Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Assessment of the consistency of H2O line intensities over the near-infrared using sun-pointing ground-based Fourier transform spectroscopy

We report on the consistency of water vapour line intensities in selected spectral regions between 800–12,000 cm−1 under atmospheric conditions using sun-pointing Fourier transform infrared spectroscopy. Measurements were made across a number of days at both a low and high altitude field site, sampling a relatively moist and relatively dry atmosphere. Our data suggests that across most of the 800–12,000 cm−1 spectral region water vapour line intensities in recent spectral line databases are generally consistent with what was observed. However, we find that HITRAN-2008 water vapour line intensities are systematically lower by up to 20% in the 8000–9200 cm−1 spectral interval relative to other spectral regions. This discrepancy is essentially removed when two new linelists (UCL08, a compilation of linelists and ab-initio calculations, and one based on recent laboratory measurements by Oudot et al. (2010) [10] in the 8000–9200 cm−1 spectral region) are used. This strongly suggests that the H2O line strengths in the HITRAN-2008 database are indeed underestimated in this spectral region and in need of revision. The calculated global-mean clear-sky absorption of solar radiation is increased by about 0.3 W m−2 when using either the UCL08 or Oudot line parameters in the 8000–9200 cm−1 region, instead of HITRAN-2008. We also found that the effect of isotopic fractionation of HDO is evident in the 2500–2900 cm−1 region in the observations.

The variability of tropical ice cloud properties as a function of the large-scale context from ground-based radar-lidar observations over Darwin, Australia

The high complexity of cloud parameterizations now held in models puts more pressure on observational studies to provide useful means to evaluate them. One approach to the problem put forth in the modelling community is to evaluate under what atmospheric conditions the parameterizations fail to simulate the cloud properties and under what conditions they do a good job. It is the ambition of this paper to characterize the variability of the statistical properties of tropical ice clouds in different tropical "regimes" recently identified in the literature to aid the development of better process-oriented parameterizations in models. For this purpose, the statistical properties of non-precipitating tropical ice clouds over Darwin, Australia are characterized using ground-based radar-lidar observations from the Atmospheric Radiation Measurement (ARM) Program. The ice cloud properties analysed are the frequency of ice cloud occurrence, the morphological properties (cloud top height and thickness), and the microphysical and radiative properties (ice water content, visible extinction, effective radius, and total concentration). The variability of these tropical ice cloud properties is then studied as a function of the large-scale cloud regimes derived from the International Satellite Cloud Climatology Project (ISCCP), the amplitude and phase of the Madden-Julian Oscillation (MJO), and the large-scale atmospheric regime as derived from a long-term record of radiosonde observations over Darwin. The vertical variability of ice cloud occurrence and microphysical properties is largest in all regimes (1.5 order of magnitude for ice water content and extinction, a factor 3 in effective radius, and three orders of magnitude in concentration, typically). 98 % of ice clouds in our dataset are characterized by either a small cloud fraction (smaller than 0.3) or a very large cloud fraction (larger than 0.9). In the ice part of the troposphere three distinct layers characterized by different statistically-dominant microphysical processes are identified. The variability of the ice cloud properties as a function of the large-scale atmospheric regime, cloud regime, and MJO phase is large, producing mean differences of up to a factor 8 in the frequency of ice cloud occurrence between large-scale atmospheric regimes and mean differences of a factor 2 typically in all microphysical properties. Finally, the diurnal cycle of the frequency of occurrence of ice clouds is also very different between regimes and MJO phases, with diurnal amplitudes of the vertically-integrated frequency of ice cloud occurrence ranging from as low as 0.2 (weak diurnal amplitude) to values in excess of 2.0 (very large diurnal amplitude). Modellers should now use these results to check if their model cloud parameterizations are capable of translating a given atmospheric forcing into the correct statistical ice cloud properties.

Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements

For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called ‘windows’) was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H2O−H2O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H2O−N2 bimolecular absorption in the Earth's atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430 K in four near-infrared windows between 1.1 and 5 μm (9000–2000 cm−1). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46 W m−2 (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer–Tobin–Clough–Kneizys–Davies) foreign-continuum model.

