Items

Advanced search

A fast H2O total column density product from GOME – Validation with in-situ aircraft measurements

Atmospheric water vapour is the most important greenhouse gas which is responsible for about 2/3 of the natural greenhouse effect, therefore changes in atmospheric water vapour in a changing climate (the water vapour feedback) is subject to intense debate. H2O is also involved in many important reaction cycles of atmospheric chemistry, e.g. in the production of the OH radical. Thus, long time series of global H2O data are highly required. Since 1995 the Global Ozone Monitoring Experiment (GOME) continuously observes atmospheric trace gases. In particular it has been demonstrated that GOME as a nadir looking UV/vis-instrument is sensitive to many tropospheric trace gases. Here we present a new, fast H2O algorithm for the retrieval of vertical column densities from GOME measurements. In contrast to existing H2O retrieval algorithms it does not depend on additional information like e.g. the climatic zone, aerosol content or ground albedo. It includes an internal cloud-, aerosol-, and albedo correction which is based on simultaneous observations of the oxygen dimer O4. From sensitivity studies using atmospheric radiative modelling we conclude that our H2O retrieval overestimates the true atmospheric H2O vertical column density (VCD) by about 4% for clear sky observations in the tropics and sub-tropics, while it can lead to an underestimation of up to -18% in polar regions. For measurements over (partly) cloud covered ground pixels, however, the true atmospheric H2O VCD might be in general systematically underestimated. We compared the GOME H2O VCDs to ECMWF model data over one whole GOME orbit (extending from the Arctic to the Antarctic) including also totally cloud covered measurements. The correlation of the GOME observations and the model data yield the following results: a slope of 0.96 (r2 = 0.86) and an average bias of 5%. Even for measurements with large cloud fractions between 50% and 100% an average underestimation of only -18% was found. This high accuracy of our GOME H2O data is also confirmed by the excellent agreement with in-situ aircraft measurements during the MINOS campaign in Greece in summer 2001 (slope of 0.97 (r2 = 0.86), and an average bias of only 0.2%). Our H2O algorithm can be directly adapted to the nadir observations of SCIAMACHY (SCanning Imaging Absorption SpectroMeter for Atmospheric CHartographY) which was launched on ENVISAT in March 2002. Near real time H2O column data from GOME and SCIAMACHY might be of great value for meteorological weather forecast.
OH in the coastal boundary layer of Crete during MINOS: Measurements and relationship with ozone photolysis

Hydroxyl radical (OH) concentrations were measured in August 2001 at Finokalia Station on the northeastern coast of Crete during the Mediterranean Intensive Oxidant Study (MINOS). OH was measured based on selected ion chemical ionization mass spectrometry (SI/CIMS) with a time resolution of 30 sec and signal integration of 5 min. The corresponding accuracy, precision, and detection limit were 20% (1σ), 11% (1σ), and 2.4 x 105 molecules cm-3 (2σ), respectively. OH levels showed a strong diurnal variability with high maxima (approximately 2 x 107 molecules cm-3) occurring around 13:30 LT (10:30 UTC) and nighttime values below the detection limit. Daily 24-hour average concentrations varied between 3.6-6.7 x 106 cm-3. For the total measurement period (6-21 August) the mean and standard deviation were 4.5 ± 1.1 x 106 cm-3. The OH data set is analyzed based on a classification into three periods: I: Aug 6-8, II: Aug 9-11, III: Aug 13-18. For each of the three periods the measured OH concentrations are described by the empirical function [OH] = a J(O1D)b, with J(O1D) being the ozone photolysis frequency and a = 1.4 x 1010 s cm-3, 1.7 x 1010 s cm-3, 2.2 x 1010 s cm-3, and b = 0.68, respectively. Taking into account the estimated precision of the OH measurements this empirical function using three values for a and one value for b explains 99% of the observed variance of OH. A detailed sensitivity analysis using a CH4-CO box model was performed to interpret this relationship, in particular the meanings of the pre-exponential factor a and the exponent b. It was found that the value of b which represents the total logarithmic dependence of [OH] on J(O1D) includes the individual contributions from the photolysis of O3, NO2, HCHO, HONO, and H2O2 which could be determined using the box model. For the conditions prevailing during the MINOS campaign the exponent b was found to be dominated by the contributions from O3- and NO2-photolysis. For the individual functional dependences between [OH] and J(O1D), [OH] and J(NO2), and J(NO2) and J(O1D) the partial logarithmic derivatives were determined to be 0.5, 0.6, and 0.3, respectively. Overall, the box model yields a value of 0.70 for the exponent b in very good agreement with the corresponding value derived from the empirical analysis of the measurements. This empirical approach in which the chemical air mass characteristics influencing the OH radical balance and thereby, the self-cleansing efficiency of the atmosphere, are represented by only two parameters which are constant over quite substantial time periods may be used in future experiments to test and compare OH measurements made in different atmospheric environments.
Mass closure on the chemical species in size-segregated atmospheric aerosol collected in an urban area of the Po Valley, Italy

