On using an aerosol thermodynamic model to calculate aerosol acidity of coarse particles.

Thermodynamic modeling is still the most widely used method to characterize aerosol acidity, a critical physicochemical property of atmospheric aerosols. However, it remains unclear whether gas-aerosol partitioning should be incorporated when thermodynamic models are employed to estimate the acidity of coarse particles. In this work, field measurements were conducted at a coastal city in northern China across three seasons, and covered wide ranges of temperature, relative humidity and NH3 concentrations. We examined the performance of different modes of ISORROPIA-II (a widely used aerosol thermodynamic model) in estimating aerosol acidity of coarse and fine particles. The M0 mode, which incorporates gas-phase data and runs the model in the forward mode, provided reasonable estimation of aerosol acidity for coarse and fine particles. Compared to M0, the M1 mode, which runs the model in the forward mode but does not include gas-phase data, may capture the general trend of aerosol acidity but underestimates pH for both coarse and fine particles; M2, which runs the model in the reverse mode, results in large errors in estimated aerosol pH for both coarse and fine particles and should not be used for aerosol acidity calculations. However, M1 significantly underestimates liquid water contents for both fine and coarse particles, while M2 provides reliable estimation of liquid water contents. In summary, our work highlights the importance of incorporating gas-aerosol partitioning when estimating coarse particle acidity, and thus may help improve our understanding of acidity of coarse particles.

Characteristics of secondary aerosol formation during shortened multiday reaction experiments in a smog chamber: Effects of relative humidity and ammonia.

Shortened multiday reaction experiments were conducted using the KIST chamber for atmospheric processes simulation (K-CAPS) to characterize the effects of ammonia (NH3) and relative humidity (RH) on the formation of secondary organic aerosols (SOA) due to photooxidation of a mixture of toluene and inorganic gases such as NOx, SO2, and NH3. UV lamps were repeatedly turned on for 3 h (daytime) and off for 6 h (nighttime), and precursors were injected to a reaction bag once (Multiday Initial injection, MI) or repeatedly (Multiday Cyclic injection, MC) to simulate high particulate matter episode due to foreign inflow episode and domestic stagnation episodes, respectively. As a result, the amount of SOA formed in the humid (RH 80 %) MI experiments with ammonia was approximately 1.1 times more than in the traditional single day experiment and approximately 1.6 times more than in the MC experiment, implying that aging processes including nighttime effects without additional emission of precursors during transport can produce more SOA as reactions progressed further under the experimental conditions of this study. The higher the initial RH, the more SOA was formed, with a slope increasing approximately 1.2 µg/m3 per unit RH, and the shorter run time required for SOA to increase to 30 µg/m3 (twice the WHO PM10 standard), with a slope decreasing approximately 0.3 h per unit RH, implying that more humid condition caused during long-range transport across the oceans is one of the possible reasons of high secondary aerosol formation. The SOA formation was reduced by approximately 60 % in the absence of ammonia, suggesting that ammonia reduction is needed to decrease not only secondary inorganic aerosols but also SOA. These results are useful to understand the major reason of high pollution of particulate matters by episode cases in urban areas.

Observational study of microphysical and chemical characteristics of size-resolved fog in different regional backgrounds in China.

To investigate the relationship between microphysical and chemical characteristics of size-resolved fog droplets in different regional backgrounds, we conducted observational experiments in urban, mountainous, rainforest, and rural areas of China. Fog water samples across different diameter ranges (4-16 µm, 16-22 µm, and >22 µm) were collected, alongside fog droplet spectra data. Our findings reveal a close relationship between pH value, electrical conductivity (EC), total ion concentration (TIC) of droplets, and droplet sizes, with smaller droplets exhibiting stronger acidity and higher ion concentrations. Significant differences in chemical composition are observed across size ranges and regional backgrounds. Droplet number concentration (N) and liquid water content (LWC) distributions in different regional backgrounds are skewed, with peak diameters of LWC spectra similar to those of N spectra, yet overall spectral distributions varied significantly. Droplet number concentrations are highest in urban area, while large droplets contribute more to overall LWC in mountainous, rainforest, and rural areas. No direct evidence linked LWC or surface area (S) to LWC ratio to water-soluble ion concentrations of size-resolved fog droplets in different regional backgrounds. However, by adjusting the contributions of S and LWC proportions of different-sized droplets to the ion concentration proportions, we find that expanding the LWC proportion to 2.43 times and decreasing the S proportion to 0.2 times for large droplets, while decreasing the LWC ratio to 0.76 times for small droplets, provided a better explanation for the distribution of ion concentrations. This study advances our understanding of the intricate relationship between the microphysical and chemical characteristics of fog, helping to develop more robust and comprehensive models for fog prediction and management.

