Chloride Depletion Research Articles

Chemical composition, source characteristics, and hygroscopic properties of organic-enriched aerosols in the high Arctic during summer

Arctic regions are extremely sensitive to global warming. Aerosols are one of the most important short-lived climate-forcing agents affecting the Arctic climate. The present study examines the summertime chemical characteristics and potential sources of various organic and inorganic aerosols at a Norwegian Arctic site, Ny-Ålesund (79°N). The results show that organic matter (OM) accounts for 60 % of the total PM10 mass, followed by sulfate (SO42−). Water-soluble organic carbon (WSOC) contributes 62 % of OC. Photochemical processes involving diverse anthropogenic and biogenic precursor compounds are identified as the major sources of WSOC, while water-insoluble organic carbon (WIOC) aerosols are predominantly linked to primary marine emissions. Despite being a remote pristine site, the aerosols show a sign of chemical aging, evidenced by a significant chloride depletion, which was about 82 % on average during the study period. Nitrogen-containing aerosols are likely stemming from migratory seabird colonies and local dust sources around the sampling site. While biogenic, crustal, and sea salt-derived SO42- account for 37%, 8%, and 5% respectively, the remaining 50% is attributed to anthropogenic SO42-. Through chemical tracers, Pearson correlation coefficient matrix, and Hierarchical Cluster Analysis (HCA), the present study identifies soil biota (terrestrial biogenic) and marine emissions, along with their photochemical oxidation processes, as potential sources of Arctic aerosols during summer, while biomass burning and combustion-related sources have a minor contribution. The chemical closure of hygroscopicity highlights that while organics predominantly control aerosol hygroscopicity in the Arctic summer, specific inorganic components like (NH4)2SO4 can significantly increase it on certain days, affecting aerosol-cloud interactions and climate processes over the Arctic during summer. The present study highlights the high abundance of organics and their vital role in the Arctic climate during summer when natural aerosols are conquered.

Pockmarks and associated fresh submarine groundwater discharge in the seafloor of Puck Bay, southern Baltic Sea

This is the first well-documented report on the occurrence of pockmarks in Puck Bay. Pockmarks in the seafloor of Puck Bay were discovered during a hydroacoustic survey carried out in 2020. They are located at a depth of 25–27 m in the southwestern part of the bay. Significant depletion of chloride (Cl−) concentrations in sediment pore water was found within the depressions. Most likely, the formation of pockmarks was due to groundwater flow through the Miocene–Pleistocene system of aquifers, which extends from land to the bay area. One-dimensional modeling of vertical Cl− concentration profiles in pore water revealed the upward flow of freshened groundwater within the pockmarks. The magnitude of submarine groundwater discharge (SGD) was estimated to vary from 1.53·10−2 to 18·10−2 L·m−2·h−1. The effect of groundwater seepage was also observed at 3 cm above the seafloor within the pockmarks, which was identified as a decrease in salinity of approximately 0.12 PSU compared to reference sites.Furthermore, due to the effect of water advection, SGD can be detected even several meters above the seafloor as a decrease in salinity values within the thermocline layer.

Harmful algal bloom aerosols and human health.

Harmful algal blooms (HABs) are increasing across many locations globally. Toxins from HABs can be incorporated into aerosols and transported inland, where subsequent exposure and inhalation can induce adverse health effects. However, the relationship between HAB aerosols and health outcomes remains unclear despite the potential for population-level exposures. In this review, we synthesized the current state of knowledge and identified evidence gaps in the relationship between HAB aerosols and human health. Aerosols from Karenia brevis, Ostreopsis sp., and cyanobacteria were linked with respiratory outcomes. However, most works did not directly measure aerosol or toxin concentrations and instead relied on proxy metrics of exposure, such as cell concentrations in nearby waterbodies. Furthermore, the number of studies with epidemiological designs was limited. Significant uncertainties remain regarding the health effects of other HAB species; threshold dose and the dose-response relationship; effects of concurrent exposures to mixtures of toxins and other aerosol sources, such as microplastics and metals; the impact of long-term exposures; and disparities in exposures and associated health effects across potentially vulnerable subpopulations. Additional studies employing multifaceted exposure assessment methods and leveraging large health databases could address such gaps and improve our understanding of the public health burden of HABs.

