Probabilistic approach to cloud and snow detection on Advanced Very High Resolution Radiometer (AVHRR) imagery

Derivation of probability estimates complementary to geophysical data sets has gained special attention over the last years. Information about a confidence level of provided physical quantities is required to construct an error budget of higher-level products and to correctly interpret final results of a particular analysis. Regarding the generation of products based on satellite data a common input consists of a cloud mask which allows discrimination between surface and cloud signals. Further the surface information is divided between snow and snow-free components. At any step of this discrimination process a misclassification in a cloud/snow mask propagates to higher-level products and may alter their usability. Within this scope a novel probabilistic cloud mask (PCM) algorithm suited for the 1 km × 1 km Advanced Very High Resolution Radiometer (AVHRR) data is proposed which provides three types of probability estimates between: cloudy/clear-sky, cloudy/snow and clear-sky/snow conditions. As opposed to the majority of available techniques which are usually based on the decision-tree approach in the PCM algorithm all spectral, angular and ancillary information is used in a single step to retrieve probability estimates from the precomputed look-up tables (LUTs). Moreover, the issue of derivation of a single threshold value for a spectral test was overcome by the concept of multidimensional information space which is divided into small bins by an extensive set of intervals. The discrimination between snow and ice clouds and detection of broken, thin clouds was enhanced by means of the invariant coordinate system (ICS) transformation. The study area covers a wide range of environmental conditions spanning from Iceland through central Europe to northern parts of Africa which exhibit diverse difficulties for cloud/snow masking algorithms. The retrieved PCM cloud classification was compared to the Polar Platform System (PPS) version 2012 and Moderate Resolution Imaging Spectroradiometer (MODIS) collection 6 cloud masks, SYNOP (surface synoptic observations) weather reports, Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) vertical feature mask version 3 and to MODIS collection 5 snow mask. The outcomes of conducted analyses proved fine detection skills of the PCM method with results comparable to or better than the reference PPS algorithm.

Antarctic Volcanic Flux Ratios from Law Dome Ice Cores

Explosive volcanic eruptions can inject large quantities of sulphur dioxide into the stratosphere. The aerosols that result from oxidation of the sulphur dioxide can produce significant cooling of the troposphere by reflecting or absorbing solar radiation. It is possible to obtain an estimate of the relative stratospheric sulphur aerosol concentration produced by different volcanoes by comparing sulphuric acid fluxes determined by analysis of polar ice cores. Here, we use a non-sea-salt sulphate time series derived from three well-dated Law Dome ice cores to investigate sulphuric acid flux ratios for major eruptions over the period AD 1301-1995. We use additional data from other cores to investigate systematic spatial variability in the ratios. Only for the Kuwae eruption (Law Dome ice date AD 1459.5) was the H2SO4 flux larger than that deposited by Tambora (Law Dome ice date AD 1816.7).

Stable-Isotope and Trace Element Time Series from Fedchenko Glacier (Pamirs) Snow/Firn Cores

In summer 2005, two pilot snow/firn cores were obtained at 5365 and 5206 m a.s.l. on Fedchenko glacier, Pamirs, Tajikistan, the world's longest and deepest alpine glacier. The well-defined seasonal layering appearing in stable-isotope and trace element distribution identified the physical links controlling the climate and aerosol concentration signals. Air temperature and humidity/precipitation were the primary determinants of stable-isotope ratios. Most precipitation over the Pamirs originated in the Atlantic. In summer, water vapor was re-evaporated from semi-arid regions in central Eurasia. The semi-arid regions contribute to non-soluble aerosol loading in snow accumulated on Fedchenko glacier. In the Pamir core, concentrations of rare earth elements, major and other elements were less than those in the Tien Shan but greater than those in Antarctica, Greenland, the Alps and the Altai. The content of heavy metals in the Fedchenko cores is 2-14 times lower than in the Altai glaciers. Loess from Afghan-Tajik deposits is the predominant lithogenic material transported to the Pamirs. Trace elements generally showed that aerosol concentration tended to increase on the windward slopes during dust storms but tended to decrease with altitude under clear conditions. The trace element profile documented one of the most severe droughts in the 20th century.