Numerical Investigation of the Performance of a Proton Exchange Membrane Water Electrolyzer under Various Outlet Manifold Structure Conditions.

The oxygen discharge process significantly affects the electrochemical performance of a proton exchange membrane water electrolyzer (PEMWE), which requires an optimal structure of the flow field implemented in the bipolar plate (BP) component. In this study, we numerically investigated the two-phase (liquid water and oxygen) flow in the PEMWE's channel region with different outlet manifold structures utilizing the volume of fluid (VOF) model. Then, the oxygen volume fraction at the liquid/gas diffusion layer (L/GDL) surface, i.e., the interface of the channel and L/GDL, obtained by the liquid water and oxygen flow model was incorporated into a three-dimensional (3D) PEMWE model, which made it possible to predict the influence of the outlet manifold structure on the multiple transfers inside the whole electrolyzer as well as the electrochemical performance. The results indicate that the existence of oxygen in the flow field significantly decreased the electrolyzer voltage at a fixed operation current density and deteriorated the uniform distribution of the oxygen amount, current density (corresponding to the electrochemical reaction rate) and temperature in the membrane electrode assembly (MEA), indicating that the rapid oxygen removal from the flow field is preferred in the operation of the electrolyzer. Moreover, slight increases in the width of the outlet manifold were helpful in relieving the oxygen accumulation in the anode CL and, hence, improved the electrolyzer performance with more uniform distribution characteristics.

Chemical characteristics and formation mechanism of secondary inorganic aerosols: The decisive role of aerosol acidity and meteorological conditions.

In recent years, there has been a growing concern about air pollution and its impact on the air quality and human health, especially for fine particulate matter (PM2.5) and its associated secondary aerosols in urban areas. This study conducted a year-long field campaign to collect PM2.5 samples day and night in an urban area of central Taiwan. Higher PM2.5 mass concentrations were observed in winter (27.7 ± 9.7 µg/m3), followed by autumn (22.5 ± 8.3 µg/m3), spring (19.2 ± 6.4 µg/m3), and summer (11.0 ± 3.1 µg/m3). The dominant formation mechanism of secondary inorganic aerosols was heterogeneous reactions of NO3- at night and homogeneous reactions of SO42- during the day. Additionally, significant correlations were observed between aerosol liquid water content (ALWC) and NO3- during nighttime, indicating the importance of aqueous-phase NO3- formation. The role of aerosol acidity was explored and a unique alkaline condition was found in spring and summer, which showed lower PM2.5 concentrations than the neutralized condition. Under the neutralized condition, higher PM2.5 concentrations were commonly found when combining the ammonium-rich regime with molar ratios of [NO3-]/[SO42-] exceeding 1.6, suggesting the importance of reducing both NH3 and NOx. Furthermore, the results showed that reducing NH3 should be prioritized under high temperature conditions, while reducing NOx became important under low temperature conditions. Clustering of backward trajectories showed that long-range transport could enhance the formation of secondary aerosols, but local emissions emerged as the main factor driving high PM2.5 concentrations. This study provides insights for policymakers to improve air quality, suggesting that different mitigation strategies should be formulated based on meteorological variables and that using clean energy for vehicles and electricity generation is important to alleviate air pollution.

Role of gas-particle conversion of ammonia in haze pollution under ammonia-rich environment in Northern China and prospects of effective emission reduction.