Relative Humidity Dependence of Growth Factor and Real Refractive Index for Sea Salt/Malonic Acid Internally Mixed Aerosols

AbstractSea salt aerosols (SSAs) often mix with organic matter via sea‐to‐air emission, photochemical oxidation, and atmospheric transport, which change particle hygroscopicity and real refractive index (RRI), thereby the radiative effects. However, the influence of water uptake and organic matters on radiative effects is not well understood. In this study, relative humidity (RH)‐dependent growth factor (GF), light scattering enhancement factor, RRI (nmea), and radiative forcing efficiency (RFE) in the visible spectrum of SSAs/malonic acid (MA) internally mixed aerosols were investigated. Our results showed that MA‐mediated SSAs readily absorbed water even at low RH but suppressed hygroscopic growth at high RH. The discrepancy between Zdanovskii‐Stokes‐Robinson predictions and measured GF indicated that the suppressing effect on size caused by produced malonate salts in chloride depletion became more evident as MA content increased. RRI in the visible spectrum decreased as MA got enriched and approached toward water's RRI at high RH, resulting in a less cooling effect. The increasing RH reduced RFE both by decreasing RRI and increasing particle size substantially. Ignoring the effect of MA on particle size and RRI under varied RH, errors in RFE at 525 nm up to 25% could be induced. Volume mixing rule performs well in predicting the RRI of mixed aerosols in dry conditions, while the retrieved difference of 0.061 between volume mixing RRI nvol and nmea would make the error in RFE up to 1.15 W·m−2·Aerosol optical depth−1 at 87% RH. Our study helps understand the impact of water content and dicarboxylic acids on the direct radiative effects of SSAs.

Fluid sources and overpressures within the central Cascadia Subduction Zone revealed by a warm, high-flux seafloor seep.

Pythia's Oasis is a newly discovered seafloor seep on the Central Oregon segment of the Cascadia Subduction Zone, where focused venting emits highly altered fluids ~9°C above the background temperature. The seep fluid chemistry is unique for Cascadia and includes extreme enrichment of boron and lithium and depletion of chloride, potassium, and magnesium. We conclude that the fluids are sourced from pore water compaction and mineral dehydration reactions with minimum source temperatures of 150° to 250°C, placing the source at or near the plate boundary offshore Central Oregon. Estimated fluid flow rates of 10 to 30 cm s-1 are orders of magnitude higher than those estimated elsewhere along the margin and are likely driven by extreme overpressures along the plate boundary. Probable draining of the overpressured reservoir along the vertical Alvin Canyon Fault indicates the important role that such faults may play in the regulation of pore fluid pressure throughout the forearc in Central Cascadia.

Direct quantification of changes in pH within single levitated microdroplets and the kinetics of nitrate and chloride depletion.

The hygroscopicity and pH of aqueous microdroplets and smaller aerosols control their impacts on human health and the climate. Nitrate depletion and chloride depletion through the partitioning of HNO3 and HCl into the gas phase are processes that are enhanced in micron-sized and smaller aqueous droplets and this depletion influences both hygroscopicity and pH. Despite a number of studies, uncertainties remain about these processes. While acid evaporation and the loss of HCl or HNO3 have been observed during dehydration, there is a question as to the rate of acid evaporation and whether this can occur in fully hydrated droplets at higher relative humidity (RH). To directly elucidate the kinetics of nitrate and chloride depletion through evaporation of HNO3 and HCl, respectively at high RH, single levitated microdroplets are probed with cavity-enhanced Raman spectroscopy. Using glycine as a novel in situ pH probe, we are able to simultaneously measure changes in microdroplet composition and pH over timescales of hours. We find that the loss of chloride from the microdroplet is faster than that of nitrate, and the calculated rate constants infer that depletion is limited by the formation of HCl or HNO3 at the air-water interface and subsequent partitioning into the gas phase.

Factors influencing aerosol and precipitation ion chemistry in urban background of Moscow megacity

