Global variability in atmospheric new particle formation mechanisms.

A key challenge in aerosol pollution studies and climate change assessment is to understand how atmospheric aerosol particles are initially formed1,2. Although new particle formation (NPF) mechanisms have been described at specific sites3-6, in most regions, such mechanisms remain uncertain to a large extent because of the limited ability of atmospheric models to simulate critical NPF processes1,7. Here we synthesize molecular-level experiments to develop comprehensive representations of 11 NPF mechanisms and the complex chemical transformation of precursor gases in a fully coupled global climate model. Combined simulations and observations show that the dominant NPF mechanisms are distinct worldwide and vary with region and altitude. Previously neglected or underrepresented mechanisms involving organics, amines, iodine oxoacids and HNO3 probably dominate NPF in most regions with high concentrations of aerosols or large aerosol radiative forcing; such regions include oceanic and human-polluted continental boundary layers, as well as the upper troposphere over rainforests and Asian monsoon regions. These underrepresented mechanisms also play notable roles in other areas, such as the upper troposphere of the Pacific and Atlantic oceans. Accordingly, NPF accounts for different fractions (10-80%) of the nuclei on which cloud forms at 0.5% supersaturation over various regions in the lower troposphere. The comprehensive simulation of global NPF mechanisms can help improve estimation and source attribution of the climate effects of aerosols.

The Pivotal Role of Heavy Terpenes and Anthropogenic Interactions in New Particle Formation on the Southeastern Qinghai-Tibet Plateau.

Aerosol particles originating from the Qinghai-Tibet Plateau (QTP) readily reach the free troposphere, potentially affecting global radiation and climate. Although new particle formation (NPF) is frequently observed at such high altitudes, its precursors and their underlying chemistry remain poorly understood. This study presents direct observational evidence of anthropogenic influences on biogenic NPF on the southeastern QTP, near the Himalayas. The mean particle nucleation rate (J1.7) is 2.6 cm-3 s-1, exceeding the kinetic limit of sulfuric acid (SA) nucleation (mean SA: 2.4 × 105 cm-3). NPF is predominantly driven by highly oxygenated organic molecules (HOMs), possibly facilitated by low SA levels. We identified 1538 ultralow-volatility HOMs driving particle nucleation and 764 extremely low-volatility HOMs powering initial particle growth, with mean total concentrations of 1.5 × 106 and 3.7 × 106 cm-3, respectively. These HOMs are formed by atmospheric oxidation of biogenic precursors, unexpectedly including sesquiterpenes and diterpenes alongside the commonly recognized monoterpenes. Counterintuitively, over half of HOMs are organic nitrates, mainly produced by interacting with anthropogenic NOx via RO2+NO terminations or NO3-initiated oxidations. These findings advance our understanding of NPF mechanisms in this climate-sensitive region and underscore the importance of heavy terpene and NOx-influenced chemistry in assessing anthropogenic-biogenic interactions with climate feedbacks.

Modeling the Formation of Organic Compounds across Full Volatility Ranges and Their Contribution to Nanoparticle Growth in a Polluted Atmosphere.

Nanoparticle growth influences atmospheric particles' climatic effects, and it is largely driven by low-volatility organic vapors. However, the magnitude and mechanism of organics' contribution to nanoparticle growth in polluted environments remain unclear because current observations and models cannot capture organics across full volatility ranges or track their formation chemistry. Here, we develop a mechanistic model that characterizes the full volatility spectrum of organic vapors and their contributions to nanoparticle growth by coupling advanced organic oxidation modeling and kinetic gas-particle partitioning. The model is applied to Nanjing, a typical polluted city, and it effectively captures the volatility distribution of low-volatility organics (with saturation vapor concentrations <0.3 µg/m3), thus accurately reproducing growth rates (GRs), with a 4.91% normalized mean bias. Simulations indicate that as particles grow from 4 to 40 nm, the relative fractions of GRs attributable to organics increase from 59 to 86%, with the remaining contribution from H2SO4 and its clusters. Aromatics contribute much to condensable organic vapors (∼37%), especially low-volatility vapors (∼61%), thus contributing the most to GRs (32-46%) as 4-40 nm particles grow. Alkanes also contribute 19-35% of GRs, while biogenic volatile organic compounds contribute minimally (<13%). Our model helps assess the climatic impacts of particles and predict future changes.