Near-infrared water vapour self-continuum at close to room temperature

The gaseous absorption of solar radiation within near-infrared atmospheric windows in the Earth's atmosphere is dominated by the water vapour continuum. Recent measurements by Baranov et al. (2011) [17] in 2500 cm−1 (4 μm) window and by Ptashnik et al. (2011) [18] in a few near-infrared windows revealed that the self-continuum absorption is typically an order of magnitude stronger than given by the MT_CKD continuum model prior to version 2.5. Most of these measurements, however, were made at elevated temperatures, which makes their application to atmospheric conditions difficult. Here we report new laboratory measurements of the self-continuum absorption at 289 and 318 K in the near-infrared spectral region 1300–8000 cm−1, using a multipass 30 m base cell with total optical path 612 m. Our results confirm the main conclusions of the previous measurements both within bands and in windows. Of particular note is that we present what we believe to be the first near-room temperature measurement using Fourier Transform Spectrometry of the self-continuum in the 6200 cm−1 (1.6 μm) window, which provides tentative evidence that, at such temperatures, the water vapour continuum absorption may be as strong as it is in 2.1 μm and 4 μm windows and up to 2 orders of magnitude stronger than the MT_CKD-2.5 continuum. We note that alternative methods of measuring the continuum in this window have yielded widely differing assessment of its strength, which emphasises the need for further measurements.

Ensemble projections for wine production in the Douro Valley of Portugal

Wine production is largely governed by atmospheric conditions, such as air temperature and precipitation, together with soil management and viticultural/enological practices. Therefore, anthropogenic climate change is likely to have important impacts on the winemaking sector worldwide. An important winemaking region is the Portuguese Douro Valley, which is known by its world-famous Port Wine. The identification of robust relationships between atmospheric factors and wine parameters is of great relevance for the region. A multivariate linear regression analysis of a long wine production series (1932–2010) reveals that high rainfall and cool temperatures during budburst, shoot and inflorescence development (February-March) and warm temperatures during flowering and berry development (May) are generally favourable to high production. The probabilities of occurrence of three production categories (low, normal and high) are also modelled using multinomial logistic regression. Results show that both statistical models are valuable tools for predicting the production in a given year with a lead time of 3–4 months prior to harvest. These statistical models are applied to an ensemble of 16 regional climate model experiments following the SRES A1B scenario to estimate possible future changes. Wine production is projected to increase by about 10 % by the end of the 21st century, while the occurrence of high production years is expected to increase from 25 % to over 60 %. Nevertheless, further model development will be needed to include other aspects that may shape production in the future. In particular, the rising heat stress and/or changes in ripening conditions could limit the projected production increase in future decades.

Surface water temperature observations of large lakes by optimal estimation

Optimal estimation (OE) and probabilistic cloud screening were developed to provide lake surface water temperature (LSWT) estimates from the series of (advanced) along-track scanning radiometers (ATSRs). Variations in physical properties such as elevation, salinity, and atmospheric conditions are accounted for through the forward modelling of observed radiances. Therefore, the OE retrieval scheme developed is generic (i.e., applicable to all lakes). LSWTs were obtained for 258 of Earth's largest lakes from ATSR-2 and AATSR imagery from 1995 to 2009. Comparison to in situ observations from several lakes yields satellite in situ differences of −0.2 ± 0.7 K for daytime and −0.1 ± 0.5 K for nighttime observations (mean ± standard deviation). This compares with −0.05 ± 0.8 K for daytime and −0.1 ± 0.9 K for nighttime observations for previous methods based on operational sea surface temperature algorithms. The new approach also increases coverage (reducing misclassification of clear sky as cloud) and exhibits greater consistency between retrievals using different channel–view combinations. Empirical orthogonal function (EOF) techniques were applied to the LSWT retrievals (which contain gaps due to cloud cover) to reconstruct spatially and temporally complete time series of LSWT. The new LSWT observations and the EOF-based reconstructions offer benefits to numerical weather prediction, lake model validation, and improve our knowledge of the climatology of lakes globally. Both observations and reconstructions are publically available from http://hdl.handle.net/10283/88.