In-depth study of aerosol and precipitation ion chemistry was carried out in order to cover an existing data gap in the seasonal-dependent ionic data in Moscow urban background atmosphere. Literature about atmospheric pollution in this megacity is, indeed, still poor, despite its peculiar climatological characteristics that make it a very interesting site for atmospheric research. Particulate matter (PM) and precipitation were collected at Moscow urban background during spring of 2018, summer, and autumn of 2019. Aerosol inorganic ions are characterized for the whole period, carboxylic acids and sugars for summer. Inorganic ions constitute a major PM10 fraction of 27% in autumn, it drops down to 16.5% in summer. Dominance of secondary inorganic aerosol (SIA) over all the other inorganic ion species is determined. Na+ and Ca2+ shows the largest variability between seasons, with maximum in summer and spring, respectively. Excess of anions in autumn is indicated by ion balance while adding carbonates, spring and summer aerosol is found electroneutral. Chloride depletion phenomenon follows the snow melt and remobilization of salt applied to roads for deicing, demonstrating the biggest impact in summer. Degree of neutralization of ammonia as sulfate and nitrate is found by the correlation between the concentration of NH4+ and calculated from SO42− and NO3−. Inorganic fraction in PM10 is higher (16.5%) than total carboxylic acids (3.5%), and total sugars and anhydrosugars (0.8%). Concentration polar plots show ion variation jointly with wind speed and wind direction and the source origin. Highest SIA concentrations relate a cluster of the prevalent air mass transportation and indicate the source in the northwestern direction in spring and summer. K+ acts as a marker of fires in spring and summer as well as of the domestic biomass burning in the region around a megacity in autumn. Source apportionment of inorganic ion and BC by Varimax analysis reveals major sources namely SIA, soil resuspension, biomass burning, deicing salt, and fossil fuel combustion. In summer, organic ions, anhydrosugars, and sugars shows additional impact of photochemistry and biological activities. Rainfall is heavier in summer than in autumn, with pH of acid rain during spring and summer. The highest concentrations for almost all ions were observed in spring, except HCO3−. Precipitation composition is described with aerosol wet removal by seasonal variability of SIA scavenging factors, decreasing in summer and increasing in autumn and spring.

Spatiotemporally Resolved pH Measurement in Aerosol Microdroplets Undergoing Chloride Depletion: An Application of In Situ Raman Microspectrometry.

Acidity is a defining property of atmospheric aerosols that profoundly affects environmental systems, human health, and climate. However, directly measuring the pH of aerosol microdroplets remains a challenge, especially when the microdroplets' composition is nonhomogeneous or dynamically evolving or both. As a result, a pH measurement technique with high spatiotemporal resolution is needed. Here, we report a spatiotemporally resolved pH measurement technique in microdroplets using spontaneous Raman spectroscopy. Our target sample was the microdroplets comprising sodium chloride and oxalic acid─laboratory surrogates of sea spray aerosols and water-soluble organic compounds, respectively. Our measurements show that the chloride depletion from the microdroplets caused a continuous increase in pH by ∼0.5 units in 2 hours. Meanwhile, the surface propensity of chloride anions triggers a stable pH gradient inside a single droplet, with the pH at the droplet surface lower than that at the core by ∼ 0.4 units. The uncertainties arising from the Raman detection limit (±0.08 pH units) and from the nonideal solution conditions (-0.06 pH units) are constrained. Our findings indicate that spontaneous Raman spectroscopy is a simple yet robust technique for precise pH measurement in aerosols with high spatiotemporal resolution.

Displacement of Strong Acids or Bases by Weak Acids or Bases in Aerosols: Thermodynamics and Kinetics.

Depletion of chloride, nitrate, or ammonium from atmospheric aerosols represents a unique class of displacement reactions in which strong acids (HCl and HNO3) or bases (NH3) are substituted by weaker ones (i.e., dicarboxylic acids or dicarboxylate salts, respectively). These reactions alter the aerosol composition and perturb the atmospheric cycle of volatile compounds, thereby affecting environmental systems and climate. Despite the profound implications, the mechanism of these unique displacement reactions remains unclear. Here, we elucidate the thermodynamics and kinetics of these reactions using the multiphase buffer theory and a diffusion-controlled mass-transfer function, respectively. On the thermodynamic aspect, we find that the effective dissociation constants of the strong acids and bases in aerosols are 2 to 10 orders of magnitude lower than those in bulk solutions. On the kinetic aspect, we find that displacement reactions occur rapidly in aerosol microdroplets with a radius below 10 μm. Within this size range, the characteristic reaction time is always shorter than the lifetime of the aerosols in the atmosphere. Our findings suggest that the unique displacement reactions can significantly modify the composition of atmospheric aerosols, and consequentially, these aerosols may manifest distinct properties unforeseen by the chemistry of homogeneous bulk systems.

