Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. 2. Time Evolution and Effect of Particle Acidity.

The present work is an extensive laboratory study of organosulfate (OS) formation from the reaction of α-pinene oxidation products or proxies with acidified ammonium sulfate aerosols in three different acidity conditions ((NH4)2SO4 0.06 M; (NH4)2SO4/H2SO4 0.06 M/0.005 M; (NH4)2SO4/H2SO4 0.03 M/0.05 M). The kinetics of the reactions of α-pinene, α-pinene oxide, isopinocampheol, pinanediol, and myrtenal with ammonium sulfate particles were studied using a quasi-static reactor. The reaction of α-pinene oxide with the highly acidic ammonium sulfate particles was determined to be 7, 10, 21, and 24 times faster than for isopinocampheol, α-pinene, pinanedial, and myrtenal, respectively, for an OS precursor concentration of 1 ppm and after 1 h reaction time. The effective rate coefficients for OS formation from α-pinene oxide were determined to be 2 orders of magnitude higher in highly acidic conditions than for the two other acidity conditions. For α-pinene oxide reactions with highly acidic ammonium sulfate particles, OS formation was observed to increase linearly with (i) the time of reaction up to 400 min (r2 > 0.95) and (ii) α-pinene oxide gas-phase concentration. However, OS formation from α-pinene oxide reactions with slightly acidic or pure ammonium sulfate particles was limited, with a plateau ([OS]max = 0.62 ± 0.03 µg) reached after around 15-20 min. Organosulfate dimers (m/z 401 and m/z 481) were detected not only with highly acidic particles but also with slightly acidic and pure ammonium sulfate particles, indicating that oligomerization processes do not require strong acidity conditions. Dehydration products of organosulfates (m/z 231 and m/z 383) were observed only under highly acidic conditions, indicating the key role of H2SO4 on the dehydration of organosulfates and the formation of olefins in the atmosphere. Finally, this kinetic study was completed with simulation chamber experiments in which the mass concentration of organosulfates was shown to depend on the available sulfate amount present in the particle phase (r2 = 0.96). In conclusion, this relative comparison between five organosulfate precursors shows that epoxide was the most efficient reactant to form organosulfates via heterogeneous gas-particle reactions and illustrates how gas-particle reactions may play an important role in OS formation and hence in the atmospheric fate of organic carbon. The kinetic data presented in this work provide strong support to organosulfate formation mechanisms proposed in part 1 ( J. Phys. Chem. A 2016 , 120 , 7909 - 7923 ).

Observation of nighttime new particle formation over the French Landes forest.

Improving the understanding of processes related to atmospheric particle sources is essential to better assess future climate. Especially, how biogenic volatile organic compounds (BVOCs) are involved in new particle formation (NPF) is still unclear, highlighting the need for field studies in sites that have not yet been explored. Weakly anthropised, mostly composed of maritime pines (known as strong monoterpene emitters), vast and under the influence of sea spray inputs, the Landes forest (located in the southwestern part of France) is a suitable ecosystem to explore these questions. The aim of the present work was to investigate for the first time NPF in the Landes forest, and to identify the conditions for NPF. During a field campaign conducted in July 2015, clear NPF was observed during nighttime, at a high frequency rate (37.5%), whereas only two daytime episodes were observed. Growth rates during NPF events were in the range 9.0-15.7nmh-1, and nucleation rates (J10) in the range 0.8-8 particles cm3s-1, typically in the range of reported values from rural sites. Nocturnal NPF started at sunset, lagging the reductions of temperature and ozone concentration as well as the increase of relative humidity, atmospheric stability and monoterpene concentration. We established that NPF occurred during more stratified atmosphere episodes, reflecting that NPF is more influenced by local processes at the Landes forest site (Bilos). Concentration of the sum of monoterpenes, here mainly α- and ß-pinene, was observed to be maximal during NPF episodes. On the contrary, ozone concentration was lower, which may indicate a larger consumption during nights where NPF episodes occur. Results strongly suggest the contribution of BVOC oxidation to nocturnal NPF, in both nucleation and the growth stages.

Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. Part I: Product Identification, Formation Mechanisms and Effect of Relative Humidity.