Toward Building a Physical Proxy for Gas-Phase Sulfuric Acid Concentration Based on Its Budget Analysis in Polluted Yangtze River Delta, East China.

Gaseous sulfuric acid (H2SO4) is a crucial precursor for secondary aerosol formation, particularly for new particle formation (NPF) that plays an essential role in the global number budget of aerosol particles and cloud condensation nuclei. Due to technology challenges, global-wide and long-term measurements of gaseous H2SO4 are currently very challenging. Empirical proxies for H2SO4 have been derived mainly based on short-term intensive campaigns. In this work, we performed comprehensive measurements of H2SO4 and related parameters in the polluted Yangtze River Delta in East China during four seasons and developed a physical proxy based on the budget analysis of gaseous H2SO4. Besides the photo-oxidation of SO2, we found that primary emissions can contribute considerably, particularly at night. Dry deposition has the potential to be a non-negligible sink, in addition to condensation onto particle surfaces. Compared with the empirical proxies, the newly developed physical proxy demonstrates extraordinary stability in all the seasons and has the potential to be widely used to improve the understanding of global NPF fundamentally.

Cycles of solar ultraviolet radiation favor periodic expansions of cyanobacterial blooms in global lakes.

Global warming and eutrophication are known to increase the prevalence of cyanobacterial blooms, posing a severe threat to the ecological stability and sustainability of water bodies. The long-term (over an annual time frame) effect of UV radiation on cyanobacterial blooms in lakes are rarely discussed though the substantial effects of high-intensity UV radiation on the growth inhibition of marine phytoplankton were studied. Here, we employed the datasets on surface solar UV radiation, nitrogen and phosphorus concentrations, and the annual scales and frequencies of cyanobacterial blooms in lakes across long-term spatial scales to probe the relationship of UV radiation with cyanobacterial blooms. The results indicated that enhanced solar UV radiation may unintentionally stimulate cyanobacterial growth and favor the expansions of cyanobacterial blooms in lakes around the world. The fluctuating UV radiation significantly affects the annual scales of cyanobacterial blooms in both eutrophic and oligotrophic lakes. Solar UV radiation enhances the positive impact of rising phosphorus levels on cyanobacterial blooms because UV radiation prompts the synthesis of polyphosphate in cyanobacteria cells, which helps cyanobacteria to alleviate the stress of UV light. The scales of cyanobacterial blooms are significantly impacted by solar UV radiation intensities as opposed to the annual frequency of cyanobacterial blooms. Furthermore, solar UV radiation fluctuation with a 9-year period over a 14-year main cycles significantly affects the periodicities of cyanobacterial blooms in global lakes, which provides a basis for predicting the peak value of the scales of cyanobacterial blooms in lakes. These findings opened up new avenues of inquiry into the mechanism and management strategies of cyanobacterial blooms in lakes worldwide.

Investigation on the budget of peroxyacetyl nitrate (PAN) in the Yangtze River Delta: Unravelling local photochemistry and regional impact.

Peroxyacetyl nitrate (PAN) is a significant indicator of atmospheric photochemical pollution, which can influence the regional distribution of ozone (O3) and hydroxyl radical (OH) through long-range transport. However, investigations of PAN incorporating comprehensive measurement and explicit modeling analysis are limited, hindering complete understandings of its temporal behavior, sources, and impacts on photochemistry. Here we conducted a 1-year continuous observation of PAN and relative atmospheric species in Nanjing located in Yangtze River Delta (YRD). The annual mean concentration of PAN was 0.62 ± 0.49 ppbv and showed a bimodal monthly variation, peaking in April-June and November-January, respectively. This pattern is different from the typical pattern of photochemistry, suggesting important contributions of other non-photochemical processes. We further analyzed the PAN budget using an observation-based model, by which, PAN from local photochemical production and regional source could be decoupled. Our results revealed that local photochemical production of PAN is the sole contributor to PAN in summer, whereas about half of the total PAN concentration is attributed to regional source in winter. Although the formation of PAN can suppress the atmospheric oxidation capacity by consuming the peroxyacetyl radical and nitrogen dioxide (NO2), our analyses suggested this effect is minor at our station (-3.2 ± 1.1 % in summer and - 7.2 ± 2.8 % in winter for O3 formation). However, it has the potential to enhance O3 and OH formation by 14.16 % and 5.93 %, if transported to cleaner environments with air pollutants halved. Overall, our study highlights the importance of both local photochemistry and regional process in PAN budget and provides a useful evaluation on the impact of PAN on atmospheric oxidation capacity.