A complete size segregated chemical characterisation was carried out for aerosol samples collected in the urban area of Bologna over a period of one year, using five-stage low pressure Berner impactors. An original dual-substrate technique was adopted to obtain samples suitable for a complete chemical characterisation. Total mass, inorganic, and organic components were analysed as a function of size, and a detailed characterisation of the water soluble organic compounds was also performed by means of a previously developed methodology, based on HPLC separation of organic compounds according to their acid character and functional group analysis by Proton Nuclear Magnetic Resonance. Chemical mass closure of the collected samples was reached to within a few percent on average in the submicron aerosol range, while a higher unknown fraction in the coarse aerosol range was attributed to soil-derived species not analysed in this experiment. Comparison of the functional group analysis results with model results simulating water soluble organic compound production by gas-to-particle conversion of anthropogenic VOCs showed that this pathway provides a minor contribution to the organic composition of the aerosol samples in the urban area of Bologna.
Nonlinear relationships between atmospheric aerosol and its gaseous precursors: Analysis of long-term air quality monitoring data by means of neural networks

The nonlinear features of the relationships between concentrations of aerosol and volatile organic compounds (VOC) and nitrogen oxides (NOx) in urban environments are revealed directly from data of long-term routine measurements of NOx, VOC, and total suspended particulate matter (PM). The main idea of the method is development of special empirical models based on artificial neural networks. These models, that are basically, the nonlinear extension of the commonly used linear statistical models provide the best fit for the real (nonlinear) PM-NOx-VOC relationships under different atmospheric conditions. Such models may be useful in the context of various scientific and practical problems related to atmospheric aerosols. The method is demonstrated on an example of two empirical models based on independent data-sets collected at two air quality monitoring stations at South Coast Air Basin, California. It is shown that in spite of a rather large distance between the monitoring stations (more than 50 km) and thus substantially different environmental conditions, the empirical models demonstrate several common qualitative features. Specifically, under definite conditions, a decrease in the level of NOx or VOC may lead to an increase in mass concentration of aerosol. It is argued that these features are due to the nonlinear dependence of hydroxyl radical on VOC and NOx.
Haze in the Klang Valley of Malaysia

