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New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN)1-4. However, the precursor vapours that drive the process are not well understood. With experiments performed under upper tropospheric conditions in the CERN CLOUD chamber, we show that nitric acid, sulfuric acid and ammonia form particles synergistically, at rates that are orders of magnitude faster than those from any two of the three components. The importance of this mechanism depends on the availability of ammonia, which was previously thought to be efficiently scavenged by cloud droplets during convection. However, surprisingly high concentrations of ammonia and ammonium nitrate have recently been observed in the upper troposphere over the Asian monsoon region5,6. Once particles have formed, co-condensation of ammonia and abundant nitric acid alone is sufficient to drive rapid growth to CCN sizes with only trace sulfate. Moreover, our measurements show that these CCN are also highly efficient ice nucleating particles-comparable to desert dust. Our model simulations confirm that ammonia is efficiently convected aloft during the Asian monsoon, driving rapid, multi-acid HNO3-H2SO4-NH3 nucleation in the upper troposphere and producing ice nucleating particles that spread across the mid-latitude Northern Hemisphere.
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A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog1,2, but how it occurs in cities is often puzzling3. If the growth rates of urban particles are similar to those found in cleaner environments (1-10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below -15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid-base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms4,5.
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Humans are known to be a continuous and potent indoor source of volatile organic compounds (VOCs). However, little is known about how personal hygiene, in terms of showering frequency, can influence these emissions and their impact on indoor air chemistry involving ozone. In this study, we characterized the VOC composition of the air in a controlled climate chamber (22.5 m3 with an air change rate at 3.2 h-1) occupied by four male volunteers on successive days under ozone-free (â¼0 ppb) and ozone-present (37-40 ppb) conditions. The volunteers either showered the evening prior to the experiments or skipped showering for 24 and 48 h. Reduced shower frequency increased human emissions of gas-phase carboxylic acids, possibly originating from skin bacteria. With ozone present, increasing the number of no-shower days enhanced ozone-skin surface reactions, yielding higher levels of oxidation products. Wearing the same clothing over several days reduced the level of compounds generated from clothing-ozone reactions. When skin lotion was applied, the yield of the skin ozonolysis products decreased, while other compounds increased due to ozone reactions with lotion ingredients. These findings help determine the degree to which personal hygiene choices affect the indoor air composition and indoor air exposures.
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Contaminación del Aire Interior , Ozono , Compuestos Orgánicos Volátiles , Humanos , Ozono/análisis , Compuestos Orgánicos Volátiles/análisis , Masculino , Higiene , AdultoRESUMEN
Ozone reaction with human surfaces is an important source of ultrafine particles indoors. However, 1-20 nm particles generated from ozone-human chemistry, which mark the first step of particle formation and growth, remain understudied. Ventilation and indoor air movement could have important implications for these processes. Therefore, in a controlled-climate chamber, we measured ultrafine particles initiated from ozone-human chemistry and their dependence on the air change rate (ACR, 0.5, 1.5, and 3 h-1) and operation of mixing fans (on and off). Concurrently, we measured volatile organic compounds (VOCs) and explored the correlation between particles and gas-phase products. At 25-30 ppb ozone levels, humans generated 0.2-7.7 × 1012 of 1-3 nm, 0-7.2 × 1012 of 3-10 nm, and 0-1.3 × 1012 of 10-20 nm particles per person per hour depending on the ACR and mixing fan operation. Size-dependent particle growth and formation rates increased with higher ACR. The operation of mixing fans suppressed the particle formation and growth, owing to enhanced surface deposition of the newly formed particles and their precursors. Correlation analyses revealed complex interactions between the particles and VOCs initiated by ozone-human chemistry. The results imply that ventilation and indoor air movement may have a more significant influence on particle dynamics and fate relative to indoor chemistry.
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Contaminantes Atmosféricos , Contaminación del Aire Interior , Ozono , Compuestos Orgánicos Volátiles , Humanos , Tamaño de la Partícula , Ozono/análisis , Ventilación/métodos , Material Particulado/análisis , Compuestos Orgánicos Volátiles/análisis , Contaminación del Aire Interior/análisis , Contaminantes Atmosféricos/análisisRESUMEN
Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements.