Response of organic aerosol characteristics to emission reduction in Yangtze River Delta region.

Organic aerosol (OA) is a major component of atmospheric particulate matter (PM) with complex composition and formation processes influenced by various factors. Emission reduction can alter both precursors and oxidants which further affects secondary OA formation. Here we provide an observational analysis of secondary OA (SOA) variation properties in Yangtze River Delta (YRD) of eastern China in response to large scale of emission reduction during Chinese New Year (CNY) holidays from 2015 to 2020, and the COVID-19 pandemic period from January to March, 2020. We found a 17% increase of SOA proportion during the COVID lockdown. The relative enrichment of SOA is also found during multi-year CNY holidays with dramatic reduction of anthropogenic emissions. Two types of oxygenated OA (OOA) influenced by mixed emissions and SOA formation were found to be the dominant components during the lockdown in YRD region. Our results highlight that these emission-reduction-induced changes in organic aerosol need to be considered in the future to optimize air pollution control measures. Electronic Supplementary Material: Supplementary material is available in the online version of this article at 10.1007/s11783-023-1714-0 and is accessible for authorized users.

Unified theoretical framework for black carbon mixing state allows greater accuracy of climate effect estimation.

Black carbon (BC) plays an important role in the climate system because of its strong warming effect, yet the magnitude of this effect is highly uncertain owing to the complex mixing state of aerosols. Here we build a unified theoretical framework to describe BC's mixing states, linking dynamic processes to BC coating thickness distribution, and show its self-similarity for sites in diverse environments. The size distribution of BC-containing particles is found to follow a universal law and is independent of BC core size. A new mixing state module is established based on this finding and successfully applied in global and regional models, which increases the accuracy of aerosol climate effect estimations. Our theoretical framework links observations with model simulations in both mixing state description and light absorption quantification.

NO at low concentration can enhance the formation of highly oxygenated biogenic molecules in the atmosphere.

The interaction between nitrogen monoxide (NO) and organic peroxy radicals (RO2) greatly impacts the formation of highly oxygenated organic molecules (HOM), the key precursors of secondary organic aerosols. It has been thought that HOM production can be significantly suppressed by NO even at low concentrations. Here, we perform dedicated experiments focusing on HOM formation from monoterpenes at low NO concentrations (0 - 82 pptv). We demonstrate that such low NO can enhance HOM production by modulating the RO2 loss and favoring the formation of alkoxy radicals that can continue to autoxidize through isomerization. These insights suggest that HOM yields from typical boreal forest emissions can vary between 2.5%-6.5%, and HOM formation will not be completely inhibited even at high NO concentrations. Our findings challenge the notion that NO monotonically reduces HOM yields by extending the knowledge of RO2-NO interactions to the low-NO regime. This represents a major advance towards an accurate assessment of HOM budgets, especially in low-NO environments, which prevails in the pre-industrial atmosphere, pristine areas, and the upper boundary layer.

The striking effect of vertical mixing in the planetary boundary layer on new particle formation in the Yangtze River Delta.

