Experimental study on HCl uptake by MgCl2 and sea salt under humid conditions.

We studied HCl uptake by MgCl2 and sea salt over a relative humidity (RH) range from 0% to 34% at 278-313 K using a differential bead-filled flow tube coupled to a high-pressure chemical ionization mass spectrometer. The results showed that dry MgCl2 and sea salt are essentially inert to gaseous HCl with a probability of less than 10-6 . However, under humid conditions, HCl was found to be efficiently taken up by wet inorganic surfaces. The HCl uptake coefficient for MgCl2 and sea salt increased squarely with RH, reaching a value of 0.00123 and 0.00171, respectively, at 29% RH and 298 K. Such wetting behavior is even enhanced at elevated temperatures, with the coefficient reaching 0.00208 and 0.00239, respectively, at 313 K. Based on the study of the dependence of γHCl on the initial HCl concentration, we estimate γHCl as 0.012 at 24% RH at a typical HCl concentration in the troposphere. In addition, the observation of the remarkable enhancement in the OH uptake by the HCl-treated salts agrees with the results of our previous investigation, which suggested that water absorption on salts enhances γOH by lowering the surface pH. The proposed mechanism of HCl uptake by sea salt aerosol has implications for ozone production in the marine boundary layer.

Understanding transmission and intervention for the COVID-19 pandemic in the United States.

The outbreak of the novel coronavirus disease (COVID-19) severely threatens the public health worldwide, but the transmission mechanism and the effectiveness of mitigation measures remain uncertain. Here we assess the role of airborne transmission in spreading the disease and the effectiveness of face covering in preventing inter-human transmission for the top-fifteen infected U.S. states during March 1 and May 18, 2020. For all fifteen states, the curve of total confirmed infections exhibits an initial sub-exponential growth and a subsequent linear growth after implementing social distancing/stay-at-home orders. The linearity extends one to two months for the six states without mandated face covering and to the onset of mandated face covering for the other nine states with this measure, reflecting a dynamic equilibrium between first-order transmission kinetics and intervention. For the states with mandated face covering, significant deviation from this linearity and curve flattening occur after the onset of this measure for seven states, with exceptions for two states. Most states exhibit persistent upward trends in the daily new infections after social distancing/stay-at-home orders, while reversed downward or slowing trends occur for eight states after implementing mandated face covering. The inadequacy of social distancing and stay-at-home measures alone in preventing inter-human transmission is reflected by the continuous linear growth in the total infection curve after implementing these measures, which is mainly driven by airborne transmission. We estimate that the number of the total infections prevented by face covering reaches ~252,000 on May 18 in seven states, which is equivalent to ~17% of the total infections in the nation. We conclude that airborne transmission and face covering play the dominant role in spreading the disease and flattening the total infection curve, respectively. Our findings provide policymakers and the public with compelling evidence that universal face covering, in conjunction with social distancing and hand hygiene, represents the maximal protection against inter-human transmission and the combination of these intervention measures with rapid and extensive testing as well as contact tracing is crucial in containing the COVID-19 pandemic.

Identifying airborne transmission as the dominant route for the spread of COVID-19.

Various mitigation measures have been implemented to fight the coronavirus disease 2019 (COVID-19) pandemic, including widely adopted social distancing and mandated face covering. However, assessing the effectiveness of those intervention practices hinges on the understanding of virus transmission, which remains uncertain. Here we show that airborne transmission is highly virulent and represents the dominant route to spread the disease. By analyzing the trend and mitigation measures in Wuhan, China, Italy, and New York City, from January 23 to May 9, 2020, we illustrate that the impacts of mitigation measures are discernable from the trends of the pandemic. Our analysis reveals that the difference with and without mandated face covering represents the determinant in shaping the pandemic trends in the three epicenters. This protective measure alone significantly reduced the number of infections, that is, by over 78,000 in Italy from April 6 to May 9 and over 66,000 in New York City from April 17 to May 9. Other mitigation measures, such as social distancing implemented in the United States, are insufficient by themselves in protecting the public. We conclude that wearing of face masks in public corresponds to the most effective means to prevent interhuman transmission, and this inexpensive practice, in conjunction with simultaneous social distancing, quarantine, and contact tracing, represents the most likely fighting opportunity to stop the COVID-19 pandemic. Our work also highlights the fact that sound science is essential in decision-making for the current and future public health pandemics.

Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation.

Secondary organic aerosol (SOA) represents a major constituent of tropospheric fine particulate matter, with profound implications for human health and climate. However, the chemical mechanisms leading to SOA formation remain uncertain, and atmospheric models consistently underpredict the global SOA budget. Small α-dicarbonyls, such as methylglyoxal, are ubiquitous in the atmosphere because of their significant production from photooxidation of aromatic hydrocarbons from traffic and industrial sources as well as from biogenic isoprene. Current experimental and theoretical results on the roles of methylglyoxal in SOA formation are conflicting. Using quantum chemical calculations, we show cationic oligomerization of methylglyoxal in aqueous media. Initial protonation and hydration of methylglyoxal lead to formation of diols/tetrol, and subsequent protonation and dehydration of diols/tetrol yield carbenium ions, which represent the key intermediates for formation and propagation of oligomerization. On the other hand, our results reveal that the previously proposed oligomerization via hydration for methylglyoxal is kinetically and thermodynamically implausible. The carbenium ion-mediated mechanism occurs barrierlessly on weakly acidic aerosols and cloud/fog droplets and likely provides a key pathway for SOA formation from biogenic and anthropogenic emissions.

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust.

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem.

An unexpected catalyst dominates formation and radiative forcing of regional haze.

Although regional haze adversely affects human health and possibly counteracts global warming from increasing levels of greenhouse gases, the formation and radiative forcing of regional haze on climate remain uncertain. By combining field measurements, laboratory experiments, and model simulations, we show a remarkable role of black carbon (BC) particles in driving the formation and trend of regional haze. Our analysis of long-term measurements in China indicates declined frequency of heavy haze events along with significantly reduced SO2, but negligibly alleviated haze severity. Also, no improving trend exists for moderate haze events. Our complementary laboratory experiments demonstrate that SO2 oxidation is efficiently catalyzed on BC particles in the presence of NO2 and NH3, even at low SO2 and intermediate relative humidity levels. Inclusion of the BC reaction accounts for about 90-100% and 30-50% of the sulfate production during moderate and heavy haze events, respectively. Calculations using a radiative transfer model and accounting for the sulfate formation on BC yield an invariant radiative forcing of nearly zero W m-2 on the top of the atmosphere throughout haze development, indicating small net climatic cooling/warming but large surface cooling, atmospheric heating, and air stagnation. This BC catalytic chemistry facilitates haze development and explains the observed trends of regional haze in China. Our results imply that reduction of SO2 alone is insufficient in mitigating haze occurrence and highlight the necessity of accurate representation of the BC chemical and radiative properties in predicting the formation and assessing the impacts of regional haze.

Adverse organogenesis and predisposed long-term metabolic syndrome from prenatal exposure to fine particulate matter.

Exposure to fine particulate matter (PM) during pregnancy is associated with high risks of birth defects/fatality and adverse long-term postnatal health. However, limited mechanistic data are available to assess the detailed impacts of prenatal PM exposure. Here we evaluate fine PM exposure during pregnancy on prenatal/postnatal organogenesis in offspring and in predisposing metabolic syndrome for adult life. Between days 0 and 18 of gestation, two groups of adult female rats (n = 10 for each) were placed in a dual-exposure chamber device, one with clean ambient air (∼3 µg·m-3) and the other with ambient air in the presence of 100 to 200 µg·m-3 of ultrafine aerosols of ammonium sulfate. At birth (postnatal day 0, PND0), four males and four females were selected randomly from each litter to be nursed by dams, whereas tissues were collected from the remaining pups. At PND21, tissues were collected from two males and two females, whereas the remaining pups were fed either a high- or low-fat diet until PND105, when tissues were obtained for biochemical and physiological analyses. Maternal exposure to fine PM increased stillbirths; reduced gestation length and birth weight; increased concentrations of glucose and free fatty acids in plasma; enhanced lipid accumulation in the liver; and decreased endothelium-dependent relaxation of aorta. This lead to altered organogenesis and predisposed progeny to long-term metabolic defects in an age-, organ-, and sex-specific manner. Our results highlight the necessity to develop therapeutic strategies to remedy adverse health effects of maternal PM exposure on conceptus/postnatal growth and development.

In utero ultrafine particulate matter exposure causes offspring pulmonary immunosuppression.