Continuous measurements of dry aerosol light scattering (Bsp) were made at two sites in the Klang Valley of Malaysia between December 1998 and December 2000. In addition 24-hour PM2.5 samples were collected on a one-day-in-six cycle and the chemical composition of the aerosol was determined. Periods of excessive haze were defined as 24-hour average Bsp values greater than 150 Mm-1 and these occurred on a number of occasions, between May and September 1999, during May 2000, and between July and September 2000. The evidence for smoke from biomass burning being a significant contributor to aerosol during periods of excessive haze is discussed. For example, during periods of excessive haze, the chemical composition of the aerosol showed enhanced concentrations of elemental carbon, organic carbon and non-seasalt potassium. The diurnal cycle of Bsp and PM10 was disturbed from its usual pattern of maxima overnight and minuma during the day with morning and afternoon traffic peaks, and instead showed a maximum peak during the middle of the day. Periods of excessive haze were coincident with the presence of forest fires on Sumatra during the southwest (SW) monsoon period, the influence of which are demonstrated by transport modelling for one week of the SW monsoon of 2000. The study highlights that whilst transboundary smoke is a major contributor to poor visibility in the Klang Valley, smoke from fires on Peninsular Malaysia is also a contributor. In addition the uniform concentration of non-seasalt sulfate in PM2.5 at both sites over the entire sampling period suggests the presence of a domestic source of secondary aerosol production in the Klang Valley.
Comprehensive two-dimensional gas chromatography (GC × GC) measurements of volatile organic compounds in the atmosphere

During the MINOS campaign in August 2001 comprehensive two-dimensional gas chromatography (GC x GC) was applied to the in situ measurements of atmospheric volatile organic compounds (VOCs) at the Finokalia ground station, Crete. The measurement system employs a thermal desorption unit for on-line sampling and injection, and a GC x GC separation system equipped with a flame ionization detector (FID) for detection. The system was optimized to resolve C7-C14 organic components. Two-dimensional chromatograms from measurements of Finokalia air samples show several hundred well-separated peaks. To facilitate peak identification, cartridge samples collected at Finokalia were analyzed using the same GC x GC system coupled with a time-of-flight mass spectrometer (TOF-MS). The resulting mass spectra were deconvoluted and compared to spectra from a database for tentative peak identification. About 650 peaks have been identified in the two-dimensional plane, with significant signal/noise ratios (>100) and high spectra similarities (>800). By comparing observed retention indices with those found in the literature, 235 of the identifications have been confirmed. 150 of the confirmed compounds show up in the C7-C14 range of the chromatogram from the in situ measurement. However, at least as many peaks remain unidentified. For quantification of the GC x GC measurements, peak volumes of measured compounds have been integrated and externally calibrated using a standard gas mixture.
Detailed modeling of mountain wave PSCs

Polar stratospheric clouds (PSCs) play a key role in polar ozone depletion. In the Arctic, PSCs can occur on the mesoscale due to orographically induced gravity waves. Here we present a detailed study of a mountain wave PSC event on 25-27 January 2000 over Scandinavia. The mountain wave PSCs were intensively observed by in-situ and remote-sensing techniques during the second phase of the SOLVE/THESEO-2000 Arctic campaign. We use these excellent data of PSC observations on 3 successive days to analyze the PSCs and to perform a detailed comparison with modeled clouds. We simulated the 3-dimensional PSC structure on all 3 days with a mesoscale numerical weather prediction (NWP) model and a microphysical box model (using best available nucleation rates for ice and nitric acid trihydrate particles). We show that the combined mesoscale/microphysical model is capable of reproducing the PSC measurements within the uncertainty of data interpretation with respect to spatial dimensions, temporal development and microphysical properties, without manipulating temperatures or using other tuning parameters. In contrast, microphysical modeling based upon coarser scale global NWP data, e.g. current ECMWF analysis data, cannot reproduce observations, in particular the occurrence of ice and nitric acid trihydrate clouds. Combined mesoscale/microphysical modeling may be used for detailed a posteriori PSC analysis and for future Arctic campaign flight and mission planning. The fact that remote sensing alone cannot further constrain model results due to uncertainities in the interpretation of measurements, underlines the need for synchronous in-situ PSC observations in campaigns.
Tropical tropospheric ozone derived using Clear-Cloudy Pairs (CCP) of TOMS measurements