New particle formation (NPF) induces a sharp increase in ultrafine particle number concentrations and potentially acts as an important source of cloud condensation nuclei (CCN). As the densely populated area of China, the Yangtze River Delta (YRD) region shows a high frequency of observed NPF events at the ground level, especially in spring. Although recent observational studies suggested a possible connection between NPF at the higher altitudes and ground level, the role played by vertical mixing, particularly in the planetary boundary layer (PBL) is not fully understood. Here we integrate measurements in Nanjing on 15-20 April 2018, and the NPF-explicit Weather Research and Forecast coupled with chemistry (WRF-Chem) model simulations to better understand the governing mechanisms of the NPF and CCN. Our results indicate that newly formed particles at the boundary layer top could be transported downward by vertical mixing as the PBL develops. A numerical sensitivity simulation created by eliminating aerosol vertical mixing suppresses both the downward transport of particles formed at a higher altitude and the dilution of particles at the ground level. The resulting higher Fuchs surface area at the ground level, together with the lack of downward transport, yields a sharp weakening of NPF strength and delayed start of NPF therein. The aerosol vertical mixing, therefore, leads to a more than double increase of surface CN10-40 and a one third decrease of boundary layer top CN10-40. Additionally, the continuous growth of nucleated ultrafine particles at the boundary layer top is strongly steered by the upward transport of condensable gases, with close to half increase of particle number concentrations in Aitken mode and CCN at a supersaturation rate of 0.75%. The findings may bridge the gap in understanding the complex interaction between PBL dynamics and NPF events, reducing the uncertainty in assessing the climate impact of aerosols.

Templateless, Plating-Free Fabrication of Flexible Transparent Electrodes with Embedded Silver Mesh by Electric-Field-Driven Microscale 3D Printing and Hybrid Hot Embossing.

Flexible transparent electrodes (FTEs) with an embedded metal mesh are considered a promising alternative to traditional indium tin oxide (ITO) due to their excellent photoelectric performance, surface roughness, and mechanical and environmental stability. However, great challenges remain for achieving simple, cost-effective, and environmentally friendly manufacturing of high-performance FTEs with embedded metal mesh. Herein, a maskless, templateless, and plating-free fabrication technique is proposed for FTEs with embedded silver mesh by combining an electric-field-driven (EFD) microscale 3D printing technique and a newly developed hybrid hot-embossing process. The final fabricated FTE exhibits superior optoelectronic properties with a transmittance of 85.79%, a sheet resistance of 0.75 Ω sq-1 , a smooth surface of silver mesh (Ra  ≈ 18.8 nm) without any polishing treatment, and remarkable mechanical stability and environmental adaptability with a negligible increase in sheet resistance under diverse cyclic tests and harsh working conditions (1000 bending cycles, 80 adhesion tests, 120 scratch tests, 100 min ultrasonic test, and 72 h chemical attack). The practical viability of this FTE is successfully demonstrated with a flexible transparent heater applied to deicing. The technique proposed offers a promising fabrication strategy with a cost-effective and environmentally friendly process for high-performance FTE.

A modelling study of OH, NO3 and H2SO4 in 2007-2018 at SMEAR II, Finland: analysis of long-term trends.

Major atmospheric oxidants (OH, O3 and NO3) dominate the atmospheric oxidation capacity, while H2SO4 is considered as a main driver for new particle formation. Although numerous studies have investigated the long-term trend of ozone in Europe, the trends of OH, NO3 and H2SO4 at specific sites are to a large extent unknown. The one-dimensional model SOSAA has been applied in several studies at the SMEAR II station and has been validated by measurements in several projects. Here, we applied the SOSAA model for the years 2007-2018 to simulate the atmospheric chemical components, especially the atmospheric oxidants OH and NO3, as well as H2SO4 at SMEAR II. The simulations were evaluated with observations from several shorter and longer campaigns at SMEAR II. Our results show that daily OH increased by 2.39% per year and NO3 decreased by 3.41% per year, with different trends of these oxidants during day and night. On the contrary, daytime sulfuric acid concentrations decreased by 2.78% per year, which correlated with the observed decreasing concentration of newly formed particles in the size range of 3-25 nm with 1.4% per year at SMEAR II during the years 1997-2012. Additionally, we compared our simulated OH, NO3 and H2SO4 concentrations with proxies, which are commonly applied in case a limited number of parameters are measured and no detailed model simulations are available.

Enhanced secondary pollution offset reduction of primary emissions during COVID-19 lockdown in China.