Early life exposure to fine particulate matter (PM) in air is associated with infant respiratory disease and childhood asthma, but limited epidemiological data exist concerning the impacts of ultrafine particles (UFPs) on the etiology of childhood respiratory disease. Specifically, the role of UFPs in amplifying Th2- and/or Th17-driven inflammation (asthma promotion) or suppressing effector T cells (increased susceptibility to respiratory infection) remains unclear. Using a mouse model of in utero UFP exposure, we determined early immunological responses to house dust mite (HDM) allergen in offspring challenged from 0 to 4 wk of age. Two mice strains were exposed throughout gestation: C57BL/6 (sensitive to oxidative stress) and BALB/C (sensitive to allergen exposure). Offspring exposed to UFPs in utero exhibited reduced inflammatory response to HDM. Compared with filtered air (FA)-exposed/HDM-challenged mice, UFP-exposed offspring had lower white blood cell counts in bronchoalveolar lavage fluid and less pronounced peribronchiolar inflammation in both strains, albeit more apparent in C57BL/6 mice. In the C57BL/6 strain, offspring exposed in utero to FA and challenged with HDM exhibited a robust response in inflammatory cytokines IL-13 and Il-17. In contrast, this response was lost in offspring exposed in utero to UFPs. Circulating IL-10 was significantly up-regulated in C57BL/6 offspring exposed to UFPs, suggesting increased regulatory T cell expression and suppressed Th2/Th17 response. Our results reveal that in utero UFP exposure at a level close to the WHO recommended PM guideline suppresses an early immune response to HDM allergen, likely predisposing neonates to respiratory infection and altering long-term pulmonary health.

Changes in Emissions of Ozone-Depleting Substances from China Due to Implementation of the Montreal Protocol.

The ozone layer depletion and its recovery, as well as the climate influence of ozone-depleting substances (ODSs) and their substitutes that influence climate, are of interest to both the scientific community and the public. Here we report on the emissions of ODSs and their substitute from China, which is currently the largest consumer (and emitter) of these substances. We provide, for the first time, comprehensive information on ODSs and replacement hydrofluorocarbon (HFC) emissions in China starting from 1980 based on reported production and usage. We also assess the impacts (and costs) of controls on ODS consumption and emissions on the ozone layer (in terms of CFC-11-equivalent) and climate (in CO2-equivalent). In addition, we show that while China's future ODS emissions are likely to be defined as long as there is full compliance with the Montreal Protocol; its HFC emissions through 2050 are very uncertain. Our findings imply that HFC controls over the next decades that are more stringent than those under the Kigali Amendment to the Montreal Protocol would be beneficial in mitigating global climate change.

Reassessing the atmospheric oxidation mechanism of toluene.

Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH (ortho) addition, the pathway of H extraction by O2 to form the cresol proceeds with a smaller barrier than O2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

Sistemas de acreditación, certificación y regulación del ejercicio de la psicología clínica en Argentina / Systems of accreditation, certification and regulation of the practice of clinical psychology in Argentina

Argentina cuenta con una importante tradición en psicología y, si bien las carreras universitarias comenzaron a mediados de la década del 50, el proceso de evaluación y acreditación voluntario se inició después de la aprobación de los estándares ocurrido en 2009. En este trabajo se presentan y analizan distintos aspectos sobre dicho proceso tanto para las carreras de grado como para las de posgrado. También se exponen los aspectos pertinentes para la práctica profesional. Se revisan las normativas legales vigentes del ejercicio profesional de la psicología clínica, primer área que cuenta con el reconocimiento oficial como especialidad otorgado por el Ministerio de salud de la Nación.

Argentina has an important tradition in psychology and although university careers began in the mid 50's, the process of voluntary evaluation and accreditation, was initiated after the approval of the standards in 2009. In this article different aspects of this process both for the undergraduate and graduate careers are presented and analyzed. Relevant aspects of professional practice are also outlined. Current legal regulations of the professional practice of clinical psychology are reviewed. This is the first area having official recognition as a specialty awarded by the National Ministry of Health.

Physical Chemistry of the Freezing Process of Atmospheric Aqueous Drops.