Using TOMS total-ozone measurements over high-altitude cloud locations and nearby paired clear locations, we describe the Clear-Cloudy Pairs (CCP) method for deriving tropical tropospheric ozone. The high-altitude clouds are identified by measured 380 nm reflectivities greater than 80% and Temperature Humidity InfraRed (THIR) measured cloud-top pressures less than 200 hPa. To account for locations without high-altitude clouds, we apply a zonal sine fitting to the stratospheric ozone derived from available cloudy points, resulting in a wave-one amplitude of about 4 DU. THIR data is unavailable after November 1984, so we extend the CCP method by using a reflectivity threshold of 90% to identify high-altitude clouds and remove the influence of high-reflectivity-but-low-altitude clouds with a lowpass frequency filter. We correct ozone retrieval errors associated with clouds, and ozone retrieval errors due to sun glint and aerosols. Comparing CCP results with Southern Hemisphere ADditional OZonesondes (SHADOZ) tropospheric ozone indicates that CCP tropospheric ozone and ozonesonde measurements agree, on average, to within 3 ± 1 DU standard error of the mean. The most significant difference between CCP and ozonesonde tropospheric ozone can be explained by the low Total Ozone Mapping Spectrometer (TOMS) version-7 retrieval efficiency of ozone in the lower troposphere.
Classification of tropospheric ozone profiles over Johannesburg based on mozaic aircraft data

Each ozone profile is a unique response to the photochemical and dynamic processes operating in the troposphere and hence is critical to our understanding of processes and their relative contributions to the tropospheric ozone budget. Traditionally, mean profiles, together with some measure of variability, averaged by season or year at a particular location have been presented as a climatology. However, the mean profile is difficult to interpret because of the counteracting influences present in the micro-structure. On the other hand, case study analysis, whilst revealing, only applies to isolated conditions. In a search for pattern and order within ozone profiles, a classification based on a cluster analysis technique has been applied in this study. Ozone profiles are grouped according to the magnitude and altitude of ozone concentration. This technique has been tested with 56 ozone profiles at Johannesburg, South Africa, recorded by aircraft as part of the MOZAIC (Measurement of Ozone and Water Vapor aboard Airbus In-service Aircraft) program. Six distinct groups of ozone profiles have been identified and their characteristics described. The widely recognized spring maximum in tropospheric ozone is identified through the classification, but a new summertime mid-tropospheric enhancement due to the penetration of tropical air masses from continental regions in central Africa has been identified. Back trajectory modeling is used to provide evidence of the different origins of ozone enhancements in each of the classes. Continental areas over central Africa are shown to be responsible for the low to mid-tropospheric enhancement in spring and the mid-tropospheric peak in summer, whereas the winter low-tropospheric enhancement is attributed to local sources. The dominance of westerly winds through the troposphere associated with the passage of a mid-latitude cyclone gives rise to reduced ozone values.
Deep convective injection of boundary layer air into the lowermost stratosphere at midlatitudes

On 22 August 2001 a measurement flight was performed with the German research aircraft FALCON from Sardinia to Crete as part of the Mediterranean Oxidant Study (MINOS). Cruising at 8.2 km, the aircraft was forced to climb to 11.2 km over the southern tip of Italy to stay clear of the anvil of a large cumulonimbus tower. During ascent into the lowermost stratosphere in-situ measurements onboard the FALCON indicated several sharp increases in the concentrations of tropospheric trace gases, e.g. CO, acetone, methanol, benzene and acetonitrile, above the anvil. During one particular event deep in the stratosphere, at O3 concentrations exceeding 200 ppv, CO increased from about 60 to 90 ppv, while the concentration of acetone and methanol increased by more than a factor of 2 (0.7 to 1.8 ppv for acetone; 0.4 to 1.4 ppv for methanol). Enhancements for the short lived species benzene are even higher, increasing from 20 pptv in the stratosphere to approx. 130 pptv. The concentrations during the event were higher than background concentrations in the upper troposphere, indicating that polluted boundary layer air was directly mixed into the lowermost stratosphere.