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49 result(s) for "Cazaunau, Mathieu"
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Complex refractive indices and single-scattering albedo of global dust aerosols in the shortwave spectrum and relationship to size and iron content
The optical properties of airborne mineral dust depend on its mineralogy, size distribution, and shape, and they might vary between different source regions. To date, large differences in refractive index values found in the literature have not been fully explained. In this paper we present a new dataset of complex refractive indices (m=n−ik) and single-scattering albedos (SSAs) for 19 mineral dust aerosols over the 370–950 nm range in dry conditions. Dust aerosols were generated from natural parent soils from eight source regions (northern Africa, Sahel, Middle East, eastern Asia, North and South America, southern Africa, and Australia). They were selected to represent the global-scale variability of the dust mineralogy. Dust was resuspended into a 4.2 m3 smog chamber where its spectral shortwave scattering (βsca) and absorption (βabs) coefficients, number size distribution, and bulk composition were measured. The complex refractive index was estimated by Mie calculations combining optical and size data, while the spectral SSA was directly retrieved from βsca and βabs measurements. Dust is assumed to be spherical in the whole data treatment, which introduces a potential source of uncertainty. Our results show that the imaginary part of the refractive index (k) and the SSA vary widely from sample to sample, with values for k in the range 0.0011 to 0.0088 at 370 nm, 0.0006 to 0.0048 at 520 nm, and 0.0003 to 0.0021 at 950 nm, as well as values for SSA in the range 0.70 to 0.96 at 370 nm, 0.85 to 0.98 at 520 nm, and 0.95 to 0.99 at 950 nm. In contrast, the real part of the refractive index (n) is mostly source (and wavelength) independent, with an average value between 1.48 and 1.55. The sample-to-sample variability in our dataset of k and SSA is mostly related to differences in the dust iron content. In particular, a wavelength-dependent linear relationship is found between the magnitude of k and SSA and the mass concentrations of both iron oxide and total elemental iron, with iron oxide better correlated than total elemental iron with both k and SSA. The value of k was found to be independent of size. When the iron oxide content exceeds 3 %, the SSA linearly decreases with an increasing fraction of coarse particles at short wavelengths (< 600 nm). Compared to the literature, our values for the real part of the refractive index and SSA are in line with past results, while we found lower values of k compared to most of the literature values currently used in climate models. We recommend that source-dependent values of the SW spectral refractive index and SSA be used in models and remote sensing retrievals instead of generic values. In particular, the close relationships found between k or SSA and the iron content in dust enable the establishment of predictive rules for spectrally resolved SW absorption based on particle composition
Global scale variability of the mineral dust long-wave refractive index: a new dataset of in situ measurements for climate modeling and remote sensing
Modeling the interaction of dust with long-wave (LW) radiation is still a challenge because of the scarcity of information on the complex refractive index of dust from different source regions. In particular, little is known about the variability of the refractive index as a function of the dust mineralogical composition, which depends on the specific emission source, and its size distribution, which is modified during transport. As a consequence, to date, climate models and remote sensing retrievals generally use a spatially invariant and time-constant value for the dust LW refractive index. In this paper, the variability of the mineral dust LW refractive index as a function of its mineralogical composition and size distribution is explored by in situ measurements in a large smog chamber. Mineral dust aerosols were generated from 19 natural soils from 8 regions: northern Africa, the Sahel, eastern Africa and the Middle East, eastern Asia, North and South America, southern Africa, and Australia. Soil samples were selected from a total of 137 available samples in order to represent the diversity of sources from arid and semi-arid areas worldwide and to account for the heterogeneity of the soil composition at the global scale. Aerosol samples generated from soils were re-suspended in the chamber, where their LW extinction spectra (3–15 µm), size distribution, and mineralogical composition were measured. The generated aerosol exhibits a realistic size distribution and mineralogy, including both the sub- and super-micron fractions, and represents in typical atmospheric proportions the main LW-active minerals, such as clays, quartz, and calcite. The complex refractive index of the aerosol is obtained by an optical inversion based upon the measured extinction spectrum and size distribution. Results from the present study show that the imaginary LW refractive index (k) of dust varies greatly both in magnitude and spectral shape from sample to sample, reflecting the differences in particle composition. In the 3–15 µm spectral range, k is between ∼ 0.001 and 0.92. The strength of the dust absorption at ∼ 7 and 11.4 µm depends on the amount of calcite within the samples, while the absorption between 8 and 14 µm is determined by the relative abundance of quartz and clays. The imaginary part (k) is observed to vary both from region to region and for varying sources within the same region. Conversely, for the real part (n), which is in the range 0.84–1.94, values are observed to agree for all dust samples across most of the spectrum within the error bars. This implies that while a constant n can be probably assumed for dust from different sources, a