As an important precursor of secondary inorganic aerosols (SIAs), ammonia (NH3) plays a key role in fine particulate matter (PM2.5) formation. In order to investigate its impacts on haze formation in the North China Plain (NCP) during winter, NH3 concentrations were observed at a high-temporal resolution of 1 min by using the SP-DOAS in Tai'an from December 2021 to February 2022. During the observation period, the average NH3 concentration was 11.84 ± 5.9 ppbv, and it was determined as an ammonia-rich environment during different air quality conditions. Furthermore, the average concentrations of sulfate (SO42-), nitrate (NO3-) and ammonium (NH4+) were 9.54 ± 5.97 µg/m3, 19.09 ± 14.18 µg/m3 and 10.72 ± 6.53 µg/m3, respectively. Under the nitrate-dominated atmospheric environment, aerosol liquid water content (ALWC) was crucial for NH3 particle transformation during haze aggravation, and the gas-particle partitioning of ammonia played an important role in the SIAs formation. The reconstruction of the molecular composition further indicated that ammonium nitrate (NH4NO3) plays a dominant role in the increase of PM2.5 during haze events. Consequently, future efforts to mitigate fine particulate pollution in this region should focus on controlling NH4NO3 levels. In ammonia-rich environments, NO3- formation is more dependent on the concentration of nitric acid (HNO3). The sensitive analysis of TNO3 (HNO3 + NO3-) and NHX (NH3 + NH4+) reduction using the thermodynamic model suggested that the NO3- concentration decreases linearly with the reduction of TNO3. And the concentration of NO3- decreases rapidly only when NHX is reduced by 50-60 %. Reducing NOX emissions is the most effective way to alleviate nitrate pollution in this region.

Size-resolved water-soluble organic carbon and its significant contribution to aerosol liquid water.

Size-segregated aerosols collected in Beijing from 2021 to 2022 were used to investigate the contribution of organic aerosols to the aerosol liquid water content (ALWC), the influencing factors of ALWC, and the concentrations and size distribution characteristics of water-soluble organic carbon (WSOC) after clean air actions. The results showed that the concentration of WSOC in particulate matter (PM)1.8 was 3.52 ± 2.43 µg/m3 during the sampling period. Obvious changes were observed in the size distribution of WSOC after clean air actions, which may be attributed to the enhancement of atmospheric oxidation capacity and the decrease in PM concentration. The contribution of organic aerosols to the ALWC in fine PM was 18.1 % during the sampling period, which was more significant at lower particles concentration and smaller particle size ranges. The ambient relative humidity (RH) and the ratio of NO3-/SO42- had an apparent influence on ALWC. The continuous increase in the nitrate proportion significantly reduced the deliquescence point of the aerosols, making them prone to hygroscopic growth at lower RH. Analysis of the relation among nitrogen oxidation ratio (sulfur oxidation ratio), ALWC and PM1.8 mass concentrations suggests that organic matter has a significant effect on the formation of secondary inorganic aerosols in the initial phase of pollution formation and plays a crucial role in aerosol pollution formation in Beijing. These results are conducive to understanding the formation mechanism of aerosols and provide scientific data and theoretical support for the formulation of more effective emission-reduction measures.

Field evidence of brown carbon absorption enhancement linked to organic nitrogen formation in Indo-Gangetic Plain.

Atmospheric brown carbon (BrC), a short-lived climate forcer, absorbs solar radiation and is a substantial contributor to the warming of the Earth's atmosphere. BrC composition, its absorption properties, and their evolution are poorly represented in climate models, especially during atmospheric aqueous events such as fog and clouds. These aqueous events, especially fog, are quite prevalent during wintertime in Indo-Gangetic Plain (IGP) and involve several stages (e.g., activation, formation, and dissipation, etc.), resulting in a large variation of relative humidity (RH) in the atmosphere. The huge RH variability allowed us to examine the evolution of water-soluble brown carbon (WS-BrC) diurnally and as a function of aerosol liquid water content (ALWC) and RH in this study. We explored links between the evolution of WS-BrC mass absorption efficiency at 365 nm (MAEWS-BrC-365) and chemical characteristics, viz., low-volatility organics and water-soluble organic nitrogen (WSON) to water-soluble organic carbon (WSOC) ratio (org-N/C), in the field (at Kanpur in central IGP) for the first time worldwide. We observed that WSON formation governed enhancement in MAEWS-BrC-365 diurnally (except during the afternoon) in the IGP. During the afternoon, the WS-BrC photochemical bleaching dwarfed the absorption enhancement caused by WSON formation. Further, both MAEWS-BrC-365 and org-N/C ratio increased with a decrease in ALWC and RH in this study, signifying that evaporation of fog droplets or bulk aerosol particles accelerated the formation of nitrogen-containing organic chromophores, resulting in the enhancement of WS-BrC absorptivity. The direct radiative forcing of WS-BrC relative to that of elemental carbon (EC) was ∼19 % during wintertime in Kanpur, and âˆ¼ 40 % of this contribution was in the UV-region. These findings highlight the importance of further examining the links between the evolution of BrC absorption behavior and chemical composition in the field and incorporating it in the BrC framework of climate models to constrain the predictions.

