 10 pyrazines, 9 pyridines, and 3 imidazole-pyrroles, explain additionally 9-69% of the light absorption, and these chromophores mainly involve four formation pathways, including previously unrecognized reactions of ammonia or methylamine with the methylglyoxal dimer for the formation of pyrroles. The pH in these reactions also shows remarkable effects on the formation and transformation of BrC chromophores; e.g., with the increase of pH from 5.0 to 7.0, the light absorption contributions of imidazoles in identified chromophores decrease from 72% to 65%, while the light absorption contributions of pyrazines increase from 5% to 13% for the methylglyoxal + ammonium reaction; meanwhile, more small nitrogen heterocycles transformed into oligomers (e.g., C9 and C12 pyrroles) via reaction with methylglyoxal. These newly identified chromophores and proposed formation pathways are instructive for future field studies of the formation and transformation of aqueous-phase BrC.

Nonagricultural emissions enhance dimethylamine and modulate urban atmospheric nucleation.

Gas-phase dimethylamine (DMA) has recently been identified as one of the most important vapors to initiate new particle formation (NPF), even in China's polluted atmosphere. Nevertheless, there remains a fundamental need for understanding the atmospheric life cycle of DMA, particularly in urban areas. Here we pioneered large-scale mobile observations of the DMA concentrations within cities and across two pan-region transects of north-to-south (∼700 km) and west-to-east (∼2000 km) in China. Unexpectedly, DMA concentrations (mean ± 1σ) in South China with scattered croplands (0.018 ± 0.010 ppbv, 1 ppbv=10-9 L/L) were over three times higher than those in the north with contiguous croplands (0.005 ± 0.001 ppbv), suggesting that nonagricultural activities may be an important source of DMA. Particularly in non-rural regions, incidental pulsed industrial emissions led to some of the highest DMA concentration levels in the world (>2.3 ppbv). Besides, in highly urbanized areas of Shanghai, supported by direct source-emission measurements, the spatial pattern of DMA was generally correlated with population (R2 = 0.31) due to associated residential emissions rather than vehicular emissions. Chemical transport simulations further show that in the most populated regions of Shanghai, residential DMA emissions can contribute for up to 78% of particle number concentrations. Shanghai is a case study for populous megacities, and the impacts of nonagricultural emissions on local DMA concentration and nucleation are likely similar for other major urban regions globally.

Recent Progress in Atmospheric Chemistry Research in China: Establishing a Theoretical Framework for the "Air Pollution Complex".

Atmospheric chemistry research has been growing rapidly in China in the last 25 years since the concept of the "air pollution complex" was first proposed by Professor Xiaoyan TANG in 1997. For papers published in 2021 on air pollution (only papers included in the Web of Science Core Collection database were considered), more than 24 000 papers were authored or co-authored by scientists working in China. In this paper, we review a limited number of representative and significant studies on atmospheric chemistry in China in the last few years, including studies on (1) sources and emission inventories, (2) atmospheric chemical processes, (3) interactions of air pollution with meteorology, weather and climate, (4) interactions between the biosphere and atmosphere, and (5) data assimilation. The intention was not to provide a complete review of all progress made in the last few years, but rather to serve as a starting point for learning more about atmospheric chemistry research in China. The advances reviewed in this paper have enabled a theoretical framework for the air pollution complex to be established, provided robust scientific support to highly successful air pollution control policies in China, and created great opportunities in education, training, and career development for many graduate students and young scientists. This paper further highlights that developing and low-income countries that are heavily affected by air pollution can benefit from these research advances, whilst at the same time acknowledging that many challenges and opportunities still remain in atmospheric chemistry research in China, to hopefully be addressed over the next few decades.

Self-Calibration Sensor for Contactless Voltage Measurement Based on Dynamic Capacitance.

Noncontact voltage measurement has the advantages of simple handling, high construction safety, and not being affected by line insulation. However, in practical measurement of noncontact voltage, sensor gain is affected by wire diameter, wire insulation material, and relative position deviation. At the same time, it is also subject to interference from interphase or peripheral coupling electric fields. This paper proposes a noncontact voltage measurement self-calibration method based on dynamic capacitance, which realizes self-calibration of sensor gain through unknown line voltage to be measured. Firstly, the basic principle of the self-calibration method for noncontact voltage measurement based on dynamic capacitance is introduced. Subsequently, the sensor model and parameters were optimized through error analysis and simulation research. Based on this, a sensor prototype and remote dynamic capacitance control unit that can shield against interference are developed. Finally, the accuracy test, anti-interference ability test, and line adaptability test of the sensor prototype were conducted. The accuracy test showed that the maximum relative error of voltage amplitude was 0.89%, and the phase relative error was 1.57%. The anti-interference ability test showed that the error offset was 0.25% when there were interference sources. The line adaptability test shows that the maximum relative error in testing different types of lines is 1.01%.

Online Calibration Study of Non-Contact Current Sensors for Three-Phase Four-Wire Power Cables.