varying k should be used both at the global and the regional scale. A linear relationship between the magnitude of the imaginary refractive index at 7.0, 9.2, and 11.4 µm and the mass concentration of calcite and quartz absorbing at these wavelengths was found. We suggest that this may lead to predictive rules to estimate the LW refractive index of dust in specific bands based on an assumed or predicted mineralogical composition, or conversely, to estimate the dust composition from measurements of the LW extinction at specific wavebands. Based on the results of the present study, we recommend that climate models and remote sensing instruments operating at infrared wavelengths, such as IASI (infrared atmospheric sounder interferometer), use regionally dependent refractive indices rather than generic values. Our observations also suggest that the refractive index of dust in the LW does not change as a result of the loss of coarse particles by gravitational settling, so that constant values of n and k could be assumed close to sources and following transport. The whole dataset of the dust complex refractive indices presented in this paper is made available to the scientific community in the Supplement
Distinct chemical and mineralogical composition of Icelandic dust compared to northern African and Asian dust
Iceland is a highly active source of natural dust. Icelandic dust has the potential to directly affect the climate via dust–radiation interaction and indirectly via dust–cloud interaction, the snow/ice albedo effect and impacts on biogeochemical cycles. The impacts of Icelandic dust depend on its mineralogical and chemical composition. However, a lack of data has prevented an accurate assessment of the role of Icelandic dust in the Earth system. Here, we collected surface sediment samples from five major Icelandic dust hotspots. Dust aerosols were generated and suspended in atmospheric chambers, and PM10 and PM20 fractions were collected for further analysis. We found that the dust samples primarily consist of amorphous basaltic materials ranging from 8 wt % (from the Hagavatn hotspot) to 60 wt %–90 wt % (other hotspots). Samples had relatively high total Fe content (10 wt %–13 wt %). Sequential extraction of Fe to determine its chemical form shows that dithionite Fe (Fe oxides such as hematite and goethite) and ascorbate Fe (amorphous Fe) contribute respectively 1 %–6 % and 0.3 %–1.4 % to the total Fe in Icelandic dust. The magnetite fraction is 7 %–15 % of total Fe and 1 %–2 wt % of PM10, which is orders of magnitude higher than in mineral dust from northern Africa. Nevertheless, about 80 %–90% of the Fe is contained in pyroxene and amorphous glass. The initial Fe solubility (ammonium acetate extraction at pH 4.7) is from 0.08 % to 0.6 %, which is comparable to low-latitude dust such as that from northern Africa. The Fe solubility at low pH (i.e. pH 2) is significantly higher than typical low-latitude dust (up to 30 % at pH 2 after 72 h). Our results revealed the fundamental differences in composition and mineralogy of Icelandic dust from low-latitude dust. We attribute these differences to the low degree of chemical weathering, the basaltic composition of the parent sediments and glacial processes. Icelandic dust contributes to the atmospheric deposition of soluble Fe and can impact primary productivity in the North Atlantic Ocean. The distinct chemical and mineralogical composition, particularly the high magnetite content (1 wt %–2 wt %), indicates a potentially significant impact of Icelandic dust on the radiation balance in the subpolar and polar regions.
Spectral- and size-resolved mass absorption efficiency of mineral dust aerosols in the shortwave spectrum: a simulation chamber study
This paper presents new laboratory measurements of the mass absorption efficiency (MAE) between 375 and 850 nm for 12 individual samples of mineral dust from different source areas worldwide and in two size classes: PM10. 6 (mass fraction of particles of aerodynamic diameter lower than 10.6 µm) and PM2. 5 (mass fraction of particles of aerodynamic diameter lower than 2.5 µm). The experiments were performed in the CESAM simulation chamber using mineral dust generated from natural parent soils and included optical and gravimetric analyses. The results show that the MAE values are lower for the PM10. 6 mass fraction (range 37–135  ×  10−3 m2 g−1 at 375 nm) than for the PM2. 5 (range 95–711  ×  10−3 m2 g−1 at 375 nm) and decrease with increasing wavelength as λ−AAE, where the Ångström absorption exponent (AAE) averages between 3.3 and 3.5, regardless of size. The size independence of AAE suggests that, for a given size distribution, the dust composition did not vary with size for this set of samples. Because of its high atmospheric concentration, light absorption by mineral dust can be competitive with black and brown carbon even during atmospheric transport over heavy polluted regions, when dust concentrations are significantly lower than at emission. The AAE values of mineral dust are higher than for black carbon (∼ 1) but in the same range as light-absorbing organic (brown) carbon. As a result, depending on the environment, there can be some ambiguity in apportioning the aerosol absorption optical depth (AAOD) based on spectral dependence, which is relevant to the development of remote sensing of light-absorbing aerosols and their assimilation in climate models. We suggest that the sample-to-sample variability in our dataset of MAE values is related to regional differences in the mineralogical composition of the parent soils. Particularly in the PM2. 5 fraction, we found a strong linear correlation between the dust light-absorption properties and elemental iron rather than the iron oxide fraction, which could ease the application and the validation of climate models that now start to include the representation of the dust composition, as well as for remote sensing of dust absorption in the UV–vis spectral region.