In supercooled aqueous solutions, ice nucleation is the initial stage of the freezing process. In this paper, we present experimental results that indicate that during the freezing of aqueous solutions, freeze-induced phase separation (FIPS) into pure ice and a freeze-concentrated solution (FCS) takes place. Our observations involve the use of an optical cryo-microscope (OC-M) to record images and movies. The results visually indicate for the first time that there are two freezing processes for (NH4)3H(SO4)2/H2O solutions: (i) contact freezing, as is the case for pure water drops, and (ii) the Wegener-Bergeron-Findeisen process, which is the growth of frozen drops (ice) at the expense of liquid ones. We also present OC-M images of frozen micrometer-scaled H2SO4/H2O drops that support our previous finding that freezing of these solutions generates mixed-phase particles, namely an ice core coated with a FCS. These results are relevant for atmospheric as well as for pharmaceutical sciences.

Visualization data on the freezing process of micrometer-scaled aqueous citric acid drops.

The visualization data (8 movies) presented in this article are related to the research article entitled "Freezing and glass transitions upon cooling and warming and ice/freeze-concentration-solution morphology of emulsified aqueous citric acid" (A. Bogdan, M.J. Molina, H. Tenhu, 2016) [1]. The movies recorded in-situ with optical cryo-miscroscopy (OC-M) demonstrate for the first time freezing processes that occur during the cooling and subsequent warming of emulsified micrometer-scaled aqueous citric acid (CA) drops. The movies are made publicly available to enable critical or extended analyzes.

Persistent sulfate formation from London Fog to Chinese haze.

Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH3 and NO2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

Freezing and glass transitions upon cooling and warming and ice/freeze-concentration-solution morphology of emulsified aqueous citric acid.

Although freeze-induced phase separation and the ice/FCS (freeze-concentration solution) morphology of aqueous solutions play an important role in fields ranging from life sciences and biotechnology to geophysics and high-altitude ice clouds, their understanding is far from complete. Herein, using differential scanning calorimetry (DSC) and optical cryo-microscope (OC-M), we have studied the freezing and glass transition behavior and the ice/FCS morphology of emulsified 10-60wt% CA (citric acid) solutions in the temperature region of ∼308and153K. We have obtained a lot of new result which are understandable and unclear. The most essential understandable results are as follows: (i) similar to bulk CA/H2O, emulsified CA/H2O also freezes upon cooling and warming and (ii) the ice/FCS morphology of frozen drops smaller than ∼3-4µm is less ramified than that of frozen bulk solutions. Unclear results, among others, are as follows: (i) in contrast to bulk solutions, which produce one freezing event, emulsified CA/H2O produces two freezing events and (ii) in emulsions, drop concentration is not uniform. Our results demonstrate that DSC thermograms and OC-M images/movies are mutually supplementary and allow us to extract important information which cannot be gained when DSC and OC-M techniques are used alone.

Improving our fundamental understanding of the role of aerosol-cloud interactions in the climate system.

The effect of an increase in atmospheric aerosol concentrations on the distribution and radiative properties of Earth's clouds is the most uncertain component of the overall global radiative forcing from preindustrial time. General circulation models (GCMs) are the tool for predicting future climate, but the treatment of aerosols, clouds, and aerosol-cloud radiative effects carries large uncertainties that directly affect GCM predictions, such as climate sensitivity. Predictions are hampered by the large range of scales of interaction between various components that need to be captured. Observation systems (remote sensing, in situ) are increasingly being used to constrain predictions, but significant challenges exist, to some extent because of the large range of scales and the fact that the various measuring systems tend to address different scales. Fine-scale models represent clouds, aerosols, and aerosol-cloud interactions with high fidelity but do not include interactions with the larger scale and are therefore limited from a climatic point of view. We suggest strategies for improving estimates of aerosol-cloud relationships in climate models, for new remote sensing and in situ measurements, and for quantifying and reducing model uncertainty.

Markedly enhanced absorption and direct radiative forcing of black carbon under polluted urban environments.

Black carbon (BC) exerts profound impacts on air quality and climate because of its high absorption cross-section over a broad range of electromagnetic spectra, but the current results on absorption enhancement of BC particles during atmospheric aging remain conflicting. Here, we quantified the aging and variation in the optical properties of BC particles under ambient conditions in Beijing, China, and Houston, United States, using a novel environmental chamber approach. BC aging exhibits two distinct stages, i.e., initial transformation from a fractal to spherical morphology with little absorption variation and subsequent growth of fully compact particles with a large absorption enhancement. The timescales to achieve complete morphology modification and an absorption amplification factor of 2.4 for BC particles are estimated to be 2.3 h and 4.6 h, respectively, in Beijing, compared with 9 h and 18 h, respectively, in Houston. Our findings indicate that BC under polluted urban environments could play an essential role in pollution development and contribute importantly to large positive radiative forcing. The variation in direct radiative forcing is dependent on the rate and timescale of BC aging, with a clear distinction between urban cities in developed and developing countries, i.e., a higher climatic impact in more polluted environments. We suggest that mediation in BC emissions achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries.