In the present study, quasi-static reactor and atmospheric simulation chamber experiments were performed to investigate the formation of α-pinene-derived organosulfates. Organosulfates (R-OSO3H) were examined for the reactions between acidified ammonium sulfate particles exposed to an individual gaseous volatile organic compound, such as α-pinene and oxidized products (α-pinene oxide, isopinocampheol, pinanediol and myrtenal). Molecular structures were elucidated by liquid chromatography interfaced to high-resolution quadrupole time-of-flight mass spectrometry equipped with electrospray ionization (LC/ESI-HR-QTOFMS). New organosulfate products were detected and identified for the first time in the present study. Reaction with α-pinene oxide was found to be a favored pathway for organosulfate formation (C10H18O5S) and to yield organosulfate dimers (C20H34O6S and C20H34O9S2) and trimers (C30H50O10S2) under dry conditions (RH < 1%) and high particle acidity and precursor concentrations (1 ppm). The role of relative humidity on organosulfate formation yields and product distribution was specifically examined. Organosulfate concentrations were found to decrease with increasing relative humidity. Mechanistic pathways for organosulfate formation from the reactions between α-pinene, α-pinene oxide, isopinocampheol, or pinanediol with acidified ammonium sulfate particles are proposed.

Implementing boundary conditions in simulations of arterial flows.

Computational hemodynamic models of the cardiovascular system are often limited to finite segments of the system and therefore need well-controlled inlet and outlet boundary conditions. Classical boundary conditions are measured total pressure or flow rate imposed at the inlet and impedances of RLR, RLC, or LR filters at the outlet. We present a new approach based on an unidirectional propagative approach (UPA) to model the inlet/outlet boundary conditions on the axisymmetric Navier-Stokes equations. This condition is equivalent to a nonreflecting boundary condition in a fluid-structure interaction model of an axisymmetric artery. First we compare the UPA to the best impedance filter (RLC). Second, we apply this approach to a physiological situation, i.e., the presence of a stented segment into a coronary artery. In that case a reflection index is defined which quantifies the amount of pressure waves reflected upon the singularity.

[Digital simulation of venous and lymphatic edema and the effects of compression]. / Simulation numérique de l'œdème veinolymphatique et des effets de la compression.

OBJECTIVE: Compression therapy for venous and lymphatic edema of the lower limbs raises a major challenge concerning the optimal pressure ensuring both efficacy and patient compliance. We present a mathematical model of tissue fluid transfers which is aimed at determining the lowest pressure required to prevent edema. METHODS: The model is based on a set of equations, derived from published experimental data, which describe the fluid and solute transfers between blood, interstitium and lymphatics, and the mechanical properties of interstitial compartment. It enables us to compute the changes in tissue volume, at the ankle level, resulting from increases of capillary pressure in case of venous insufficiency, and from an impairment of lymph drainage; as well as the effect of various external pressures upon this volume. RESULTS: An increase of capillary pressure to 40 and 50 mmHg results in an ankle edema which is completely prevented by an external pressure of 10 mmHg. This result is in keeping with the observation by Partsch that vesperal leg swelling is reduced by low compression stockings. The dose effect reported in this study is also found by simulation. The complete blockade of lymphatic return leads to an edema, the prevention of which requires a counterpressure of at least 30 mmHg. When an increase of venous pressure to 60 mmHg, and a reduction by 2/3 of lymphatic drainage are combined, simulating chronic venous insufficiency, the resulting edema is prevented by a 25 mmHg counterpressure. CONCLUSION: These first results of simulation are in reasonable agreement with clinical experience. As nearly every combination of disturbances may be simulated, the computer model could help to understand and treat edemas, as long as their cause can be identified.

Mechanical properties of rat thoracic and abdominal aortas.

Mechanical properties of abdominal and thoracic arteries of 2mm in diameter were determined from adults Wistar rats. A tensile testing instrument was used to obtain stress/strain curves with arteries immersed in physiological buffer at 37 degrees C. A displacement was applied on all arteries with various frequencies (1-7.5Hz) and strains (5-60%). From each curve a Young modulus was obtained using a mathematical model based on a nonlinear soft tissue model. No influence of frequency on modulus was evidenced in the tested range. Abdominal aortas, which were found slightly thicker than thoracic aortas, were characterized by a higher modulus. Due to the interest of decellularized biological materials, we also used SDS/Triton treated arteries, and found that the chemical treatment increased modulus of thoracic arteries. Tensile tests were also performed on thoracic aortas in the longitudinal and transversal directions. Longitudinal moduli were found higher than transversal moduli and the difference could be related to the longitudinal orientation of collagen fibers. These data and mathematical model seem useful in the design of new vascular synthetic or biological prostheses for the field of tissue engineering.