Diurnal fluxes of HONO above a crop rotation
Nitrous acid (HONO) fluxes were measured above an agricultural field site near Paris during different seasons. Above bare soil, different crops were measured using the aerodynamic gradient (AG) method. Two LOPAPs (LOng Path Absorption Photometer) were used to determine the HONO gradients between two heights. During daytime mainly positive HONO fluxes were observed, which showed strong correlation with the product of the NO2 concentration and the long wavelength UV light intensity, expressed by the photolysis frequency J(NO2). These results are consistent with HONO formation by photosensitized heterogeneous conversion of NO2 on soil surfaces as observed in recent laboratory studies. An additional influence of the soil temperature on the HONO flux can be explained by the temperature-dependent HONO adsorption on the soil surface. A parameterization of the HONO flux at this location with NO2 concentration, J(NO2), soil temperature and humidity fits reasonably well all flux observations at this location.
Infrared optical signature reveals the source–dependency and along–transport evolution of dust mineralogy as shown by laboratory study
Advancing knowledge of the mineralogical composition of dust is key for understanding and predicting its climate and environmental impacts. The variability of dust mineralogy from one source to another and its evolution during atmospheric transport is not measured at large scale. In this study we use laboratory measurements to demonstrate that the extinction signature of suspended dust aerosols in the 740 − 1250 cm −1 atmospheric window can be used to derive dust mineralogy in terms of the main infrared − active minerals, namely quartz, clays, feldspars and calcite. Various spectral signatures in dust extinction enable to distinguish between multiple global sources with changing composition, whereas modifications of the dust extinction spectra with time inform on size − dependent particles mineralogy changes during transport. The present study confirms that spectral and hyperspectral infrared remote sensing observations offer great potential for elucidating the size − segregated mineralogy of airborne dust at regional and global scales.
Murine in utero exposure to simulated complex urban air pollution disturbs offspring gut maturation and microbiota during intestinal suckling-to-weaning transition in a sex-dependent manner
Background Emerging data indicate that prenatal exposure to air pollution may lead to higher susceptibility to several non-communicable diseases. Limited research has been conducted due to difficulties in modelling realistic air pollution exposure. In this study, pregnant mice were exposed from gestational day 10–17 to an atmosphere representative of a 2017 pollution event in Beijing, China. Intestinal homeostasis and microbiota were assessed in both male and female offspring during the suckling-to-weaning transition. Results Sex-specific differences were observed in progeny of gestationally-exposed mice. In utero exposed males exhibited decreased villus and crypt length, vacuolation abnormalities, and lower levels of tight junction protein ZO-1 in ileum. They showed an upregulation of absorptive cell markers and a downregulation of neonatal markers in colon. Cecum of in utero exposed male mice also presented a deeply unbalanced inflammatory pattern. By contrast, in utero exposed female mice displayed less severe intestinal alterations, but included dysregulated expression of Lgr5 in colon, Tjp1 in cecum, and Epcam , Car2 and Sis in ileum. Moreover, exposed female mice showed dysbiosis characterized by a decreased weighted UniFrac β -diversity index, a higher abundance of Bacteroidales and Coriobacteriales orders, and a reduced Firmicutes/Bacteroidetes ratio. Conclusion Prenatal realistic modelling of an urban air pollution event induced sex-specific precocious alterations of structural and immune intestinal development in mice.