Multiple molecular mechanisms are involved in the activation of the kidney sodium-chloride cotransporter by hypokalemia

Low potassium intake activates the kidney sodium-chloride cotransporter (NCC) whose phosphorylation and activity depend on the With-No-Lysine kinase 4 (WNK4) that is inhibited by chloride binding to its kinase domain. Low extracellular potassium activates NCC by decreasing intracellular chloride thereby promoting chloride dissociation from WNK4 where residue L319 of WNK4 participates in chloride coordination. Since the WNK4-L319F mutant is constitutively active and chloride-insensitive invitro, we generated mice harboring this mutation that displayed slightly increased phosphorylated NCC and mild hyperkalemia when on a 129/sv genetic background. On a low potassium diet, upregulation of phosphorylated NCC was observed, suggesting that in addition to chloride sensing by WNK4, other mechanisms participate which may include modulation of WNK4 activity and degradation by phosphorylation of the RRxS motif in regulatory domains present in WNK4 and KLHL3, respectively. Increased levels of WNK4 and kidney-specific WNK1 and phospho-WNK4-RRxS were observed in wild-type and WNK4L319F/L319F mice on a low potassium diet. Decreased extracellular potassium promoted WNK4-RRxS phosphorylation invitro and exvivo as well. These effects might be secondary to intracellular chloride depletion, as reduction of intracellular chloride in HEK293 cells increased phospho-WNK4-RRxS. Phospho-WNK4-RRxS levels were increased in mice lacking the Kir5.1 potassium channel, which presumably have decreased distal convoluted tubule intracellular chloride. Similarly, phospho-KLHL3 was modulated by changes in intracellular chloride in HEK293 cells. Thus, our data suggest that multiple chloride-regulated mechanisms are responsible for NCC upregulation by low extracellular potassium.

Time series of hydrothermal vent fluid chemistry at Main Endeavour Field, Juan de Fuca Ridge: Remote sampling using the NEPTUNE cabled observatory

Seafloor hydrothermal fluids play a critical role in regulating a wide range of geochemical and biological processes. Chemical and physical changes to venting fluids undoubtedly occur in response to geological events, at depth or near the seafloor, with corresponding effects on vent fluid chemistry, mineralization, and biological activity. However, the uncertain timing of such events makes it impractical to anticipate their occurrence. Thus, the temporal evolution of seafloor vent fluids and coexisting mineral deposits is most often inferred from observations made using conventional deep submergence assets that may be non-continuous for a specific vent field. The recent development of submarine volcanic observatories operated by Ocean Networks Canada (ONC) and the Ocean Observatory Initiative (OOI) in the U.S. that deliver power to instruments on the seafloor and communications via high-speed fiber optic cable permits real-time communication and monitoring of seafloor vents. Here, we describe the development and application of a remotely operated hydrothermal fluid sampler that enables repeat on-demand sampling of high-temperature vent fluids triggered through the internet. The sampler was deployed from September 2019 to June 2020 at the S&M vent area, in the southern portion of Main Endeavour Field (MEF), Juan de Fuca Ridge, on ONC's NEPTUNE ocean observatory. Nine vent fluid samples were acquired over a period of nine months. Analyses of these samples confirm the moderately high-temperature origin of the source fluid, as indicated, for example, by dissolved chloride depletion relative to seawater (vapor-rich) and moderately high silica concentrations. These and other dissolved species, such as methane, a known hallmark of MEF vent fluids, are in excellent agreement with the reported composition of S&M vent fluids over the past 15 years or more, suggesting overall chemical stability and rock-dominated alteration processes. On the other hand, short-term variability of dissolved Mg, sulfate and barium indicate entrainment of conductively heated and partially reacted seawater. Both before and after the incursion of the “secondary” seawater derived fluid, however, samples reveal the lowest Mg and sulfate concentrations yet reported for seafloor hydrothermal vent fluid samples. Accordingly, these data provide new insight on the solubility of these and other elements coexisting with minerals close to the Axial Magma Chamber (AMC), from which the primary source fluid is ultimately derived. A separate noteworthy event characterized by ∼20 °C decrease in temperature and associated 24–77% decrease in dissolved Fe concentration was observed toward the end of the deployment, with implications for hydrothermal transition metal fluxes and linked biogeochemical processes. On-demand remote acquisition of a continuous series of high-temperature vent fluid samples from a single vent permits the temporal evolution of heat and mass transfer processes to be studied with a heretofore unavailable perspective. Furthermore, deployment of this sampler within the NEPTUNE ocean observatory opens the door to future studies based on comparative analysis of contemporaneous datasets.

