ALBERT

Description: This study was conducted to examine potentially differential effects of day and night warming on soil respiration in a temperate steppe in northern China. A full factorial design with day and night warming was used in this study, including control (C), day (6 a.m.–6 p.m., local time; D) warming, night (6 p.m.–6 a.m.; N) warming, and diurnal warming (W). Day warming showed neutral effect on soil respiration, whereas night warming significantly increased soil respiration by 7.1% over the first 3 growing seasons. The insignificant effect of day warming on soil respiration could be attributable to the offset of the direct positive effects by the indirect negative effects via aggravating water limitation and suppressing ecosystem C assimilation. The positive effects of night warming on soil respiration were largely due to the stimulation of ecosystem C uptake and substrate supply via over-compensation of plant photosynthesis. In addition, day and night warming showed antagonistic effects on soil respiration, which could be ascribed to their contrasting effects on ecosystem C assimilation. The results suggest differential and non-additive effects of day and night warming on soil respiration, which was driven by the treatment-induced changes in substrate supply.

Description: The magnitude of daily minimum temperature increase is greater than that of daily maximum temperature increase under climate warming. This study was conducted to examine whether changes in soil respiration under diurnal warming are equal to the summed changes under day and night warming in a temperate steppe in northern China. A full factorial design with day and night warming was used in this study, including control, day (06:00 a.m.–06:00 p.m., local time) warming, night (06:00 p.m.–06:00 a.m.) warming, and diurnal warming. Day warming showed no effect on soil respiration, whereas night warming significantly increased soil respiration by 7.1% over the 3 growing seasons in 2006–2008. The insignificant effect of day warming on soil respiration could be attributable to the offset of the direct positive effects of increased temperature by the indirect negative effects via aggravating water limitation and suppressing ecosystem C assimilation. The positive effects of night warming on soil respiration were largely due to the stimulation of ecosystem C uptake and substrate supply via overcompensation of plant photosynthesis. Changes in both soil respiration (+20.7 g C m−2 y−1) and GEP (−2.8 g C m−2 y−1) under diurnal warming are smaller than their summed changes (+40.0 and +24.6 g C m−2 y−1, respectively) under day and night warming. Our findings that the effects of diurnal warming on soil respiration and gross ecosystem productivity are not equal to the summed effects of day and night warming are critical for model simulation and projection of climate-carbon feedback.

Description: To understand and predict the role of mineral aerosol particles processed by reactive nitrogen species in the atmosphere, the hygroscopic properties of both Ca(NO3)2 and Ca(NO3)2-containing mineral particles must be well understood. Using a micro-Raman system, the dehydration and hydration processes of micro-sized individual Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles were investigated systematically. In addition to accurate quantification of the dependence of water content on relative humidity (RH), significant new spectroscopic evidence related to chemical structure was also obtained to confirm the occurrence of amorphous solid state and to better understand the phase transition process. The Ca(NO3)2 particles exhibit reversible behavior in the dehydration and hydration processes; they are in the state of solution droplets above 10% RH and amorphous hydrates below 7% RH, and phase transition occurs at 7–10% RH. The hygroscopic behavior of Ca(NO3)2/CaCO3 particles is identical to that of pure Ca(NO3)2 particles, suggesting a negligible effect of the inclusion of slightly soluble CaCO3.

Description: The influence is investigated of the assumed ice particle microphysical and optical model on inferring ice cloud optical thickness (τ) from satellite measurements of the Earth's reflected shortwave radiance. Ice cloud τ are inferred, and subsequently compared, using products from MODIS (MODerate resolution Imaging Spectroradiometer) and POLDER (POLarization and Directionality of the Earth's Reflectances). POLDER τ values are found to be substantially smaller than those from collocated MODIS data. It is shown that this difference is caused primarily by the use of different ice particle bulk scattering models in the two retrievals, and more specifically, the scattering phase function. Furthermore, the influence of the ice particle model on the derivation of ice cloud radiative forcing (CRF) from satellite retrievals is studied. Three sets of shortwave CRF are calculated using different combinations of the retrieval and associated ice particle models. It is shown that the uncertainty associated with an ice particle model may lead to two types of errors in estimating CRF from satellite retrievals. One stems from the retrieval itself and the other is due to the optical properties, such as the asymmetry factor, used for CRF calculations. Although a comparison of the CRFs reveals that these two types of errors tend to cancel each other, significant differences are still found between the three CRFs, which indicates that the ice particle model affects not only optical thickness retrievals but also CRF calculations. In addition to CRF, the effect of the ice particle model on the derivation of seasonal variation of τ from satellite measurements is discussed. It is shown that optical thickness retrievals based on the same MODIS observations, but derived using different assumptions of the ice particle model, can be substantially different. These differences can be divided into two parts. The first-order difference is mainly caused by the differences in the asymmetry factor. The second-order difference is related to seasonal changes in the sampled scattering angles and therefore dependent on the sun-satellite viewing geometry. Because of this second-order difference, the use of different ice particle models may lead to a different understanding of the seasonal variation of τ.