Direct Measurement of Aerosol Liquid Water Content: A Case Study in Summer in Nanjing, China.

Aerosol liquid water content (ALWC) affects the mass loading, optical properties, and toxicity of aerosols. However, the measurement of ALWC is very rare due to its requirement of sophisticated instruments and its high operational costs. In this work, we improved on our previous simple, low-cost method by using a combination of one real-time fine particulate matter (PM2.5) monitor and two turbidimeters and successfully applied these for the direct measurement of ALWC in PM2.5 in Nanjing during the summer of 2023. The average ALWC during this measurement period occupied ~1/6 of the total PM2.5 mass, and this contribution was even greater with the elevation in the PM2.5 concentration. The ALWC was, as anticipated, closely related to the relative humidity (RH) and PM2.5 concentrations, but it did not always increase with the air quality index (AQI) due to the fact that polluted periods in summer were often governed by high O3 levels, not PM2.5 levels. The ALWC also had a great impact on visibility; it could decrease the visibility rapidly to hazy conditions when the dry PM2.5 was not high (~30 µg m-3) or the AQI was "good" (75~100), indicating that the air quality classified as "good" using the dry PM2.5 concentration might actually be "lightly polluted" if the ALWC is included. We also found that the air mass originating from Northeast China had the lowest PM2.5 mass concentration yet the highest ALWC values due to its high RH. Moreover, the quantification of ALWC levels can help us understand the solubility/bioavailability and thus the toxic effects of some specific components (for example, heavy metals or organics). Moreover, the influence of ALWC on air quality classifications should also be considered in the assessment of the health effects of air pollution and in public health early warning and protection.

Spectroscopic studies of the role of dissolved organic matter in acenaphthene photodegradation in liquid water and ice.

The effect of concentration and origin of dissolved organic matter (DOM) on acenaphthene (Ace) photodegradation in liquid water and ice was investigated, and the components in DOM which were involved in Ace photodegradation were identified. The DOM samples included Suwannee River fulvic acid (SRFA), Elliott soil humic acid (ESHA), and an effluent organic matter (EfOM) sample. Due to the production of hydroxyl radical (•OH) and triplet excited-state DOM (3DOM*) which react with Ace, DOM had promotion effects on Ace photodegradation. However, the promotion effects of DOM were prevailed over by their suppressing effect of DOM including screening light effect, intermediates reducing effect and RS quenching effect, and thus, the photodegradation rates of Ace decreased in the presence of the three DOM with concentrations of 0.5-7.5 mg C/L in liquid water and ice. ESHA had higher light absorption and thus had higher screening light effect on Ace photodegradation in liquid water than SRFA and EfOM. At each DOM concentration, ESHA exhibited higher promotion effect on Ace photodegradation than SRFA and EfOM, in liquid water and ice. The binding of Ace with DOM was indicated by decreases in fluorescence intensity of Ace when coexisted with DOM. However, the binding of Ace to DOM played an unimportant role in suppressing Ace photodegradation. The photodegradation behavior of fluorophores in Ace with DOM present in ice was not similar to that in liquid water. C-O, C═O, carboxyl groups O-H and aliphatic C-H functional groups in DOM were involved in the interaction of DOM with Ace. The presence of Ace seemed to have no influence on the photodegradation behavior of functional groups in DOM.

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols.

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (•OH), singlet molecular oxygen (1O2*), and triplet excited states of organic compounds (3C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase •OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with •OH, 1O2*, and 3C* in cloud droplets and aerosol liquid water. We investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

Secondary inorganic aerosols and aerosol acidity at different PM2.5 pollution levels during winter haze episodes in the Sichuan Basin, China.