A clear north-to-south spatial gradience of chloride in marine aerosol in Chinese seas under the influence of East Asian Winter Monsoon

Particulate chloride is a major component of sea salt particles and plays a key role in atmospheric chemistry. Anthropogenic pollutants over the northeastern Asia can be transported to the adjacent seas through the northwest monsoon, which profoundly influences the chloride chemistry over the seas. In this study, spatial distribution of particulate chloride and its sources over the Chinese seas were investigated based on shipboard particle samplings especially online Single Particle Aerosol Mass Spectrometer (SPAMS) over Bohai Sea, North Yellow Sea, and South Yellow Sea (SYS) during a cruise in November 2012. A strong north-to-south (N-S) gradience in marine aerosol composition was found. The Cl−/Na+ ratios in PM2.5 and single particle composition by SPAMS indicated remarkable chloride enrichment in marine aerosol in the north (Bohai Sea), while depletion in southern SYS. The results of size distribution showed that particulate chloride had higher concentration in coarse particles, while the Cl−/Na+ ratio was much higher in submicron particles. In the north (38–40°N), biomass burning, carbonaceous, and Pb-rich type particles had high fractions in all chloride-containing particles identified by SPAMS (on average 66%). Combining chemical composition with back trajectory, it was found that fine-mode chloride enrichment in the north was mainly due to anthropogenic emission especially coal combustion and biomass burning from northern China. However, the high fine-mode chloride depletion in the south (32–34°N) was probably due to acid replacement by sulfate in aged aerosol during atmospheric transport. Our new findings reveal that marine aerosol in Chinese seas would show a clear N-S pattern of more fresh and anthropogenic enriched particles in the north, but more aged aerosol in the south during the East Asia Winter Monsoon, which provides new insights for the quantitative assessment of anthropogenic impact on marine aerosol and future modeling study.

Insights into tropical cloud chemistry in Réunion (Indian Ocean): results from the BIO-MAÏDO campaign

Abstract. We present here the results obtained during an intensive field campaign conducted in the framework of the French “BIO-MAÏDO” (Bio-physico-chemistry of tropical clouds at Maïdo (Réunion Island): processes and impacts on secondary organic aerosols' formation) project. This study integrates an exhaustive chemical and microphysical characterization of cloud water obtained in March–April 2019 in Réunion (Indian Ocean). Fourteen cloud samples have been collected along the slope of this mountainous island. Comprehensive chemical characterization of these samples is performed, including inorganic ions, metals, oxidants, and organic matter (organic acids, sugars, amino acids, carbonyls, and low-solubility volatile organic compounds, VOCs). Cloud water presents high molecular complexity with elevated water-soluble organic matter content partly modulated by microphysical cloud properties. As expected, our findings show the presence of compounds of marine origin in cloud water samples (e.g. chloride, sodium) demonstrating ocean–cloud exchanges. Indeed, Na+ and Cl− dominate the inorganic composition contributing to 30 % and 27 %, respectively, to the average total ion content. The strong correlations between these species (r2 = 0.87, p value: < 0.0001) suggest similar air mass origins. However, the average molar Cl-/Na+ ratio (0.85) is lower than the sea-salt one, reflecting a chloride depletion possibly associated with strong acids such as HNO3 and H2SO4. Additionally, the non-sea-salt fraction of sulfate varies between 38 % and 91 %, indicating the presence of other sources. Also, the presence of amino acids and for the first time in cloud waters of sugars clearly indicates that biological activities contribute to the cloud water chemical composition. A significant variability between events is observed in the dissolved organic content (25.5 ± 18.4 mg C L−1), with levels reaching up to 62 mg C L−1. This variability was not similar for all the measured compounds, suggesting the presence of dissimilar emission sources or production mechanisms. For that, a statistical analysis is performed based on back-trajectory calculations using the CAT (Computing Atmospheric Trajectory Tool) model associated with the land cover registry. These investigations reveal that air mass origins and microphysical variables do not fully explain the variability observed in cloud chemical composition, highlighting the complexity of emission sources, multiphasic transfer, and chemical processing in clouds. Even though a minor contribution of VOCs (oxygenated and low-solubility VOCs) to the total dissolved organic carbon (DOC) (0.62 % and 0.06 %, respectively) has been observed, significant levels of biogenic VOC (20 to 180 nmol L−1) were detected in the aqueous phase, indicating the cloud-terrestrial vegetation exchange. Cloud scavenging of VOCs is assessed by measurements obtained in both the gas and aqueous phases and deduced experimental gas-/aqueous-phase partitioning was compared with Henry's law equilibrium to evaluate potential supersaturation or unsaturation conditions. The evaluation reveals the supersaturation of low-solubility VOCs from both natural and anthropogenic sources. Our results depict even higher supersaturation of terpenoids, evidencing a deviation from thermodynamically expected partitioning in the aqueous-phase chemistry in this highly impacted tropical area.