Hydrofluorocarbon (HFC) Emissions in China: An Inventory for 2005-2013 and Projections to 2050.

Many hydrofluorocarbons (HFCs) that are widely used as substitutes for ozone-depleting substances (now regulated under the Montreal Protocol) are very potent greenhouse gases (GHGs). China's past and future HFC emissions are of great interest because China has emerged as a major producer and consumer of HFCs. Here, we present for the first time a comprehensive inventory estimate of China's HFC emissions during 2005-2013. Results show a rapid increase in HFC production, consumption, and emissions in China during the period and that the emissions of HFC with a relatively high global warming potential (GWP) grew faster than those with a relatively low GWP. The proportions of China's historical HFC CO2-equivalent emissions to China's CO2 emissions or global HFC CO2-equivalent emissions increased rapidly during 2005-2013. Using the "business-as-usual" (BAU) scenario, in which HFCs are used to replace a significant fraction of hydrochlorofluorocarbons (HCFCs) in China (to date, there are no regulations on HFC uses in China), emissions of HFCs are projected to be significant components of China's and global future GHG emissions. However, potentials do exist for minimizing China's HFC emissions (for example, if regulations on HFC uses are established in China). Our findings on China's historical and projected HFC emission trajectories could also apply to other developing countries, with important implications for mitigating global GHG emissions.

Multiple glass transitions and freezing events of aqueous citric acid.

Calorimetric and optical cryo-microscope measurements of 10-64 wt % citric acid (CA) solutions subjected to moderate (3 K/min) and slow (0.5 and 0.1 K/min) cooling/warming rates and also to quenching/moderate warming between 320 and 133 K are presented. Depending on solution concentration and cooling rate, the obtained thermograms show one freezing event and from one to three liquid-glass transitions upon cooling and from one to six liquid-glass and reverse glass-liquid transitions, one or two freezing events, and one melting event upon warming of frozen/glassy CA/H2O. The multiple freezing events and glass transitions pertain to the mother CA/H2O solution itself and two freeze-concentrated solution regions, FCS1 and FCS2, of different concentrations. The FCS1 and FCS2 (or FCS22) are formed during the freezing of CA/H2O upon cooling and/or during the freezing upon warming of partly glassy or entirely glassy mother CA/H2O. The formation of two FCS1 and FCS22 regions during the freezing upon warming to our best knowledge has never been reported before. Using an optical cryo-microscope, we are able to observe the formation of a continuous ice framework (IF) and its morphology and reciprocal distribution of IF/(FCS1 + FCS2). Our results provide a new look at the freezing and glass transition behavior of aqueous solutions and can be used for the optimization of lyophilization and freezing of foods and biopharmaceutical formulations, among many other applications where freezing plays a crucial role.

Visualization of freezing process in situ upon cooling and warming of aqueous solutions.

The freezing of aqueous solutions and reciprocal distribution of ice and a freeze-concentrated solution (FCS) are poorly understood in spite of their importance in fields ranging from biotechnology and life sciences to geophysics and climate change. Using an optical cryo-microscope and differential scanning calorimetry, we demonstrate that upon cooling of citric acid and sucrose solutions a fast freezing process results in a continuous ice framework (IF) and two freeze-concentrated solution regions of different concentrations, FCS1 and FCS2. The FCS1 is maximally freeze-concentrated and interweaves with IF. The less concentrated FCS2 envelops the entire IF/FCS1. We find that upon further cooling, the FCS1 transforms to glass, whereas the slow freezing of FCS2 continues until it is terminated by a FCS2-glass transition. We observe the resumed slow freezing of FCS2 upon subsequent warming. The net thermal effect of the resumed freezing and a reverse glass-FCS1 transition produces the Ttr2-transition which before has only been observed upon warming of frozen hydrocarbon solutions and which nature has remained misunderstood for decades.