A High-Resolution Record of Atmospheric Dust Composition and Variability Since Ad 1650 from a Mount Everest Ice Core

A Mount Everest ice core analyzed at high resolution for major and trace elements (Sr, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi, U, Tl, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co) and spanning the period A. D. 1650- 2002 is used to investigate the sources of and variations in atmospheric dust through time. The chemical composition of dust varies seasonally, and peak dust concentrations occur during the winter-spring months. Significant correlations between the Everest dust record and dust observations at stations suggest that the Everest record is representative of regional variations in atmospheric dust loading. Back-trajectory analysis in addition to a significant correlation of Everest dust concentrations and the Total Ozone Mapping Spectrometer (TOMS) aerosol index indicates that the dominant winter sources of dust are the Arabian Peninsula, Thar Desert, and northern Sahara. Factors that contribute to dust generation at the surface include soil moisture and temperature, and the long-range transport of dust aerosols appears to be sensitive to the strength of 500-mb zonal winds. There are periods of high dust concentration throughout the 350-yr Mount Everest dust record; however, there is an increase in these periods since the early 1800s. The record was examined for recent increases in dust emissions associated with anthropogenic activities, but no recent dust variations can be conclusively attributed to anthropogenic inputs of dust.

Monsoonal Circulation of the McMurdo Dry Valleys, Ross Sea Region, Antarctica: Signal from the Snow Chemistry

McMurdo Dry Valleys (MDV, Ross Sea region, Antarctica) precipitation exhibits extreme seasonality in ion concentration, 3-5 orders of magnitude between summer and winter precipitation. To identify aerosol sources and investigate causes for the observed amplitude in concentration variability, four snow pits were sampled along a coast-Polar Plateau transect across the MDV. The elevation of the sites ranges from 50 to 2400 m and the distance from the coast from 8 to 93 km. Average chemistry gradients along the transect indicate that most species have either a predominant marine or terrestrial source in the MDV. Empirical orthogonal function analysis on the snow-chemistry time series shows that at least 57% of aerosol deposition occurs concurrently. A conceptual climate model, based on meteorological observations, is used to explain the strong seasonality in the MDV. Our results suggest that radiative forcing of the ice-free valleys creates a surface low-pressure cell during summer which promotes air-mass flow from the Ross Sea. The associated precipitating air mass is relatively warm, humid and contains a high concentration of aerosols. During winter, the MDV are dominated by air masses draining off the East Antarctic ice sheet, that are characterized by cold, dry and low concentrations of aerosols. The strong differences between these two air-mass sources create in the MDV a polar version of the monsoonal flow, with humid, warm summers and dry, cold winters.

Impact of solar versus volcanic activity variations on tropospheric temperatures and precipitation during the Dalton Minimum

The aim of this work is to elucidate the impact of changes in solar irradiance and energetic particles versus volcanic eruptions on tropospheric global climate during the Dalton Minimum (DM, AD 1780–1840). Separate variations in the (i) solar irradiance in the UV-C with wavelengths λ < 250 nm, (ii) irradiance at wavelengths λ > 250 nm, (iii) in energetic particle spectrum, and (iv) volcanic aerosol forcing were analyzed separately, and (v) in combination, by means of small ensemble calculations using a coupled atmosphere–ocean chemistry–climate model. Global and hemispheric mean surface temperatures show a significant dependence on solar irradiance at λ > 250 nm. Also, powerful volcanic eruptions in 1809, 1815, 1831 and 1835 significantly decreased global mean temperature by up to 0.5 K for 2–3 years after the eruption. However, while the volcanic effect is clearly discernible in the Southern Hemispheric mean temperature, it is less significant in the Northern Hemisphere, partly because the two largest volcanic eruptions occurred in the SH tropics and during seasons when the aerosols were mainly transported southward, partly because of the higher northern internal variability. In the simulation including all forcings, temperatures are in reasonable agreement with the tree ring-based temperature anomalies of the Northern Hemisphere. Interestingly, the model suggests that solar irradiance changes at λ < 250 nm and in energetic particle spectra have only an insignificant impact on the climate during the Dalton Minimum. This downscales the importance of top–down processes (stemming from changes at λ < 250 nm) relative to bottom–up processes (from λ > 250 nm). Reduction of irradiance at λ > 250 nm leads to a significant (up to 2%) decrease in the ocean heat content (OHC) between 0 and 300 m in depth, whereas the changes in irradiance at λ < 250 nm or in energetic particles have virtually no effect. Also, volcanic aerosol yields a very strong response, reducing the OHC of the upper ocean by up to 1.5%. In the simulation with all forcings, the OHC of the uppermost levels recovers after 8–15 years after volcanic eruption, while the solar signal and the different volcanic eruptions dominate the OHC changes in the deeper ocean and prevent its recovery during the DM. Finally, the simulations suggest that the volcanic eruptions during the DM had a significant impact on the precipitation patterns caused by a widening of the Hadley cell and a shift in the intertropical convergence zone.