Long-range transport of anthropogenic air pollutants into the marine air: insight into fine particle transport and chloride depletion on sea salts

Abstract. Long-range transport of anthropogenic air pollutants from East Asia can affect the downwind marine air quality during spring and winter. Long-range transport of continental air pollutants and their interaction with sea salt aerosol (SSA) significantly modify the radiative forcing of marine aerosols and influence ocean biogeochemical cycling. Previous studies poorly characterize variations of aerosol particles along with air mass transport from the continental edge to the remote ocean. Here, the research ship R/V Dongfanghong 2 traveled from the eastern China seas (ECS) to the northwestern Pacific Ocean (NWPO) to understand what and how air pollutants were transported from the highly polluted continental air to clean marine air in spring. A transmission electron microscope (TEM) was used to find the long-range transported anthropogenic particles and the possible Cl-depletion phenomenon of SSA in marine air. Anthropogenic aerosols (e.g., sulfur (S)-rich, S-soot, S-metal/fly ash, organic matter (OM)-S, and OM coating particles) were identified and dramatically declined from 87 % to 8 % by number from the ECS to remote NWPO. For the SSA aging, 87 % of SSA particles in the ECS were identified as fully aged, while the proportion of fully aged SSA particles in the NWPO decreased to 29 %. Our results highlight that anthropogenic acidic gases in the troposphere (e.g., SO2, NOx, and volatile organic compounds) could be transported to remote marine air and exert a significant impact on aging of SSA particles in the NWPO. The study shows that anthropogenic particles and gases from East Asia significantly perturb different aerosol chemistry from coastal to remote marine air. More attention should be given to the modification of SSA particles in remote marine areas due to the influence of anthropogenic gaseous pollutants.

Strong Acids or Bases Displaced by Weak Acids or Bases in Aerosols: Reactions Driven by the Continuous Partitioning of Volatile Products into the Gas Phase

Aerosols are ubiquitous in the atmosphere and profoundly affect climate systems and human health. To gain more insights on their broad impacts, we need to comprehensively understand the fundamental properties of atmospheric aerosols. Since aerosols are multiphase, a dispersion of condensed matter (solid particles or liquid droplets, hereafter particles) in gas, partitioning of volatile matter between the condensed and the gas phases is one defining characteristic of aerosols. For example, water content partitioning under different relative humidity conditions, known as aerosol hygroscopicity, has been extensively investigated in the past decades. Meanwhile, partitioning of volatile organic or inorganic components, which is referred to as aerosol volatility, remains understudied. Commonly, a bulk solution system is treated as a single phase, with volatility mainly determined by the nature of its components, and the composition partitioning between solution and gas phase is limited. Aerosols, however, comprise an extensive gas phase, and their volatility can also be induced by component reactions. These reactions occurring within aerosols are driven by the formation of volatile products and their continuous partitioning into the gas phase. As a consequence, the overall aerosol systems exhibit prominent volatility. Noteworthily, such volatility induced by reactions is a phenomenon exclusively observed in the multiphase aerosol systems, and it is trivial in bulk solutions due to the limited extent of liquid-gas partitioning. Take the chloride depletion in sea salt particles as an example. Recent findings have revealed that chloride depletion can be caused by reactions between NaCl and weak organic acids, which release HCl into the gas phase. Such a reaction can be described as a strong acid displaced by a weak acid, which is hardly observed in bulk phase. Generally, this unique partitioning behavior of aerosol systems and its potential to alter aerosol composition, size, reactivity, and other physicochemical properties merits more attention by atmospheric community.This Account focuses on the recent advancements in the research of component reactions that induce aerosol volatility. These reactions can be categorized into four types: chloride depletion, nitrate depletion, ammonium depletion, and salt hydrolysis. The depletion of chloride or nitrate can be regarded as a displacement reaction, in which a strong acid is displaced by a weak acid. Such a reaction releases highly volatile HCl or HNO3 into the gas phase and leads to a loss of chloride or nitrate within the particles. Likewise, ammonium depletion is a displacement reaction in which a strong base is displaced by a weak base, resulting in release of ammonia and substantial changes in aerosol hygroscopicity. In addition, aerosol volatility can also be induced by salt hydrolysis in a specific case, which is sustained by the coexistence of proton acceptor and hydroxide ion acceptor within particles. Furthermore, we quantitatively discuss these displacement reactions from both thermodynamic and kinetic perspectives, by using the extended aerosol inorganic model (E-AIM) and Maxwell steady-state diffusive mass transfer equation, respectively. Given the ubiquity of component partitioning in aerosol systems, our discussion may provide a new perspective on the underlying mechanisms of aerosol aging and relevant climate effects.