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PURPOSE: Anterior knee pain is a major reason for unsatisfied patients after total knee arthroplasty (TKA). Since malposition and increased retropatellar peak pressure are supposed to contribute to pain, we conducted this in vitro study to analyse the influence of mediolateral tibial component position on tibiofemoral and patella kinematics as well as retropatellar pressure. METHODS: Eight fresh frozen cadaver specimens were tested after a fixed-bearing TKA. To evaluate the influence of mediolateral tibial component position, special inlays with 3 mm of medialization and lateralization were constructed. For the analysis, a weight-bearing knee rig under a loaded squat from 20° to 120° of flexion was used. Tibiofemoral and patella kinematics were measured with an ultrasonic-based three-dimensional motion analysis system. Additionally, retropatellar pressure distribution was registered with a pressure-sensitive film. RESULTS: Alteration of mediolateral tibial component position by 3 mm did not reveal a significant influence on retropatellar peak pressure (7.5 ± 2.5 vs. 7.2 ± 2.6 MPa). Regarding tibiofemoral kinematics, 3-mm medialization of the tibial baseplate significantly increased lateral femoral rollback and femorotibial external rotation. Medialization of 3 mm also significantly increased the relative medial patella shift and decreased lateral patella tilt. DISCUSSION: Medialization of the tibial baseplate came along with more lateral rollback and external femorotibial rotation. For the positioning of the tibial baseplate, rotational alignment seems to be more important than mediolateral orientation. Since retropatellar peak pressure remained rather unchanged, the tibial baseplate should be placed by the surgeon looking for a maximal tibial coverage without overhang.
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Artroplastia de Reemplazo de Rodilla/métodos , Articulación de la Rodilla/fisiología , Rótula/fisiología , Anciano , Anciano de 80 o más Años , Fenómenos Biomecánicos , Cadáver , Femenino , Fémur/cirugía , Humanos , Articulación de la Rodilla/cirugía , Masculino , Persona de Mediana Edad , Rótula/cirugía , Presión , Rango del Movimiento Articular , Rotación , Tibia/cirugía , Soporte de PesoRESUMEN
PURPOSE: Although continuous improvements have been made, there is still a considerable amount of unsatisfied patients after total knee arthroplasty (TKA). A main reason for this high percentage is anterior knee pain, which is supposed to be provoked by post-operative increased retropatellar peak pressure. Since rotational malalignment of the implant is believed to contribute to post-operative pain, the aim of this study was to examine the influence of tibial component rotation on knee kinematics and retropatellar pressure. METHODS: Eight fresh-frozen knee specimens were tested in a weight-bearing knee rig after fixed-bearing TKA under a loaded squat from 20° to 120° of flexion. To examine tibial components with different rotations, special inlays with 3° internal rotation and 3° external rotation were produced and retropatellar pressure distribution was measured with a pressure-sensitive film. The kinematics of the patella and the femorotibial joint were recorded with an ultrasonic-based motion analysis system. RESULTS: Retropatellar peak pressure decreased significantly from 3° internal rotation to neutral position and 3° external rotation of the tibial component (8.5 ± 2.3 vs. 8.2 ± 2.4 vs. 7.8 ± 2.5 MPa). Regarding knee kinematics femorotibial rotation and anterior-posterior translation, patella rotation and tilt were altered significantly, but relative changes remained minimal. CONCLUSION: Changing tibial rotation revealed a high in vitro influence on retropatellar peak pressure. We recommend the rotational alignment of the tibial component to the medial third of the tibial tuberosity or even more externally beyond that point to avoid anterior knee pain after TKA.