Wintertime fine particle (PM2.5) pollution remains to be perplexing air quality problems in many parts of China. In this study, PM2.5 compositions and aerosol acidity at different pollution levels at an urban cite in the southwest China's Sichuan Basin were investigated during a sustained winter haze episode. Organic matter was the most abundant component of PM2.5, followed by nitrate, sulfate and ammonium. Shares of organic aerosol in PM2.5 mass decreased with the elevated PM2.5 levels, while the enhancements of sulfate and secondary organic aerosol were much less than that of nitrate and ammonium during heavy pollution with increased ratios of nitrate to sulfate, implying a significant role of nitrate in the haze formation. Results also suggest the nighttime chemistry might contribute substantially to the formation of nitrate under severe pollutions. The daily average aerosol pH showed a decreasing trend with the elevated levels of PM2.5, and this increased aerosl acidity was mainly due to the fast rising secondary inorganic aerosol (SIA) concentration, with the increase in hydronium ion concentration in air (Hair+) surpassing the dilution effect of elevated aerosol liquid water content (LWC). Thermodynamic model calculations revealed that the air environment was NH3-rich with total NHx (NH3 + NH4+) greater than required NHx, and the aerosol pH exponentially declined with the decreasing excess NHx (p < 0.01). This study demonstrated that under air stagnation and NH3-rich environment during winter, the raised relative humidity (RH) would lead to an increase in LWC and thereby facilitate the aqueous chemistry processes with the neutralization capacity of NH3 to form sulfate and nitrate, which would further increase the LWC and lower the pH. This self-amplifying SIA formation might be crucial to the severe PM2.5 pollution and haze events during winter, and therefore cutting both NOx and NH3 emissions would benefit stopping the self-amplification.

Boosting the Viable Water Harvesting in Solar Vapor Generation: From Interfacial Engineering to Devices Design.

Continuously increasing demand for the life-critical water resource induces severe global water shortages. It is imperative to advance effective, economic, and environmentally sustainable strategies to augment clean water supply. The present work reviews recent reports on the interfacial engineering to devices design of solar vapor generation (SVG) system for boosting the viability of drinkable water harvesting. Particular emphasis is placed on the basic principles associated with the interfacial engineering of solar evaporators capable of efficient solar-to-thermal conversion and resulting freshwater vapor via eliminating pollutants from quality-impaired water sources. The critical configurations manufacturing of the devices for fast condensation is then highlighted to harvest potable liquid water. Fundamental and practical challenges, along with prospects for the targeted materials architecture and devices modifications of SVG system are also outlined, aiming to provide future directions and inspiring critical research efforts in this emerging and exciting field.

Impact of ozonation on the formation of particulate nitrosodi-methylamine (NDMA) in atmosphere.

The contribution of ozonation to the formation of particulate nitrosodi-methylamine (NDMA) in the aqueous aerosol phase was investigated using measurement data from 2018 in Seoul, Republic of Korea and a box model. The correlation between the NDMA concentration and aerosol liquid water content and box model results showed that aqueous aerosol phase reactions, including nitrosation and ozonation, might contribute to the formation of NDMA. The concentration of NDMA and the ratio of O3/dimethylamine exhibited a negative correlation, suggesting that the contribution of ozonation to NDMA formation may not be significant. Furthermore, when the daily concentration of NDMA exceeded 10 ng/m3, the pH was 3.96 ± 0.48, indicating that the impact of ozonation on NDMA concentration might not be significant. To quantitatively investigate the contribution of ozonation, the ozonation mechanism that forms NDMA was included in the box model developed in our previous study. The model results showed that the ozonation contributed to the ambient concentration of NDMA (7.9 ± 3.8% (winter); 1.9 ± 3.0% (spring); 10.0 ± 0.77% (summer); 3.6 ± 7.3% (autumn)). It is estimated that the relatively higher O3/NOx ratio in summer (1.63 ± 0.69; 0.64 ± 0.52 (winter); 1.14 ± 0.92 (spring); 0.52 ± 0.54 (autumn)) could enhance ozonation and that relatively lower pH in summer (2.2 ± 0.4; 5.3 ± 1.2 (winter); 3.9 ± 1.2 (spring); 3.9 ± 0.7 (autumn)) could hinder nitrosation compared to that in other seasons.