Seasonal Variation in Chemical Composition of Size-Segregated Aerosols Over the Northeastern Arabian Sea

Water-soluble species constitute a significant fraction (up to 60–70%) of the total aerosol loading in the marine atmospheric boundary layer (MABL). The “indirect” effects, that is, climate forcing due to modification of cloud properties depend on the water-soluble composition of aerosols. Thus, the characterization of aerosols over the MABL is of greater relevance. Here, we present 1-year long aerosol chemical composition data of PM10 and PM2.5 at a costal location in the northeastern Arabian Sea (Goa; 15.45°N, 73.20°E, 56 m above the sea level). Average water-soluble ionic concentration (sum of anion and cation) is highest (25.5 ± 6.9 and 19.6 ± 5.8 μg·m−3 for PM10 and PM2.5, respectively) during winter season and lowest during post-monsoon (17.3 ± 9.1 and 14.4 ± 8.1 μg·m−3 for PM10 and PM2.5, respectively). Among water-soluble ionic spices, SO42- ion was found to be dominant species in anions and NH4+ is dominant in cations, for both PM10 and PM2.5 during all the seasons. These observations clearly hint to the contribution from anthropogenic emission and significant secondary inorganic species formation. Sea-salt (calculated based on Na+ and Cl−) concentration shows significant temporal variability with highest contribution during summer seasons in both fractions. Sea-salt corrected Ca2+, an indicator of mineral dust is found mostly during summer months, particularly in PM10 samples, indicates contribution from mineral dust emissions from arid/semiarid regions located in the north/northwestern India and southwest Asia. These observations are corroborated with back-trajectory analyses, wherein air parcels were found to derive from the desert area in summer and Indo-Gangetic Plains (a hot spot for anthropogenic emissions) during winter. In addition, we also observe the presence of nss-K+ (sea-salt corrected), for PM2.5, particularly during winter months, indicating influence of biomass burning emissions. The impact on aerosol chemistry is further assessed based on chloride depletion. Chloride depletion is observed very significant during post-monsoon months (October and November), wherein more than 80 up to 100% depletion is found, mediated by excess sulfates highlighting the role of secondary species in atmospheric chemistry. Regional scale characterization of atmospheric aerosols is important for their better parameterization in chemical transport model and estimation of radiative forcing.

Chemical characteristics of sulfur-containing aerosol particles across the western North Pacific and the Arctic Ocean

The characteristics of aerosol methanesulfonic acid (MSA), non-sea-salt sulfate (nss-SO42−) and MSA/nss-SO42− ratio, were measured at high-time resolution (1 h) over the East sea/sea of Japan (R1, 31° - 47°N, 121° - 145°E), western North Pacific Ocean (R2, 47° - 58°N, 145° - 176°E), subarctic western North Pacific (R3, 58° - 66°N, 176°E - 169°W) and Arctic Ocean (R4, 66° - 85°N, 150–174°W) during July–September 2018. The highest MSA levels were observed in R2, with an average of 0.22 ± 0.18 μg m−3. These levels were 3–10 times higher than in other regions, correlating with biological productivity. The concentration of nss-SO42− decreased with distance from Eurasia. The MSA/nss-SO42− ratios were 0.10 ± 0.27, 0.38 ± 0.43, 0.30 ± 0. 36 and 0.39 ± 0.48 over R1, R2, R3 and R4, respectively. Biological sources were larger contributors of nss-SO42− in R2 while nss-SO42− were affected more by continental anthropogenic sources in R1. Positive and negative relationships between the MSA/nss-SO42− ratio and temperature were observed, indicating that temperature may have a different influence on the MSA/nss-SO42− ratio. Four high level regions of MSA were observed over the R4, wind speed and temperature were critical factors that affected MSA levels over the R4. Significant depletion of chloride was observed and areas that were more affected by terrestrial sources had a greater chlorine depletion in this study, which means that the magnitude of the chlorine depletion followed the order R1 > R3 > R2 > R4.