Three-phase four-wire power cables are a primary kind of power transmission method in low-voltage distribution networks. This paper addresses the problem that calibration currents are not easily electrified during the transporting of three-phase four-wire power cable measurements, and proposes a method for obtaining the magnetic field strength distribution in the tangential direction around the cable, finally enabling online self-calibration. The simulation and experimental results show that this method can self-calibrate the sensor arrays and reconstruct the phase current waveforms in three-phase four-wire power cables without calibration currents, and this method is not affected by disturbances such as wire diameter, current amplitudes, and high-frequency harmonics. This study reduces the time and equipment costs required to calibrate the sensing module compared to related studies using calibration currents. This research offers the possibility of fusing sensing modules directly with running primary equipment, and the development of hand-held measurement devices.

Direct emissions of particulate glyoxal and methylglyoxal from biomass burning and coal combustion.

Glyoxal (Gly) and methylglyoxal (Mgly) are key precursors globally for secondary organic aerosol (SOA) formation. These two species were often thought to be formed in the atmosphere via photochemical oxidation of organics from biogenic and anthropogenic origins, although few studies have shown their direct emissions. In this study, we report direct emissions of particulate Gly and Mgly from different residential fuels typically used in north China. The emission ratios (ERs) and emission factors (EFs) of particulate Gly and Mgly for biomass burning were approximate 5-fold and 7-fold higher than those for coal combustion, respectively. The large variances in emissions of Gly and Mgly could be attributed to the different combustion processes, which influenced by the fuel types and combustion conditions. The averaged ERs and EFs of particulate Gly and Mgly were about one order of magnitude lower than their gaseous counterparts due to the low Henry's law constant, which was also consistent with the low particle-to-gas ratio of Gly (0.04) and Mgly (0.02). Our results suggest that the direct emissions of Gly and Mgly from emission sources should be considered when estimating the formation of SOA from Gly and Mgly.

Accumulation of dissolved organic matter in the transition from fresh to aged seasonal snow in an industrial city in NE China.

Dissolved organic matter (DOM) plays a significant role in the reduction of snow albedo and the acceleration of snowmelt, but its accumulation in snow remains poorly understood. This study investigated the accumulation of DOM in seasonal snow including its accumulation rate, molecular characteristics, and biological and chemical processing. Sixteen snow samples of both fresh and aged snow were collected at one-day interval in Changchun, a typical industrial city in NE China. The snow DOM contents increased linearly with accumulation time at a rate of 30.3 µg L-1 d-1. The optical properties, including fluorescence intensity and optical absorption coefficient, of snowmelt increased exponentially with time owing to the rapid accumulation of terrestrial humic-like fluorophores through snow-soil exchange and deposition of soil-derived substances. Fourier transform-ion cyclotron resonance-mass spectrometry highlighted the properties of DOM at a molecular level, indicating that compounds derived from underlying soil and vascular plants make the largest contribution to DOM. Microbe-derived compounds contribute 35.5 % to the DOM pool. Degrees of saturation and oxidation increase slightly after accumulation, with the impacts of photo- and bio-chemistry on DOM molecules being non-negligible. This study provides a new perspective concerning the accumulation and fate of organic contaminants in snow ecosystems.

Staggered-peak production is a mixed blessing in the control of particulate matter pollution.

Staggered-peak production (SP)-a measure to halt industrial production in the heating season-has been implemented in North China Plain to alleviate air pollution. We compared the variations of PM1 composition in Beijing during the SP period in the 2016 heating season (SPhs) with those in the normal production (NP) periods during the 2015 heating season (NPhs) and 2016 non-heating season (NPnhs) to investigate the effectiveness of SP. The PM1 mass concentration decreased from 70.0 ± 54.4 µg m-3 in NPhs to 53.0 ± 56.4 µg m-3 in SPhs, with prominent reductions in primary emissions. However, the fraction of nitrate during SPhs (20.2%) was roughly twice that during NPhs (12.7%) despite a large decrease of NOx, suggesting an efficient transformation of NOx to nitrate during the SP period. This is consistent with the increase of oxygenated organic aerosol (OOA), which almost doubled from NPhs (22.5%) to SPhs (43.0%) in the total organic aerosol (OA) fraction, highlighting efficient secondary formation during SP. The PM1 loading was similar between SPhs (53.0 ± 56.4 µg m-3) and NPnhs (50.7 ± 49.4 µg m-3), indicating a smaller difference in PM pollution between heating and non-heating seasons after the implementation of the SP measure. In addition, a machine learning technique was used to decouple the impact of meteorology on air pollutants. The deweathered results were comparable with the observed results, indicating that meteorological conditions did not have a large impact on the comparison results. Our study indicates that the SP policy is effective in reducing primary emissions but promotes the formation of secondary species.

Research on a Non-Contact Multi-Electrode Voltage Sensor and Signal Processing Algorithm.