Aerosol liquid water in PM2.5 and its roles in secondary aerosol formation at a regional site of Yangtze River Delta.

Aerosol liquid water content (ALWC) plays an important role in secondary aerosol formation. In this study, a whole year field campaign was conducted at Shanxi in north Zhejiang Province during 2021. ALWC estimated by ISORROPIA-II was then investigated to explore its characteristics and relationship with secondary aerosols. ALWC exhibited a highest value in spring (66.38 µg/m3), followed by winter (45.08 µg/m3), summer (41.64 µg/m3), and autumn (35.01 µg/m3), respectively. It was supposed that the secondary inorganic aerosols (SIA) were facilitated under higher ALWC conditions (RH > 80%), while the secondary organic species tended to form under lower ALWC levels. Higher RH (> 80%) promoted the NO3- formation via gas-particle partitioning, while SO42- was generated at a relative lower RH (> 50%). The ALWC was more sensitive to NO3- (R = 0.94) than SO42- (R = 0.90). Thus, the self-amplifying processes between the ALWC and SIA enhanced the particle mass growth. The sensitivity of ALWC and OX (NO2 + O3) to secondary organic carbon (SOC) varied in different seasons at Shanxi, more sensitive to aqueous-phase reactions (daytime R = 0.84; nighttime R = 0.54) than photochemical oxidation (daytime R = 0.23; nighttime R = 0.41) in wintertime with a high level of OX (daytime: 130-140 µg/m3; nighttime: 100-140 µg/m3). The self-amplifying process of ALWC and SIA and the aqueous-phase formation of SOC will enhance aerosol formation, contributing to air pollution and reduction of visibility.

Predicting Atmospheric Water-Soluble Organic Mass Reversibly Partitioned to Aerosol Liquid Water in the Eastern United States.

Water-soluble organic matter (WSOM) formed through aqueous processes contributes substantially to total atmospheric aerosol, however, the impact of water evaporation on particle concentrations is highly uncertain. Herein, we present a novel approach to predict the amount of evaporated organic mass induced by sample drying using multivariate polynomial regression and random forest (RF) machine learning models. The impact of particle drying on fine WSOM was monitored during three consecutive summers in Baltimore, MD (2015, 2016, and 2017). The amount of evaporated organic mass was dependent on relative humidity (RH), WSOM concentrations, isoprene concentrations, and NOx/isoprene ratios. Different models corresponding to each class were fitted (trained and tested) to data from the summers of 2015 and 2016 while model validation was performed using summer 2017 data. Using the coefficient of determination (R2) and the root-mean-square error (RMSE), it was concluded that an RF model with 100 decision trees had the best performance (R2 of 0.81) and the lowest normalized mean error (NME < 1%) leading to low model uncertainties. The relative feature importance for the RF model was calculated to be 0.55, 0.2, 0.15, and 0.1 for WSOM concentrations, RH levels, isoprene concentrations, and NOx/isoprene ratios, respectively. The machine learning model was thus used to predict summertime concentrations of evaporated organics in Yorkville, Georgia, and Centerville, Alabama in 2016 and 2013, respectively. Results presented herein have implications for measurements that rely on sample drying using a machine learning approach for the analysis and interpretation of atmospheric data sets to elucidate their complex behavior.

Probing the self-ionization of liquid water with ab initio deep potential molecular dynamics.

The chemical equilibrium between self-ionized and molecular water dictates the acid-base chemistry in aqueous solutions, yet understanding the microscopic mechanisms of water self-ionization remains experimentally and computationally challenging. Herein, Density Functional Theory (DFT)-based deep neural network (DNN) potentials are combined with enhanced sampling techniques and a global acid-base collective variable to perform extensive atomistic simulations of water self-ionization for model systems of increasing size. The explicit inclusion of long-range electrostatic interactions in the DNN potential is found to be crucial to accurately reproduce the DFT free energy profile of solvated water ion pairs in small (64 and 128 H2O) cells. The reversible work to separate the hydroxide and hydronium to a distance [Formula: see text] is found to converge for simulation cells containing more than 500 H2O, and a distance of [Formula: see text] 8 Å is the threshold beyond which the work to further separate the two ions becomes approximately zero. The slow convergence of the potential of mean force with system size is related to a restructuring of water and an increase of the local order around the water ions. Calculation of the dissociation equilibrium constant illustrates the key role of long-range electrostatics and entropic effects in the water autoionization process.