Individual particle investigation on the chloride depletion of inland transported sea spray aerosols during East Asian summer monsoon

Inland transported sea spray aerosol (SSA) particles along with multiphase reactions are essential to drive the regional circulation of nitrogen, sulfur and halogen species in the atmosphere. Specially, the physicochemical properties of SSA will be significantly affected by the displacement reaction of chloride. However, the role of organic species and the mixing state on the chloride depletion of SSA during long-range inland transport remains unclear. Hence, a single particle aerosol mass spectrometer (SPAMS) was employed to investigate the particle size and chemical composition of individual SSA particles over inland southern China during the East Asian summer monsoon. Based on the variation of chemical composition, SSA particles were clustered into SSA-Aged, SSA-Bio and SSA-Ca. SSA-Aged was regarded as the aged Na-rich SSA particles. In comparison to the SSA-Aged, SSA-Bio involved some extra organic species associated with biological origin (i.e., organic nitrogen and phosphate). Each type occupies for approximately 50% of total detected SSA particles. Besides, SSA-Ca may relate to organic shell of Na-rich SSA particles, which is negligible (~3%). Tight correlation between Na and diverse organic acids was exhibited for the SSA-Aged (r2 = 0.52, p < 0.01) and SSA-Bio (r2 = 0.61, p < 0.01), reflecting the impact of organic acids to the chloride displacement during inland transport SSA particles. The chloride depletion occupied by organic acids is estimated to be up to 34%. It is noted that distinctly different degree of chloride depletion was observed between SSA-Aged and SSA-Bio. It is more likely to be attributed to the associated organic coatings for the SSA-Bio particles, which inhibits the displacement reactions between acids and chloride. As revealed from the mixing state of SSA-Bio, defined hourly mean peak area ratio of Cl / Na increases with the increasing phosphate and organic nitrogen. This finding provides additional basis for the improvement of modeling simulations in chlorine circulation and a comprehensive understanding of the effects of organics on chloride depletion of SSA particles.

Dietary Chloride Deficiency Syndrome: Pathophysiology, History, and Systematic Literature Review.

Metabolic alkalosis may develop as a consequence of urinary chloride (and sodium) wasting, excessive loss of salt in the sweat, or intestinal chloride wasting, among other causes. There is also a likely underrecognized association between poor salt intake and the mentioned electrolyte and acid–base abnormality. In patients with excessive loss of salt in the sweat or poor salt intake, the maintenance of metabolic alkalosis is crucially modulated by the chloride–bicarbonate exchanger pendrin located on the renal tubular membrane of type B intercalated cells. In the late 1970s, recommendations were made to decrease the salt content of foods as part of an effort to minimize the tendency towards systemic hypertension. Hence, the baby food industry decided to remove added salt from formula milk. Some weeks later, approximately 200 infants (fed exclusively with formula milks with a chloride content of only 2–4 mmol/L), were admitted with failure to thrive, constipation, food refusal, muscular weakness, and delayed psychomotor development. The laboratory work-up disclosed metabolic alkalosis, hypokalemia, hypochloremia, and a reduced urinary chloride excretion. In all cases, both the clinical and the laboratory features remitted in ≤7 days when the infants were fed on formula milk with a normal chloride content. Since 1982, 13 further publications reported additional cases of dietary chloride depletion. It is therefore concluded that the dietary intake of chloride, which was previously considered a “mendicant” ion, plays a crucial role in acid–base and salt balance.

Origin of chronoamperometric responses associated with impacts of single electrolyte droplets at a polarized liquid/liquid interface

Chronoamperometric measurements at a constant potential are used to study the single impacts of the water-in-DCE emulsion droplets containing an electrolyte (tetrapropylammonium chloride, TPrACl) at a polarized water(W)/1,2-dichloroethane (DCE) interface. The impacts give rise to the spike-like current transients, which are characterized by the initial current step (time constant less than 2 ms) followed by a slower exponential current decay with a time constant in tens of milliseconds. It is shown that the theoretical treatment of the current spikes can be based on a modification of the bulk electrolysis model including (1) the droplet collision at the W/DCE interface, (2) a partial coalescence (fusion) of the droplet with the impacted interface, (3) a reorganization of the electric double layer leading to the propagation of the interfacial potential difference from the impacted interface to the surface of the droplet, and (4) stripping (bulk electrolysis) of TPrA+ from the droplet to the DCE phase accompanied by the chloride depletion into the bulk water phase. On assuming that the stripping of TPrA+ is the rate-determining step of the impact event, the theoretical relationships for the current transient are derived, which are confirmed by the experimental data. An analysis of the current transients yields the charge corresponding to the ionic content of the droplets, which is used to evaluate the droplet diameter. Droplet size distribution with the droplet diameter of around 8 μm is verified by an analysis of the microscopic images of the W-in-DCE emulsion, and in part also by the dynamic laser scattering measurements. It is shown that the frequency of the droplet collisions with the W/DCE interface (1–10 Hz) is controlled by migration of the negatively charged droplets towards the interface.