Validity of the local nonlinear arterial flow theory: influence of the upstream and downstream conditions.

The "local flow" theory provides a simple way to take into account the nonlinear convective terms associated with blood flow in large arteries. The assumption that blood velocity profiles vary slowly with the longitudinal coordinate allows a simple nonlinear resolution via a mathematical approximation. Although validated in vitro by its authors, this theory still needs to be verified in accordance with the range of variation of the hemodynamical parameters. This constitutes the aim of this work where we assess the validity of two models issued from this theory: the "direct model" using the pressure-gradient as an input for the calculations and the "indirect model" using the centre-line velocity. The assessment of these models is made by comparing their solutions to those of the linear theory using numerical simulations. Our main conclusion is that the indirect model has a wide range of validity while the direct one fails in the presence of a strong reflected wave.

Incoherent light transport in an anisotropic random medium: a probe of human erythrocyte aggregation and deformation.

This paper investigates the flow induced disaggregation, deformation and orientation of several modified human red blood cells suspended in concentrated, physiological like conditions (volume fraction in erythrocytes of 0.4). The aim is to determine simultaneously, and under flow, the aggregate sizes as well as the deformation and orientation of the cells. The measurement method uses steady, incoherent, unpolarized light transport while the sample is sheared in a flow cell controlled by a rheometer. Several blood samples were prepared to alter the erythrocyte's aggregating, deformability and shape properties. The measurements using these samples show a clear relationship between the intrinsic properties of the cells and the evolution of aggregate sizes, average cell orientation and anisotropy as a function of the applied shear, which may lead to clinical applications. In other words, the careful analysis of the incoherent light transport in concentrated media provides quantitative insight into their microscopic details. In particular, the topological properties (average anisotropy and orientation) and size of the suspended objects can be determined.

Intramuscular pressure and surface EMG in voluntary ankle dorsal flexion: Influence of elastic compressive stockings.

Intramuscular pressure (IMP) is of major importance in blood flow and is often taken as a good estimate of muscular tension. However, its measurement remains invasive. The aims of the present work were: (1) to re-examine the possibility of evaluating IMP and muscular tension changes by means of surface electromyographic recordings, and (2) to clarify the influence of elastic compressive stockings (ECS). Surface EMG of muscles tibialis anterior (TA), soleus, gastrocnemius, and IMP from the anterior tibial compartment (ATC), deep posterior compartment (DPC), superficial posterior compartment (SPC) of the right leg, were simultaneously recorded in nine healthy subjects. Subjects performed series of voluntary concentric TA contractions (right ankle dorsal flexions) and TA isometric contractions, with or without elastic ECS, in a decubitus posture. Rest IMP mean values, measured over 60 s, ranged between 12.3 and 26.6 mmHg, i.e. in the range or slightly higher than those reported in the literature. When ECS were applied, mean IMP increase was 6.4 mmHg in ATC, 8.7 mmHg in DPC and 21.0 mmHg in SPC, while the corresponding EMG amplitude decreased. In ankle dorsal flexion movements, instantaneous values of TA-EMG amplitudes were linearly correlated to ATC-IMP instantaneous values, over the whole of the EMG rising part of every movement. When ECS were applied, the relationships between TA-EMG amplitude and ATC-IMP amplitude remained linear but where shifted towards higher IMP, in agreement with the increase in rest IMP. Because of antagonist co-contractions, IMP from DPC and SPC were also linearly correlated with ATC-IMP but with low coefficients of proportionality. As in TA concentric contractions, TA-EMG amplitudes were linearly correlated to ATC-IMP instantaneous values in isometric contractions, but the slopes of the latter were always greater. This result is explained by the relationship between muscle tension and shortening velocity. Al the results showed that: (1) instantaneous changes in surface EMG amplitude may provide a good estimate of IMP changes during the rising part of isometric, but also of concentric voluntary contractions; (2) elastic compressive stockings do not impair subjects relaxation capacity but actually increase the ratio IMP/muscle activation. As a consequence, ECS may actually increase the venous return during voluntary contractions.

Infrared line collisional parameters of HCl in argon, beyond the impact approximation: measurements and classical path calculations.