Description: Calcium nitrate (Ca(NO3)2) was observed in mineral dust and could change the hygroscopic and optical properties of mineral dust significantly due to its strong water solubility. The reaction of calcium carbonate (CaCO3) with nitric acid (HNO3) is believed the main reason for the observed Ca(NO3)2 in the mineral dust. In the atmosphere, the concentration of nitrogen dioxide (NO2) is orders of magnitude higher than that of HNO3; however, little is known about the reaction of NO2 with CaCO3. In this study, the heterogeneous reaction of NO2 on the surface of CaCO3 particles was investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) under wet and dry conditions. Nitrate formation was observed in both conditions, and nitrite was observed under wet conditions, indicating the reaction of NO2 on the CaCO3 surface produced nitrate and probably nitrous acid (HONO). Relative humidity (RH) influenced both the initial uptake coefficient and the reaction mechanism. With RH52%, a monolayer of water formed on the surface of the CaCO3 particles, which reacted with NO2 as a first order reaction, forming HNO3 and HONO. The initial uptake coefficient γ0 was determined to be (1.66±0.38)×10−7 under dry conditions and up to (0.84±0.44)×10−6 under wet conditions. Considering that NO2 concentrations in the atmosphere are orders of magnitude higher than those of HNO3, the reaction of NO2 on CaCO3 particle should have similar importance as that of HNO3 in the atmosphere and could also be an important source of HONO in the atmosphere.

Description: To understand and predict the role of mineral aerosol particles processed by reactive nitrogen species in the atmosphere, the hygroscopic properties of both Ca(NO3)2 and Ca(NO3)2-containing mineral particles must be well understood. Using a micro-Raman system, the hygroscopic behaviors of micro-sized individual Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles in both dehumidifying and humidifying processes were investigated systematically. In addition to accurate quantification of the dependence of water content on relative humidity (RH), significant new spectroscopic evidence related to chemical structure was also obtained to confirm the occurrence of amorphous solid state and to better understand the phase transition process. The Ca(NO3)2 particles exhibit reversible behavior in the dehumidifying and humidifying processes; they are in the state of solution droplets above 10% RH and amorphous hydrates below 7% RH, and phase transition occurs at 7–10% RH. The hygroscopic behavior of Ca(NO3)2/CaCO3 particles is identical to that of pure Ca(NO3)2 particles, suggesting a negligible effect of the slightly soluble CaCO3 inclusion on the hygroscopic behavior of a(NO3)2/CaCO3 particles.

Description: Daily PM2.5 (aerosol particles with an aerodynamic diameter of less than 2.5 μm) samples were collected at an urban site in Chengdu, an inland megacity in southwest China, during four 1-month periods in 2011, with each period in a different season. Samples were subject to chemical analysis for various chemical components ranging from major water-soluble ions, organic carbon (OC), element carbon (EC), trace elements to biomass burning tracers, anhydrosugar levoglucosan (LG), and mannosan (MN). Two models, the ISORROPIA II thermodynamic equilibrium model and the positive matrix factorization (PMF) model, were applied to explore the likely chemical forms of ionic constituents and to apportion sources for PM2.5. Distinctive seasonal patterns of PM2.5 and associated main chemical components were identified and could be explained by varying emission sources and meteorological conditions. PM2.5 showed a typical seasonality of waxing in winter and waning in summer, with an annual mean of 119 μg m−3. Mineral soil concentrations increased in spring, whereas biomass burning species elevated in autumn and winter. Six major source factors were identified to have contributed to PM2.5 using the PMF model. These were secondary inorganic aerosols, coal combustion, biomass burning, iron and steel manufacturing, Mo-related industries, and soil dust, and they contributed 37 ± 18, 20 ± 12, 11 ± 10, 11 ± 9, 11 ± 9, and 10 ± 12%, respectively, to PM2.5 masses on annual average, while exhibiting large seasonal variability. On annual average, the unknown emission sources that were not identified by the PMF model contributed 1 ± 11% to the measured PM2.5 mass. Various chemical tracers were used for validating PMF performance. Antimony (Sb) was suggested to be a suitable tracer of coal combustion in Chengdu. Results of LG and MN helped constrain the biomass burning sources, with wood burning dominating in winter and agricultural waste burning dominating in autumn. Excessive Fe (Ex-Fe), defined as the excessive portion in measured Fe that cannot be sustained by mineral dust, is corroborated to be a straightforward useful tracer of iron and steel manufacturing pollution. In Chengdu, Mo / Ni mass ratios were persistently higher than unity, and considerably distinct from those usually observed in ambient airs. V / Ni ratios averaged only 0.7. Results revealed that heavy oil fuel combustion should not be a vital anthropogenic source, and additional anthropogenic sources for Mo are yet to be identified. Overall, the emission sources identified in Chengdu could be dominated by local sources located in the vicinity of Sichuan, a result different from those found in Beijing and Shanghai, wherein cross-boundary transport is significant in contributing pronounced PM2.5. These results provided implications for PM2.5 control strategies.