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Artroplastia de Reemplazo de Rodilla , Articulación de la Rodilla/cirugía , Rótula/fisiología , Presión , Rotación , Tibia/fisiología , Anciano , Anciano de 80 o más Años , Fenómenos Biomecánicos , Desviación Ósea , Cadáver , Femenino , Humanos , Técnicas In Vitro , Masculino , Persona de Mediana Edad , Rango del Movimiento Articular , Soporte de PesoRESUMEN
BACKGROUND: Manual interpretation of single-lead ECGs (SL-ECGs) is often required to confirm a diagnosis of atrial fibrillation. However accuracy in detecting atrial fibrillation via SL-ECGs may vary according to clinical expertise and choice of smart device. AIMS: To compare the accuracy of cardiologists, internal medicine residents and medical students in detecting atrial fibrillation via SL-ECGs from five different smart devices (Apple Watch, Fitbit Sense, KardiaMobile, Samsung Galaxy Watch, Withings ScanWatch). Participants were also asked to assess the quality and readability of SL-ECGs. METHODS: In this prospective study (BaselWearableStudy, NCT04809922), electronic invitations to participate in an online survey were sent to physicians at major Swiss hospitals and to medical students at Swiss universities. Participants were asked to classify up to 50 SL-ECGs (from ten patients and five devices) into three categories: sinus rhythm, atrial fibrillation or inconclusive. This classification was compared to the diagnosis via a near-simultaneous 12-lead ECG recording interpreted by two independent cardiologists. In addition, participants were asked their preference of each manufacturer's SL-ECG. RESULTS: Overall, 450 participants interpreted 10,865 SL-ECGs. Sensitivity and specificity for the detection of atrial fibrillation via SL-ECG were 72% and 92% for cardiologists, 68% and 86% for internal medicine residents, 54% and 65% for medical students in year 4-6 and 44% and 58% for medical students in year 1-3; p <0.001. Participants who stated prior experience in interpreting SL-ECGs demonstrated a sensitivity and specificity of 63% and 81% compared to a sensitivity and specificity of 54% and 67% for participants with no prior experience in interpreting SL-ECGs (p <0.001). Of all participants, 107 interpreted all 50 SL-ECGs. Diagnostic accuracy for the first five interpreted SL-ECGs was 60% (IQR 40-80%) and diagnostic accuracy for the last five interpreted SL-ECGs was 80% (IQR 60-90%); p <0.001. No significant difference in the accuracy of atrial fibrillation detection was seen between the five smart devices; p = 0.33. SL-ECGs from the Apple Watch were considered as having the best quality and readability by 203 (45%) and 226 (50%) participants, respectively. CONCLUSION: SL-ECGs can be challenging to interpret. Accuracy in correctly identifying atrial fibrillation depends on clinical expertise, while the choice of smart device seems to have no impact.
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Fibrilación Atrial , Humanos , Fibrilación Atrial/diagnóstico , Estudios Prospectivos , Sensibilidad y Especificidad , ElectrocardiografíaRESUMEN
Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 â IOIO4 and (R2) IOIO4 + H2O â HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.
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Yodatos , Yodo , AerosolesRESUMEN
Retropatellar complications after total knee arthroplasty (TKA) such as anterior knee pain and subluxations might be related to altered patellofemoral biomechanics, in particular to trochlear design and femorotibial joint positioning. A method was developed to test femorotibial and patellofemoral joint modifications separately with 3D-rapid prototyped components for in vitro tests, but material differences may further influence results. This pilot study aims at validating the use of prostheses made of photopolymerized rapid prototype material (RPM) by measuring the sliding friction with a ring-on-disc setup as well as knee kinematics and retropatellar pressure on a knee rig. Cobalt-chromium alloy (standard prosthesis material, SPM) prostheses served as validation standard. Friction coefficients between these materials and polytetrafluoroethylene (PTFE) were additionally tested as this latter material is commonly used to protect pressure sensors in experiments. No statistical differences were found between friction coefficients of both materials to PTFE. UHMWPE shows higher friction coefficient at low axial loads for RPM, a difference that disappears at higher load. No measurable statistical differences were found in knee kinematics and retropatellar pressure distribution. This suggests that using polymer prototypes may be a valid alternative to original components for in vitro TKA studies and future investigations on knee biomechanics.