Traditional contact voltage measurement requires a direct electrical connection to the system, which is not easy to install and maintain. The voltage measurement based on the electric field coupling plate capacitance structure does not need to be in contact with the measured object or the ground, which can avoid the above problems. However, most of the existing flat-plate structure voltage measurement sensors are not only expensive to manufacture, but also bulky, and when the relative position between the wire under test and the sensor changes, it will bring great measurement errors, making it difficult to meet actual needs. Aiming to address the above problems, this paper proposes a multi-electrode array structure non-contact voltage sensor and signal processing algorithm. The sensor is manufactured by the PCB process, which effectively reduces the manufacturing cost and process difficulty. The experimental and simulation results show that, when the relative position of the wire and the sensor is offset by 10 mm in the 45° direction, the relative error of the traditional single-electrode voltage sensor is 17.62%, while the relative error of the multi-electrode voltage sensor designed in this paper is only 0.38%. In addition, the ratio error of the sensor under the condition of power frequency of 50 Hz is less than ±1% and the phase difference is less than 4°. The experimental results show that the sensor has good accuracy and linearity.

Heterogeneous iodine-organic chemistry fast-tracks marine new particle formation.

The gas-phase formation of new particles less than 1 nm in size and their subsequent growth significantly alters the availability of cloud condensation nuclei (CCN, >30-50 nm), leading to impacts on cloud reflectance and the global radiative budget. However, this growth cannot be accounted for by condensation of typical species driving the initial nucleation. Here, we present evidence that nucleated iodine oxide clusters provide unique sites for the accelerated growth of organic vapors to overcome the coagulation sink. Heterogeneous reactions form low-volatility organic acids and alkylaminium salts in the particle phase, while further oligomerization of small α-dicarbonyls (e.g., glyoxal) drives the particle growth. This identified heterogeneous mechanism explains the occurrence of particle production events at organic vapor concentrations almost an order of magnitude lower than those required for growth via condensation alone. A notable fraction of iodine associated with these growing particles is recycled back into the gas phase, suggesting an effective transport mechanism for iodine to remote regions, acting as a "catalyst" for nucleation and subsequent new particle production in marine air.

A large contribution of methylsiloxanes to particulate matter from ship emissions.

The chemical and stable carbon isotopic composition of the organic aerosol particles (OA) emitted by a shuttle passenger ship between mainland Naples and island Capri in Italy were investigated. Various methylsiloxanes and derivatives were found in particulate ship emissions for the first time, as identified in the mass spectra of a thermal desorption - proton transfer reaction - mass spectrometer (TD-PTR-MS) based on the natural abundance of silicon isotopes. Large contributions of methylsiloxanes to OA (up to 59.3%) were found under inefficient combustion conditions, and considerably lower methylsiloxane emissions were observed under cruise conditions (1.2% of OA). Furthermore, the stable carbon isotopic composition can provide a fingerprint for methylsiloxanes, as they have low δ13C values in the range of -44.91‰ ± 4.29‰. The occurrence of methylsiloxanes was therefore further supported by low δ13C values of particulate organic carbon (OC), ranging from -34.7‰ to -39.4‰, when carbon fractions of methylsiloxanes in OC were high. The δ13C values of OC increased up to around -26.7‰ under cruise conditions, when carbon fractions of methylsiloxanes in OC were low. Overall, the δ13C value of OC decreased linearly with increasing carbon fraction of methylsiloxanes in OC, and the slope is consistent with a mixture of methylsiloxanes and fuel combustion products. The methylsiloxanes in ship emissions may come from engine lubricants.

Chemical signature and fractionation of trace elements in fine particles from anthropogenic and natural sources.

The health effects of trace metal elements in atmospheric fine particulate matter (PM2.5) are widely recognized, however, the emission factor profiles and chemical fractionation of metal elements in different sources were poorly understand. In this study, sixteen metal elements, including Cd, Pb, V, Zn, Ba, Sb, As, Fe, Sr, Cr, Rb, Co, Mn, Cu, Ni and Sn from biomass burning, bituminite and anthracite combustion, as well as dust, were quantified. The results show different emission sources were associated with distinct emission profiles, holding important implications for source apportionment of ambient particulate metals. Specifically, Fe was the dominant metal species (28-1922 mg/kg) for all samples, and was followed by different metals for different samples. For dust, Mn (39.9 mg/kgdust) had the second-highest emission factor, while for biomass burning, it was Cr and Ba (7.5 and 7.4 mg/kgbiomass, respectively). For bituminous coal combustion, the emission factor of Zn and Ba was 6.2 and 6.0 mg/kgbituminous, respectively, while for anthracite combustion the corresponding emission factor was 5.6 and 4.3 mg/kganthracite, respectively. Moreover, chemical fractionation (i.e., the exchangeable, reducible fraction, oxidizable, and residual fraction) and the bioavailability index (BI) values of the metal elements from different sources were further investigated to reveal the link between different emission sources and the potential health risk. The findings from this study hold important implications for source apportionment and source-specific particulate metal-associated health effects.