Description: With increasing NO2 concentration in the troposphere, the importance of NO2 reaction with mineral dust in the atmosphere needs to be evaluated. Until now, little is known about the reaction of NO2 with CaCO3. In this study, the heterogeneous reaction of NO2 on the surface of CaCO3 particles was investigated at 296 K and NO2 concentrations between 4.58×1015 molecules cm−3 to 1.68×1016 molecules cm−3, using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), under wet and dry conditions. Nitrate formation was observed under both conditions, while nitrite was observed under wet conditions, indicating the reaction of NO2 on the CaCO3 surface produced nitrate and probably nitrous acid (HONO). Relative humidity (RH) influences both the initial uptake coefficient and the reaction mechanism. At low RH, surface −OH is formed through dissociation of the surface adsorbed water via oxygen vacancy, thus determining the reaction order. As RH increases, water starts to condense on the surface and the gas-liquid reaction of NO2 with the condensed water begins. With high enough RH (〉52% in our experiment), the gas-liquid reaction of NO2 with condensed water becomes dominant, forming HNO3 and HONO. The initial uptake coefficient γ0 was determined to be (4.25±1.18)×10−9 under dry conditions and up to (6.56±0.34)×10−8 under wet conditions. These results suggest that the reaction of NO2 on CaCO3 particle is unable to compete with that of HNO3 in the atmosphere. Further studies at lower NO2 concentrations and with a more accurate assessment of the surface area for calculating the uptake coefficient of the reaction of NO2 on CaCO3 particle and to examine its importance as a source of HONO in the atmosphere are needed.

Description: The influence is investigated of the assumed ice particle microphysical and optical model on inferring ice cloud optical thickness (τ) from satellite measurements of the Earth's reflected shortwave radiance. Ice cloud τ are inferred, and subsequently compared, using products from MODIS (MODerate resolution Imaging Spectroradiometer) and POLDER (POLarization and Directionality of the Earth's Reflectances). POLDER τ values are found to be substantially smaller than those from collocated MODIS data. It is shown that this difference is caused primarily by the use of different ice particle bulk scattering models in the two retrievals, and more specifically, the scattering phase function. Furthermore, the influence of the ice particle model on the derivation of ice cloud radiative forcing (CRF) from satellite retrievals is studied. Three sets of shortwave CRF are calculated using different combinations of the retrieval and associated ice particle models. It is shown that the uncertainty associated with an ice particle model may lead to two types of errors in estimating CRF from satellite retrievals. One stems from the retrieval itself and the other is due to the optical properties, such as the asymmetry factor, used for CRF calculations. Although a comparison of the CRFs reveals that these two types of errors tend to cancel each other, significant differences are still found between the three CRFs, which indicates that the ice particle model affects not only optical thickness retrievals but also CRF calculations. In addition to CRF, the effect of the ice particle model on the derivation of seasonal variation of τ from satellite measurements is discussed. It is shown that optical thickness retrievals based on the same MODIS observations, but derived using different assumptions of the ice particle model, can be substantially different. These differences can be divided into two parts. The first-order difference is mainly caused by the differences in the asymmetry factor. The second-order difference is related to seasonal changes in the sampled scattering angles and therefore dependent on the sun-satellite viewing geometry. Because of this second-order difference, the use of different ice particle models may lead to a different understanding of the seasonal variation of τ.

Description: Isoprene epoxydiol (IEPOX) isomers are key gas-phase intermediates of isoprene atmospheric oxidation. Secondary organic aerosols derived from such intermediates have important impacts on air quality and health. We report here convergent and unambiguous pathways developed for the synthesis of isomeric IEPOX species and the rearrangement products cis- and trans-3-methyl-3,4-dihydroxytetrahydrofuran in good yield. The availability of such compounds is necessary to expedite research on isoprene atmospheric oxidation mechanisms and subsequent aerosol formation as well as the toxicological properties of the aerosols.