Measurements of nitrous acid (HONO) in urban area of Shanghai, China
Nitrous acid (HONO), as a precursor of the hydroxyl radical (OH), plays an important role in the photochemistry of the troposphere, especially in the polluted urban atmosphere. A field campaign was conducted to measure atmospheric HONO concentration and that of other pollutants (such as NO₂ and particle mass concentration) in the autumn of 2009 at Shanghai urban areas. HONO mixing ratios were simultaneously measured by three different techniques: long path absorption photometer (LOPAP), differential optical absorption spectroscopy (DOAS) and chemical ionization mass spectrometer (CIMS). The measurements showed that the mixing ratios of HONO were highly variable and depended strongly on meteorological parameters. The HONO levels ranged from 0.5 to 7 ppb with maximum values during early morning and minimum levels during late afternoon. The three instruments reproduced consistent diurnal pattern of HONO concentrations with higher concentration during the night compared to the daylight hours. Comparison of HONOLOPAP/HONOCIMS ratios during daytime and nighttime periods exhibited a non-systematic disagreement of 0.93 and 1.16, respectively. This would indicate different chemical compositions of sampled air for the LOPAP and the CIMS instruments during daytime and nighttime periods, which have possibly affected measurements. Mean HONO concentration reported by LOPAP was 33 % higher than by DOAS on the whole period with no significant difference between daytime and nighttime periods. This revealed a systematic deviation from both instruments. The present data provides complementary information of HONO ambient levels in the atmosphere of Shanghai urban areas.
Highly oxygenated molecules formation from the oxidation of α- and β-phellandrenes by NO.sub.3 radicals
Nighttime NO.sub.3 -initiated oxidation of monoterpenes plays a crucial role as source of organic nitrates (ONs) and secondary organic aerosol (SOA), impacting climate, air quality, and human health. Nevertheless, monoterpene reactions with NO.sub.3 remain poorly understood. This study provides an in-depth investigation of the NO.sub.3 -initiated oxidation of α- and β-phellandrenes through simulation chamber experiments and a combination of various analytical techniques (FTIR, PTR-ToF-MS, ACSM, nitrate-CI-APi-ToF-MS, Orbitrap, SMPS). SOA yields were measured, and oxidation products, including highly oxygenated organic molecules (HOMs), were investigated in gas and aerosol phases. Numerical simulations were also performed to investigate the dominant chemical regimes for RO.sub.2 radicals. We found that α- and β-phellandrenes are efficient SOA precursors with yields reaching up to 35 % and 60 %, respectively, with β-phellandrene generating significantly more SOA than α-phellandrene. Both monoterpenes produce large quantities of ONs in gas and aerosol phases with total molar yields of 40 %-60 %. Similar gas-phase products were detected for α- and β-phellandrenes. In particular, carbonyl nitrates, dicarbonyl nitrates, and dicarbonyls were detected as first-generation products. Autooxidation processes were also shown to occur with numerous gas-phase HOM monomers and dimers detected. Chemical mechanisms have been proposed to explain the formation of the detected products. Since gas-phase products were similar for both monoterpenes, they do not explain the differences in SOA yields. However, some differences in aerosol-phase composition were observed, which may explain why β-phellandrene is a more efficient SOA precursor. This study is the first mechanistic investigation of the reactions of α- and β-phellandrenes with the NO.sub.3 radical.
Highly oxygenated molecules (HOMs) and secondary organic aerosol (SOA) formation from the oxidation of α - and β -phellandrenes by NO 3 radicals
Nighttime NO3-initiated oxidation of monoterpenes plays a crucial role as source of organic nitrates (ONs) and secondary organic aerosol (SOA), impacting climate, air quality, and human health. Nevertheless, monoterpene reactions with NO3 remain poorly understood. This study provides an in-depth investigation of the NO3-initiated oxidation of α- and β-phellandrenes through simulation chamber experiments and a combination of various analytical techniques (FTIR, PTR-ToF-MS, ACSM, nitrate-CI-APi-ToF-MS, Orbitrap, SMPS). SOA yields were measured, and oxidation products, including highly oxygenated organic molecules (HOMs), were investigated in gas and aerosol phases. Numerical simulations were also performed to investigate the dominant chemical regimes for RO2 radicals. We found that α- and β-phellandrenes are efficient SOA precursors with yields reaching up to 35 % and 60 %, respectively, with β-phellandrene generating significantly more SOA than α-phellandrene. Both monoterpenes produce large quantities of ONs in gas and aerosol phases with total molar yields of 40 %–60 %. Similar gas-phase products were detected for α- and β-phellandrenes. In particular, carbonyl nitrates, dicarbonyl nitrates, and dicarbonyls were detected as first-generation products. Autooxidation processes were also shown to occur with numerous gas-phase HOM monomers and dimers detected. Chemical mechanisms have been proposed to explain the formation of the detected products. Since gas-phase products were similar for both monoterpenes, they do not explain the differences in SOA yields. However, some differences in aerosol-phase composition were observed, which may explain why β-phellandrene is a more efficient SOA precursor. This study is the first mechanistic investigation of the reactions of α- and β-phellandrenes with the NO3 radical.