Measurement of room temperature absorption by HCl-Ar mixtures in the 1-0 and 2-0 bands have been made for pressures between 10 and 50 atm. Fits of these spectra are made for the determination of the width, spectral shift, asymmetry, and intensity of individual lines. The broadening and shifting parameters are in satisfactory agreement with previous determinations but provide the first complete and self-consistent sets covering P(15)-R(14) and P(7)-R(8) in the 1-0 and 2-0 bands, respectively. The asymmetries of the profiles, which have been studied for the first time, are smaller than typically 10(-3) atm(-1) and cannot be determined experimentally. On the other hand, the intensities of the low j lines show a significant linear decrease with increasing Ar pressure. Calculations of all measured quantities are made with a classical path approach and an accurate vibrational-dependent HCl-Ar potential energy surface (PES). Comparisons with experimental values show that widths and shifts are well predicted, confirming the quality of the PES and of the theoretical model, and the calculations confirm that asymmetries are small. The damping factors of the intensities are analyzed by considering three contributions: The first is due to the formation of van der Waals complexes, the second results from the finite duration of collisions, and the last comes from initial correlations. Calculations indicate that the last process has negligible consequences but that the first two processes lead to effects of the same order and explain most of the observed decrease of the intensities, even if some discrepancies persist for the mid R:mmid R:=1 rotational components.

Experimental and theoretical study of line mixing in NH3 spectra. II. Effect of the perturber in infrared parallel bands.

In a previous paper [J. Chem. Phys. 116, 7544 (2002) (Paper I)] a model, based on the energy corrected sudden approximation, was proposed for the construction of the line-mixing relaxation matrix. It was successfully tested by comparisons with measured infrared spectra of ammonia-helium mixtures. The present paper extends this preliminary study by considering mixtures of NH3 with H2 and Ar. Measurements have been made at room temperature in the regions of the nu2 and nu1 bands for pressures up to several hundred atmospheres. As in Paper I, the relaxation operator is constructed, within the impact approximation, using the ECS approximation. The data required are dynamical factors (which can be predicted from the NH3-X potential energy surface) and a scaling length (adjusted using line broadening data). Comparisons between measured and calculated absorptions demonstrate the quality of the model which satisfactory corrects for the large deviations with respect to the purely Lorentzian behavior. Line-mixing effects for NH3-Ar and NH3-H2 are qualitatively similar to those observed for NH3-He but quantitative differences exist, particularly when intra- and interbranch couplings are considered. Finally, the proposed model leads to very satisfactory results in the wings of both the purely rotational and nu2 bands of NH3 diluted in H2, opening promising perspectives for the remote sensing study of planetary atmospheres.

Experimental evidence of a potentially increased thrombo-embolic disease risk by domestic electromagnetic field exposure.

We have used the EaHy926 endothelial cell line, able to secrete both pro and anti-aggregant platelet agents, as a model for thrombo-embolic diseases. We experimentally established, by comparing these two secretions with or without a Faraday cage, that the environmental electromagnetic field significantly increases the thrombo-embolic risks in this endothelial cell line.

A digital model for the venous junctions.

The venous network in the lower limbs is composed of a considerable number of confluent junctions. Each of these singularities introduces some blood flow disturbances. Each physiological junction is unique, in terms of its geometry as well as the blood flow rate. In order to account for this great variability, we developed a numerical model based on the use of the N3S code (a software package for solving Navier-Stokes equations). To test the validity of the model, one of the numerical simulations is compared with the data obtained in the corresponding experimental configuration. The velocity measurements were carried out with an ultrasonic pulsed Doppler velocimeter. We also measured pressure differences using differential sensors. The numerical computations were then used to obtain the values of the flow variables at any point, with various geometrical and flow configurations. As far as the velocity field is concerned, a very marked three-dimensional pattern with swirls was observed. The pressure evolution was also strongly disturbed, with a non-linear decrease. All these data indicate that confluence effects cannot be neglected when evaluating pressure decreases. With a tool of this kind, it is possible to accurately predict the disturbances associated with any geometrical configuration or any flow rate.

Non-linear analysis of the arterial pulsatile flow: assessment of a model allowing a non-invasive ultrasonic functional exploration.