Effects of sources and meteorology on particulate matter in the Western Mediterranean Basin: An overview of the DAURE campaign

DAURE (Determination of the Sources of Atmospheric Aerosols in Urban and Rural Environments in the Western Mediterranean) was a multidisciplinary international field campaign aimed at investigating the sources and meteorological controls of particulate matter in the Western Mediterranean Basin (WMB). Measurements were simultaneously performed at an urban-coastal (Barcelona, BCN) and a rural-elevated (Montseny, MSY) site pair in NE Spain during winter and summer. State-of-the-art methods such as 14C analysis, proton-transfer reaction mass spectrometry, and high-resolution aerosol mass spectrometry were applied for the first time in the WMB as part of DAURE. WMB regional pollution episodes were associated with high concentrations of inorganic and organic species formed during the transport to inland areas and built up at regional scales. Winter pollutants accumulation depended on the degree of regional stagnation of an air mass under anticyclonic conditions and the planetary boundary layer height. In summer, regional recirculation and biogenic secondary organic aerosols (SOA) formation mainly determined the regional pollutant concentrations. The contribution from fossil sources to organic carbon (OC) and elemental carbon (EC) and hydrocarbon-like organic aerosol concentrations were higher at BCN compared with MSY due to traffic emissions. The relative contribution of nonfossil OC was higher at MSY especially in summer due to biogenic emissions. The fossil OC/EC ratio at MSY was twice the corresponding ratio at BCN indicating that a substantial fraction of fossil OC was due to fossil SOA. In winter, BCN cooking emissions were identified as an important source of modern carbon in primary organic aerosol.

Polychlorinated Biphenyls in Glaciers. 2. Model Results of Deposition and Incorporation Processes

In previous work, Alpine glaciers have been identified as a secondary source of persistent organic pollutants (POPs). However, detailed understanding of the processes organic chemicals undergo in a glacial system was missing. Here, we present results from a chemical fate model describing deposition and incorporation of polychlorinated biphenyls (PCBs) into an Alpine glacier (Fiescherhorn, Switzerland) and an Arctic glacier (Lomonosovfonna, Norway). To understand PCB fate and dynamics, we investigate the interaction of deposition, sorption to ice and particles in the atmosphere and within the glacier, revolatilization, diffusion and degradation, and discuss the effects of these processes on the fate of individual PCB congeners. The model is able to reproduce measured absolute concentrations in the two glaciers for most PCB congeners. While the model generally predicts concentration profiles peaking in the 1970s, in the measurements, this behavior can only be seen for higher-chlorinated PCB congeners on Fiescherhorn glacier. We suspect seasonal melt processes are disturbing the concentration profiles of the lower-chlorinated PCB congeners. While a lower-chlorinated PCB congener is mainly deposited by dry deposition and almost completely revolatilized after deposition, a higher-chlorinated PCB congener is predominantly transferred to the glacier surface by wet deposition and then is incorporated into the glacier ice. The incorporated amounts of PCBs are higher on the Alpine glacier than on the Arctic glacier due to the higher precipitation rate and aerosol particle concentration on the former. Future studies should include the effects of seasonal melt processes, calculate the quantities of PCBs incorporated into the entire glacier surface, and estimate the quantity of chemicals released from glaciers to determine the importance of glaciers as a secondary source of organic chemicals to remote aquatic ecosystems.

Diurnal cycle of fossil and nonfossil carbon using radiocarbon analyses during CalNex

Radiocarbon (14C) analysis is a unique tool to distinguish fossil/nonfossil sources of carbonaceous aerosols. We present 14C measurements of organic carbon (OC) and total carbon (TC) on highly time resolved filters (3–4 h, typically 12 h or longer have been reported) from 7 days collected during California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 in Pasadena. Average nonfossil contributions of 58% ± 15% and 51% ± 15% were found for OC and TC, respectively. Results indicate that nonfossil carbon is a major constituent of the background aerosol, evidenced by its nearly constant concentration (2–3 μgC m−3). Cooking is estimated to contribute at least 25% to nonfossil OC, underlining the importance of urban nonfossil OC sources. In contrast, fossil OC concentrations have prominent and consistent diurnal profiles, with significant afternoon enhancements (~3 μgC m−3), following the arrival of the western Los Angeles (LA) basin plume with the sea breeze. A corresponding increase in semivolatile oxygenated OC and organic vehicular emission markers and their photochemical reaction products occurs. This suggests that the increasing OC is mostly from fresh anthropogenic secondary OC (SOC) from mainly fossil precursors formed in the western LA basin plume. We note that in several European cities where the diesel passenger car fraction is higher, SOC is 20% less fossil, despite 2–3 times higher elemental carbon concentrations, suggesting that SOC formation from gasoline emissions most likely dominates over diesel in the LA basin. This would have significant implications for our understanding of the on-road vehicle contribution to ambient aerosols and merits further study.

