Observation and origin of organochlorine compounds and polycyclic aromatic hydrocarbons in the free troposphere over central Europe (original) (raw)
Related papers
Long-range atmospheric transpod and fate of persistent organic pollutants in remote mountain areas
2004
Index Chapter 6 Results Article 1. Semivolatile organochlorine compounds in the free troposphere of the Northeastern Atlantic Article 2. Deposition of semi-volatile organochlorine compounds in the free troposphere of the eastern North Atlantic Ocean Article 3. Influence of soot carbon on the soil-air partitioning of polycyclic aromatic hydrocarbons Article 4. Atmospheric semi-volatile organochlorine compounds in European high mountian areas (Central Pyrenees and High Tatras) Article 5. PCBs in Pinus uncinata, the uppermost growing tree species of Central Pyrenean high mountains (Catalonia, Spain) Article 6. Passive sampling of atmospheric organochlorine compounds by SPMDs in a high-mountain area (Central Pyrenees) Article 7. Persistent organochlorine compounds in soils and sediments of European high altitude mountain lakes Article 8. Polycyclic aromatic hydrocarbon composition in soils and sediments of high altitude lakes Article 9. Congener specific assessment of global atmospheric PCB pool Chapter 7 Discussion 7.1 Atmospheric transport and fate of POP in the subtropical troposphere 7.1.1 Organochlorine compounds 7.1.2 Polycyclic aromatic hydrocarbons 7.2 Atmospheric transport and fate of POP in European high-mountain areas 7.
Atmospheric Chemistry and Physics
Polycyclic aromatic hydrocarbons (PAHs) were analysed in bulk atmospheric deposition samples collected at four European high-mountain areas, Gossenköllesee (Tyrolean Alps), Redon (Central Pyrenees), Skalnate Pleso (High Tatra Mountains), and Lochnagar (Grampian Mountains) between 2004 and 2006. Sample collection was performed monthly in the first three sites and biweekly in Lochnagar. The number of sites, period of study and sampling frequency provide the most comprehensive description of PAH fallout in high mountain areas addressed so far.
Distributions of brominated organic compounds in the troposphere and lower stratosphere
Journal of Geophysical Research, 1999
A comprehensive suite of brominated organic compounds was measured from whole air samples collected during the 1996 NASA Stratospheric Tracers of Atmospheric Transport aircraft campaign and the 1996 NASA Global Tropospheric Experiment Pacific Exploratory Mission-Tropics aircraft campaign. Measurements of individual species and total organic bromine were utilized to describe latitudinal and vertical distributions in the troposphere and lower stratosphere, fractional contributions to total organic bromine by individual species, fractional dissociation of the long-lived species relative to CFC-11, and the Ozone Depletion Potential of the halons and CH3Br. Spatial differences in the various organic brominated compounds were related to their respective sources and chemical lifetimes. The difference between tropospheric mixing ratios in the Northern and Southern Hemispheres for halons was approximately equivalent to their annual tropospheric growth rates, while the interhemispheric ratio of CH3Br was 1.18. The shorter-lived brominated organic species showed larger tropospheric mixing ratios in the tropics relative to midlatitudes, which may reflect marine biogenic sources. Significant vertical gradients in the troposphere were observed for the shortlived species with upper troposphere values 40-70% of the lower troposphere values. Much smaller vertical gradients (3-14%) were observed for CH3Br, and no significant vertical gradients were observed for the halons. Above the tropopause, the decrease in organic bromine compounds was found to have some seasonal and latitudinal differences. The combined losses of the individual compounds resulted in a loss of total organic bromine between the tropopause and 20 km of 38-40% in the tropics and 75-85% in midlatitUdes. The fractional dissociation of the halons and CH3Br relative to CFC-11 showed latitudinal differences, with larger values in the tropics. bromochloromethane (CH2BrC1), bromodichloromethane (CHBrC12), and dibromochloromethane (CHBr2C1) [Schauffier et al., 1998]. The total amount of organic bromine source gases at the tropical tropopause in 1996 was 17.4:t0.9 ppt with most of the variability due to variations in the mixing ratios of short-lived halogenated methanes [Schauffier et al., 1998]. The participation of bromine in stratospheric ozone loss occurs via catalytic cycles that also involve C1 x, NO x, and HO x species [Solomon et al., 1986; McElroy et al., 1986; Anderson et al., 1989; Solomon, 1990; Salawitch et al., 1993; Garcia and Solomon, 1994; Wennberg et al., 1994]. Bromine is more efficient than an equivalent amount of chlorine in the catalytic destruction of ozone because a larger fraction of the total inorganic bromine is in a reactive form relative to that of inorganic chlorine [Solomon et al., 1992; Garcia and Solomon, 1994]. The magnitude of the efficiency difference between bromine and chlorine has been estimated to be from 40 to 400 [Solomon et al., 1992; Garcia and Solomon, 1994; Daniel et al., 1995]. This efficiency difference, or a, is variable with altitude and chlorine loading in the stratosphere. Bromine may be placed on an equivalent scale with chlorine by multiplying c• by the total 21,513 21,514 SCHAUFFLER ET AL.: BROMINATED ORGANIC COMPOUNDS IN ATMOSPHERE amount of inorganic bromine. This value is then added to the inorganic chlorine to give an equivalent chlorine loading [Daniel et al., 1995; Montzka et al., 1996]. Equivalent effective stratospheric chlorine (EESC), calculated with an • of 40, was used by Daniel et al. [ 1995] to evaluate halogen loading, ozone loss, and the resulting effects on radiative forcing between 1950 and 2100. Montzka et al. [1996] used effective equivalent chlorine calculations based on an • of 100 and tropospheric measurements of chlorine and bromine source gases to determine the effects of recent changes in the growth rates of these gases on chlorine loading in the stratosphere. In studies such as these, accurate measurements of organic source gases in the lower stratosphere provide important constraints on the amount of inorganic bromine available from these sources. High-resolution measurements of organic