Ultrasonic measurements and modelling of blood flow in large vessels allows non-invasive evaluation of clinically interesting hemodynamic variables. To this aim, a non-linear mathematical model for the pulsatile arterial flow is proposed using the approximation of "local flow" theory. The model requires only measurements of instantaneous radius and centre-line blood velocity, and the knowledge of the tube distensibility to calculate blood velocity profiles, pressure gradient and wall shear stress. Evaluation of the proposed model using experimental data obtained from the literature proved that it can provide reliable results. In addition, as shown by assessing significance of various non-linear terms, results did not significantly change when a linear pressure-radius relationship was used instead of a non-linear relationship. Also, the model was found to be moderately sensitive to arterial tapering. Thus, the proposed model is suitable for a non-invasive clinical arterial exploration since it only requires three measurements which can be easily and precisely obtained in vivo using ultrasonic methods: the instantaneous radius, the centre-line velocity and the mean pulse wave velocity, this last variable characterizing the tube distensibility when assuming a linear pressure-radius relationship.

Modeling of the deformation of flexible tubes using a single law: application to veins of the lower limb in man.

The topic of this study mainly concerns a representative model of the behavior of flexible ducts such as elastic tubes or veins. This model is based on a phenomenological approach of the inflation and collapse of the tube. It leads to a single "universal" analytical expression of the tube law, valid fir a wide range of' positive and negative transmural pressures, which presents a significant improvement compared to previous theoretical studies defined with different expressions on restricted ranges of pressure. Moreover, the theoretical approaches most often require simplif'ing hypotheses--no longitudinal tension, no surrounding tissues--which are quite unrealistic both in the physiological case and in the experimental setup. These theoretical models can therefore be expected only roughly to describe the actual behavior of such vessels. The representative model, on the contrary, allows one to account for the deformation--inflating as well as collapse--of elastic tubes or veins with better accuracy. The tube law is a function of six parameters chosen in order to fit the experimental data. A comparison between results obtained in our laboratory using silicone tubes and representative models is presented. The model is then applied to physiological data obtained in vivo on human leg veins.

Hemorheology in asymptomatic HIV-infected patients.

Although cardiac and vascular complications have been recognized among patients infected with the Human Immunodeficiency Virus-1 (HIV-1), their vascular biology and rheology have not been studied. Rheology of red blood cells (RBC) was assessed with an erythroaggregometer in 22 HIV-1 infected asymptomatic patients (pts) and 17 healthy HIV negative controls (C). All participants were normotensive, nondiabetics, had normal lipid levels and had an hematocrit ranging from 37 to 44% and hemoglobin levels > or = 12 g/100 ml. Patients had a shorter RBC aggregation characteristic time than controls (1.49 +/- 0.17 vs. 2.04 +/- 0.41 s, p = 0.001) and an increased disaggregation shear rate (166 +/- 34.9 vs. 122 +/- 25.4 s(-1), p = 0.001). This hyperaggregation tendancy was associated with increased gamma-globulin (18.3 +/- 3.3 vs. 13.7 +/- 1.9 g/l, p = 0.01) and fibrinogen (3.52 +/- 0.57 vs 3.03 +/- 0.48 g/l, p = 0.003) levels and with an increased erythrocyte sedimentation rate (ESR) (25 +/- 14.3 vs. 12.3 +/- 7.5 mm, p = 0.02). Even in patients with ESRs ranging within normal values (< or = 20 mm), the aggregation characteristic time was found lower in patients than in controls (p = 0.004). There was no correlation between these rheological changes and the CD4+ T-cell count. The 17 patients receiving an antiviral therapy had lower CD4+ T-cell counts than their 5 untreated counterparts (244.7 +/- 167 vs. 410 +/- 106/mm3, p = 0.025), and a higher disaggregation shear rate (177.4 +/- 38.2 vs. 127 +/- 25.4, p = 0.01). Thus, an impairment of rheological characteristics is observed in asymptomatic HIV-I infected patients in association with changes in plasma proteins.

Deconvolution process in measurement of arterial velocity profiles via an ultrasonic pulsed Doppler velocimeter for evaluation of the wall shear rate.

A numerically based simulation of pulsed Doppler ultrasound convolution and deconvolution of theoretical hemodynamic velocity profiles yields two major conclusions on performing a deconvolution process. First, the most important parameter to be accounted for is the size of the sample volume. Second, a deconvolution process with an overestimated sample volume size is revealed by high-frequency noise on the resulting profile. A deconvolution process is presented for in vivo arterial velocity profiles, which has the advantage of being systematic and not needing experimental testing for determining the size or the shape of the sample volume. It is also independent of the observation angle. Finally, an example of an application to in vivo human velocity profiles is given. Evaluation of the wall shear rate from the corrected deconvolved profiles shows a noticeable improvement with respect to that using the directly convolved Doppler profiles.