CONSTRAINING THE ATMOSPHERIC COMPOSITION OF THE DAY-NIGHT TERMINATORS OF HD 189733b: ATMOSPHERIC RETRIEVAL WITH AEROSOLS

A number of observations have shown that Rayleigh scattering by aerosols dominates the transmission spectrum of HD 189733b at wavelengths shortward of 1 μm. In this study, we retrieve a range of aerosol distributions consistent with transmission spectroscopy between 0.3-24 μm that were recently re-analyzed by Pont et al. To constrain the particle size and the optical depth of the aerosol layer, we investigate the degeneracies between aerosol composition, temperature, planetary radius, and molecular abundances that prevent unique solutions for transit spectroscopy. Assuming that the aerosol is composed of MgSiO3, we suggest that a vertically uniform aerosol layer over all pressures with a monodisperse particle size smaller than about 0.1 μm and an optical depth in the range 0.002-0.02 at 1 μm provides statistically meaningful solutions for the day/night terminator regions of HD 189733b. Generally, we find that a uniform aerosol layer provide adequate fits to the data if the optical depth is less than 0.1 and the particle size is smaller than 0.1 μm, irrespective of the atmospheric temperature, planetary radius, aerosol composition, and gaseous molecules. Strong constraints on the aerosol properties are provided by spectra at wavelengths shortward of 1 μm as well as longward of 8 μm, if the aerosol material has absorption features in this region. We show that these are the optimal wavelengths for quantifying the effects of aerosols, which may guide the design of future space observations. The present investigation indicates that the current data offer sufficient information to constrain some of the aerosol properties of HD189733b, but the chemistry in the terminator regions remains uncertain.

Representativeness and seasonality of major ion records derived from NEEM firn cores

The seasonal and annual representativeness of ionic aerosol proxies (among others, calcium, sodium, ammonium and nitrate) in various firn cores in the vicinity of the NEEM drill site in northwest Greenland have been assessed. Seasonal representativeness is very high as one core explains more than 60 % of the variability within the area. The inter-annual representativeness, however, can be substantially lower (depending on the species) making replicate coring indispensable to derive the atmospheric variability of aerosol species. A single core at the NEEM site records only 30 % of the inter-annual atmospheric variability in some species, while five replicate cores are already needed to cover approximately 70 % of the inter-annual atmospheric variability in all species. The spatial representativeness is very high within 60 cm, rapidly decorrelates within 10 m but does not diminish further within 3 km. We attribute this to wind reworking of the snow pack leading to sastrugi formation. Due to the high resolution and seasonal representativeness of the records we can derive accurate seasonalities of the measured species for modern (AD 1990–2010) times as well as for pre-industrial (AD 1623–1750) times. Sodium and calcium show similar seasonality (peaking in February and March respectively) for modern and pre-industrial times, whereas ammonium and nitrate are influenced by anthro pogenic activities. Nitrate and ammonium both peak in May during modern times, whereas during pre-industrial times ammonium peaked during July–August and nitrate during June–July.

Emerging Areas in Atmospheric Photochemistry

Sunlight is a major driving force of atmospheric processes. A detailed knowledge of atmospheric photochemistry is therefore required in order to understand atmospheric chemistry and climate. Considerable progress has been made in this field in recent decades. This contribution will highlight a set of new and emerging ideas (and will therefore not provide a complete review of the field) mainly dealing with long wavelength photochemistry both in the gas phase and on a wide range of environmental surfaces. Besides this, some interesting bulk photochemistry processes are discussed. Altogether these processes have the potential to introduce new chemical pathways into tropospheric chemistry and may impact atmospheric radical formation.

Liquid–Vapor Interface of Formic Acid Solutions in Salt Water: A Comparison of Macroscopic Surface Tension and Microscopic in Situ X-ray Photoelectron Spectroscopy Measurements

The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.