Effect of dissolved organic matter on sulfachloropyridazine photolysis in liquid water and ice.

Dissolved organic matter (DOM) is an ubiquitous component of environmental snow and ice, which can absorb light and produce reactive species (RS) and thus is of importance in ice photochemistry. The photodegradation of sulfachloropyridazine (SCP) without and with DOM present in liquid water and ice were investigated in this study. The photodegradation rate constants for SCP without DOM present was enhanced by 52.5 % in ice relative to liquid water, likely due to the enhanced role of SCP self-sensitized RS in ice. DOM significantly promoted SCP photolysis in both liquid water and ice, which was mainly attributed to roles of singlet oxygen (1O2) and triplet excited-state DOM (3DOM*) generated from DOM. 1O2 production from DOM was significantly enhanced in ice relative to liquid water. Hydroxyl radical (•OH) production from DOM in ice was similar to those in liquid water. Enhancement in 3DOM* production in ice was observed at low DOM concentrations. Suwannee River Fulvic Acid (SRFA) and Elliott Soil Humic Acid (ESHA) exhibited differences in RS production in liquid water and ice, as well as in enhancement of 1O2 and 3DOM* produced in ice relative to liquid water. DOM induced reaction pathways of SCP different from those without DOM present, and therefore affected toxicity of SCP photoproducts. There were differences in photodegradation pathways of SCP as well as in toxicity of SCP photoproducts between liquid water and ice.

Predicting Atmospheric Particle Phase State Using an Explainable Machine Learning Approach Based on Particle Rebound Measurements.

The particle phase state plays a vital role in the gas-particle partitioning, multiphase reactions, ice nucleation activity, and particle growth in the atmosphere. However, the characterization of the atmospheric phase state remains challenging. Herein, based on measured aerosol chemical composition and ambient relative humidity (RH), a machine learning (ML) model with high accuracy (R2 = 0.952) and robustness (RMSE = 0.078) was developed to predict the particle rebound fraction, f, which is an indicator of the particle phase state. Using this ML model, the f of particles in the urban atmosphere was predicted based on seasonal average aerosol chemical composition and RH. Regardless of seasons, aerosols remain in the liquid state of mid-high latitude cities in the northern hemisphere and in the semisolid state over semiarid regions. In the East Asian megacities, the particles remain in the liquid state in spring and summer and in the semisolid state in other seasons. The effects of nitrate, which is becoming dominant in fine particles in several urban areas, on the particle phase state were evaluated. More nitrate led the particles to remain in the liquid state at an even lower RH. This study proposed a new approach to predict the particle phase state in the atmosphere based on RH and aerosol chemical composition.

FLIIMP - a community software for the processing, calibration, and reporting of liquid water isotope measurements on cavity-ring down spectrometers.

Precise and accurate measurements of the stable isotope composition from precipitation, land ice, runoff, and oceans provide critical information on Earth's water cycle. The analysis, post-processing, and calibration of raw analytical signals from laser spectrometers during sample analysis involves a number of critical procedures to counteract instrumental drift, inter-sample memory effects, and the quantification of total uncertainty. We present a new software tool for the post-processing and calibration named FLIIMP (FARLAB Liquid Water Isotope Measurement Processor). FLIIMP facilitates sample processing by (1) a graphical user interface that guides the user along the processing steps from corrections for memory effects, drift, and mixing ratio to calibration, and (2) allows to monitor long-term measurement system behaviour, currently for Picarro-brand water isotope analysers. Final data files are accompanied by a detailed calibration report. Being an open-source software for the major operating systems, users can adapt FLIIMP to their laboratory environment, and the community can contribute the software development. •FLIIMP facilitates post-processing, calibration and reporting for stable water isotope liquid sample analysis.•The stepwise, interactive graphical user interface reduces possibility of errors and shortens processing time.•Open source software enables future development of FLIIMP by the user community.