source gases of bromine across the tropopause in various latitude regimes are required to describe the vertical structures that result from both local chemistry and transport. Vertical distributions of individual organic bromine compounds may be used: (1) to accurately determine the amount and distribution of organic bromine in both the troposphere and lower stratosphere; (2) to evaluate the variability of organic bromine in these regions; (3) to calculate the amount of inorganic bromine in the lower stratosphere; (4) to evaluate loss processes in both regimes; and (5) to calculate the vertical distribution of individual species contributions to total organic and inorganic bromine. In addition, the measured correlations between organic halogen trace gases are a useful tool in evaluating model chemical schemes [Availone and Prather, JZhang et al. [ 1997]. CHBrCI 2 0.1g nd <0.5 h SCHAUFFLER ET AL.' BROMINATED ORGANIC COMPOUNDS IN ATMOSPHERE 21,515 released will continue to be an important source of bromine to the stratosphere over the next few decades [Butler et al., 1998]. Methyl bromide represents ~55% of the organic bromine at the tropical tropopause [Schau•ler et al., 1998; Kourtidis et al., 1998]. Methyl bromide has both natural and anthropogenic sources. Recent summaries of published information on CH3Br are given by Butler and Rodriguez [1996] and Penkett et al. [1995]. The primary use of industrially produced CH3Br is fumigation. Additional sources of CH3Br are from burning of leaded gasoline and from biomass burning [Penkett et al., 1995; Andreae et al., 1996; N.J. Blake et al., 1996; Thomas et al., 1997]. A primary natural source is believed to be the oceans, which also represent an important sink [Lobert et al., 1995; Yvon-Lewis and Butler, 1997; Lobert et al., 1997]. Additional ensure a negligible source of uncertainty from inhomogeneities in halocarbon abundance during the filling of a given canister. Canisters were analyzed within 2-14 days after sample collection. Whole air samples from PEM Tropics •vere collected by the University of California, Irvine (UCB, whole air sampling systems on board the NASA P3 and DC8 aircraft. The UCI PEM Tropics samples were collected in the Pacific region from 73øS to 45øN and from near the surface to -12 km (Figure lb). The UCI system includes a metal bellows pump, a stainless steel manifold, and electropolished stainless steel canisters [D.R. Blake et al., 1996]. A maximum of 168 samples were collected per flight. The canisters were filled to -40 psi and analyzed at UCI for a variety of hydrocarbons and halocarbons. A subsample of the total number of canisters was then shipped to NCAR for analysis of halocarbons and other compounds. The UCI canisters were analyzed at UCI within 2-10 days after sample collection and were analyzed at NCAR within 30-60 days after sample collection.
The occurrence and the fate of organic pollutants in the atmosphere
Water, Air, & Soil Pollution, 1993
The transport and cycling of both natural and anthropogenic chemicals in the environment is an extremely dynamic process that is important for the well being of all earth's inhabitants. The atmosphere plays a major role in the transport and cycling of chemicals, especially those that are volatile or semi-volatile in nature. Atmospheric water, in the form of snow, fog, and rain can provide major transport pathways for chemicals that are distributed both regionally and globally.
Organic material in the global troposphere
Reviews of Geophysics, 1983
Interest in the global tropospheric chemistry of organic materials has been growing rapidly over the past decade. In addition to a basic concern about the fundamental biogeochemical cycles of organic matter, this interest has arisen largely because of concern about the oxidant-forming potential of natural hydrocarbons, the possible importance of nonmethane hydrocarbons as a source for atmospheric CO, and the role played by organic material in the formation of secondary aerosol particles. In this review we consider the information presently available on concentration distribution, sources, sinks, and atmospheric transformation reactions of organic matter in the global troposphere. The data base for tropospheric organic compounds is very small. However, it is apparent that while anthropogenic sources often dominate the atmospheric chemistry of organic material in urban and near-urban air, a key to understanding the global cycling of tropospheric organic substances is a clear understanding of the interaction of the atmosphere with the terrestrial and marine biosphere.
Measurements of halogenated organic compounds near the tropical tropopause
Geophysical Research Letters, 1993
The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8øN and 25.3ON during AASE II. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 _+ 0.06 ppbv and 21.1 + 0.8 pptv, respectively. CH3C1 represented 15.1% of the total organic chlorine, with CFC 11 (CC13F) and CFC 12 (CC12F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CC14, CH3CC13, and CFC 113 (CC12FCC1F2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude midtroposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHC13, CH2C12, CH2Br2, and CH3CC13. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere. . Nature, 318, 550, 1985. Montzka, S.A., et al., Nitrous Oxide and Halocarbons
Environmental Science and Pollution Research, 2021
Chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs) are persistent organic pollutants that are ubiquitous in the atmospheric environment. The sources, fate, and sinks in the atmosphere of these substances are largely unknown. One of the reasons is the lack of widely accessible analytical instrumentation. In this study, a new analytical method for ClPAHs and BrPAHs using gas-chromatography coupled with triple quadrupole mass spectrometry is presented. The method was applied to determine ClPAHs and BrPAHs in total deposition samples collected at two sites in central Europe. Deposition fluxes of ClPAHs and BrPAHs ranged 580 (272–962) and 494 (161–936) pg m−2 day−1, respectively, at a regional background site, Košetice, and 547 (351–724) and 449 (202–758) pg m−2 day−1, respectively, at a semi-urban site, Praha-Libuš. These fluxes are similar to those of PCBs and more than 2 orders of magnitude lower than those of the parent PAHs in the region. Seasonal variat...