Urban integrated meteorological observations: practice and experience in Shanghai, China

Observations of atmospheric conditions and processes in citiesare fundamental to understanding the interactions between the urban surface and weather/climate, improving the performance of urban weather, air quality and climate models, and providing key information for city end-users (e.g. decision-makers, stakeholders, public). In this paper, Shanghai's urban integrated meteorological observation network (SUIMON) and some examples of intended applications are introduced. Its characteristics include being: multi- purpose (e.g. forecast, research, service), multi-function (high impact weather, city climate, special end-users), multi-scale (e.g. macro/meso-, urban-, neighborhood, street canyon), multi-variable (e.g. thermal, dynamic, chemical, bio-meteorological, ecological), and multi- platform (e.g. radar, wind profiler, ground-based, satellite based, in-situ observation/ sampling). Underlying SUIMON is a data management system to facilitate exchange of data and information. The overall aim of the network is to improve coordination strategies and instruments; to identify data gaps based on science and user driven requirements; and to intelligently combine observations from a variety of platforms by using a data assimilation system that is tuned to produce the best estimate of the current state of the urban atmosphere.

Urban-scale Environmental Prediction Systems

Weather, climate, water and related environmental conditions, including air quality, all have profound effects on cities. A growing importance is being attached to understanding and predicting atmospheric conditions and their interactions with other components of the Earth System in cities, at multiple scales. We highlight the need for: (1) development of high-resolution coupled environmental prediction models that include realistic city-specific processes, boundary conditions and fluxes; (2) enhanced observational systems to support (force, constrain, evaluate) these models to provide high quality forecasts for new urban services; (3) provision of meteorological and related environmental variables to aid protection of human health and the environment; (4) new targeted and customized delivery platforms using modern communication techniques, developed with users to ensure that services, advice and warnings result in appropriate action; and (5) development of new skill and capacity to make best use of technologies to deliver new services in complex, challenging and evolving city environments. We highlight the importance of a coordinated and strategic approach that draws on, but does not replicate, past work to maximize benefits to stakeholders.

Understanding inter-satellite biases of microwave humidity sounders using global simultaneous nadir overpasses

Simultaneous nadir overpasses (SNOs) of polar-orbiting satellites are most frequent in polar areas but can occur at any latitude when the equatorial crossing times of the satellites become close owing to orbital drift. We use global SNOs of polar orbiting satellites to evaluate the intercalibration of microwave humidity sounders from the more frequent high-latitude SNOs. We have found based on sensitivity analyses that optimal distance and time thresholds for defining collocations are pixel centers less than 5 km apart and time differences less than 300 s. These stringent collocation criteria reduce the impact of highly variable surface or atmospheric conditions on the estimated biases. Uncertainties in the estimated biases are dominated by the combined radiometric noise of the instrument pair. The effects of frequency changes between different versions of the humidity sounders depend on the amount of water vapor in the atmosphere. There are significant scene radiance and thus latitude dependencies in the estimated biases and this has to taken into account while intercalibrating microwave humidity sounders. Therefore the results obtained using polar SNOs will not be representative for moist regions, necessitating the use of global collocations for reliable intercalibration.

Seasonal surface urban energy balance and wintertime stability simulated using three land-surface models in the high-latitude city Helsinki

The performance of three urban land surface models, run in offline mode, with their default external parameters, is evaluated for two distinctly different sites in Helsinki: Torni and Kumpula. The former is a dense city centre site with 22% vegetation, while the latter is a suburban site with over 50% vegetation. At both locations the models are compared against sensible and latent heat fluxes measured using the eddy covariance technique, along with snow depth observations. The cold climate experienced by the city causes strong seasonal variations that include snow cover and stable atmospheric conditions. Most of the time the three models are able to account for the differences between the study areas as well as the seasonal and diurnal variability of the energy balance components. However, the performances are not systematic across the modelled components, season and surface type. The net all-wave radiation is well simulated, with the greatest uncertainties related to snowmelt timing, when the fraction of snow cover has a key role, particularly in determining the surface albedo. For the turbulent fluxes, more variation between the models is seen which can partly be explained by the different methods in their calculation and partly by surface parameter values. For the sensible heat flux, simulation of wintertime values was the main problem, which also leads to issues in predicting near-surface stabilities particularly at the dense city centre site. All models have the most difficulties in simulating latent heat flux. This study particularly emphasizes that improvements are needed in the parameterization of anthropogenic heat flux and thermal parameters in winter, snow cover in spring and evapotranspiration in order to improve the surface energy balance modelling in cold climate cities.

Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a central European cave (NW Switzerland)

Deuterium (dD) and oxygen (d18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of d17O and d18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (dD, d17O and d18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean dD, d18O and d17O are �71.0‰, �9.9‰, �5.2‰ for precipitation, �60.3‰, �8.7‰, �4.6‰ for cave drip water and �61.3‰, �8.3‰, �4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (D of ~ þ 10‰ for dD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8e10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first d17O measurement in speleothem fluid inclusions, as well as the first comparison of the d17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems. This study on precipitation, drip water and fluid inclusions will be used as a speleothem proxy calibration for Milandre cave in order to reconstruct paleotemperatures and moisture source variations for Western Central Europe.

Climate perspective on the large-scale circulation associated with the transition of the first South Atlantic hurricane

The landfall of Cyclone Catarina on the Brazilian coast in March 2004 became known as the first documented hurricane in the South Atlantic Ocean, promoting a new view oil how large-scale features can contribute to tropical transition. The aim of this paper is to put the large-scale circulation associated with Catarina`s transition in climate perspective. This is discussed in the light of a robust pattern of spatial correlations between thermodynamic and dynamic variables of importance for hurricane formation. A discussion on how transition mechanisms respond to the present-day circulation is presented. These associations help in understanding why Catarina was formed in a region previously thought to be hurricane-free. Catarina developed over a large-scale area of thermodynamically favourable air/sea temperature contrast. This aspect explains the paradox that such a rare system developed when the sea surface temperature was slightly below average. But, although thermodynamics played an important role, it is apparent that Catarina would not have formed without the key dynamic interplay triggered by a high latitude blocking. The blocking was associated with an extreme positive phase of the Southern Annular Mode (SAM) both hemispherically and locally, and the nearby area where Catarina developed is found to be more cyclonic during the positive phase of the SAM. A conceptual model is developed and a `South Atlantic index` is introduced as a useful diagnostic of potential conditions leading to tropical transition in the area, where large-scale indices indicate trends towards more favourable atmospheric conditions for tropical cyclone formation. Copyright (c) 2008 Royal Meteorological Society

Two case studies of sulfate scavenging processes in the Amazon region (Rondonia)

The scavenging processes of chemical species have been previously studied with numerical modeling, in order to understand the gas and particulate matter intra-reservoir transferences. In this study, the atmospheric (RAMS) and scavenging (B.V.2) models were used, in order to simulate sulfate concentrations in rainwater using scavenging processes as well as the local atmospheric conditions obtained within the LBA Project in the State of Rondonia, during a dry-to-wet transition season. Two case studies were conducted. The RAMS atmospheric simulation of these events presented satisfactory results, showing the detailed microphysical processes of clouds in the Amazonian region. On the other hand, with cloud entrainments, observed values have been overestimated. Modeled sulfate rainwater concentration, using exponential decay and cloud heights of 16 km and no entrainments, presented the best results, reaching 97% of the observed value. The results, using shape parameter 5, are the best, improving the overall result. (C) 2008 Elsevier Ltd. All rights reserved.

The exposure of the hybrid detector of the Pierre Auger Observatory

The Pierre Auger Observatory is a detector for ultra-high energy cosmic rays. It consists of a surface array to measure secondary particles at ground level and a fluorescence detector to measure the development of air showers in the atmosphere above the array. The ""hybrid"" detection mode combines the information from the two subsystems. We describe the determination of the hybrid exposure for events observed by the fluorescence telescopes in coincidence with at least one water-Cherenkov detector of the surface array. A detailed knowledge of the time dependence of the detection operations is crucial for an accurate evaluation of the exposure. We discuss the relevance of monitoring data collected during operations, such as the status of the fluorescence detector, background light and atmospheric conditions, that are used in both simulation and reconstruction. (C) 2010 Elsevier B.V. All rights reserved.