To control the spread of the 2019 novel coronavirus (COVID-19), China imposed nationwide restrictions on the movement of its population (lockdown) after the Chinese New Year of 2020, leading to large reductions in economic activities and associated emissions. Despite such large decreases in primary pollution, there were nonetheless several periods of heavy haze pollution in eastern China, raising questions about the well-established relationship between human activities and air quality. Here, using comprehensive measurements and modeling, we show that the haze during the COVID lockdown was driven by enhancements of secondary pollution. In particular, large decreases in NOx emissions from transportation increased ozone and nighttime NO3 radical formation, and these increases in atmospheric oxidizing capacity in turn facilitated the formation of secondary particulate matter. Our results, afforded by the tragic natural experiment of the COVID-19 pandemic, indicate that haze mitigation depends upon a coordinated and balanced strategy for controlling multiple pollutants.

Secondary aerosol formation and its linkage with synoptic conditions during winter haze pollution over eastern China.

Eastern China has been facing severe winter haze pollution due mainly to secondary aerosol. Existing studies have suggested that stagnant weather or fast chemical production led to frequent haze in this region. However, few works focus on the linkage between secondary production of sulfate, nitrate, and ammonium (SNA) and synoptic conditions, and their joint contribution to PM2.5. In this study, by combining in-situ measurements on meteorology and aerosol chemical composition at three main cities together with a regional model with improved diagnose scheme, we investigated the chemical formation and accumulation of main secondary composition, i.e. SNA under typical synoptic conditions. It is indicated that SNA did play a vital role in haze pollution across eastern China, contributing more than 40% to PM2.5 mass concentration. As most fast developing region, the Yangtze River Delta (YRD) was slightly polluted during stable weather with local chemical production accounting for 61% SNA pollution. While under the influence of cold front, the pollution was aggravated and advection transport became the predominant contributive process (85%). Nevertheless, the chemical production of SNA was notably enhanced due to the uplift of air pollutant and elevated humidity ahead of the cold front, which then facilitated the heterogeneous and aqueous-phase oxidation of precursors. We also found the substantial difference in the phase equilibrium of nitrate over the land surface and ocean due to changes in temperature, ammonia availability and dry deposition. This study highlights the close link between synoptic weather and chemical production, and the resultant vertical and spatial heterogeneity of pollution.

Ozone from fireworks: Chemical processes or measurement interference?

Fireworks have been identified as one ozone source by photolyzing NO2 or O2 and are believed to potentially be important for the nighttime ozone during firework events. In this study, we conducted both lab and field experiments to test two types of fireworks with low and high energy with the goal to distinguish whether the visible ozone signal during firework displays is real. The results suggest that previous understanding of the ozone formation mechanism during fireworks is misunderstood. Ultraviolet ray (UV)-based ozone monitors are interfered by aerosols and some specific VOCs. High-energy fireworks emit high concentrations of particular matters and low VOCs that the artificial ozone can be easily removed by an aerosol filter. Low-energy fireworks emit large amounts of VOCs mostly from the combustion of the cardboard from fireworks that largely interferes with the ozone monitor. Benzene and phenol might be major contributors to the artificial ozone signal. We further checked the nighttime ozone concentration in Jinan and Beijing, China, during Chinese New Year, a period with intense fireworks. A signal of 3-8ppbv ozone was detected and positively correlated to NO and SO2, suggesting a considerable influence of these chemicals in interfering with ambient ozone monitoring.

Polluted dust promotes new particle formation and growth.

Understanding new particle formation and their subsequent growth in the troposphere has a critical impact on our ability to predict atmospheric composition and global climate change. High pre-existing particle loadings have been thought to suppress the formation of new atmospheric aerosol particles due to high condensation and coagulation sinks. Here, based on field measurements at a mountain site in South China, we report, for the first time, in situ observational evidence on new particle formation and growth in remote ambient atmosphere during heavy dust episodes mixed with anthropogenic pollution. Both the formation and growth rates of particles in the diameter range 15-50 nm were enhanced during the dust episodes, indicating the influence of photo-induced, dust surface-mediated reactions and resulting condensable vapor production. This study provides unique in situ observations of heterogeneous photochemical processes inducing new particle formation and growth in the real atmosphere, and suggests an unexpected impact of mineral dust on climate and atmospheric chemistry.