ALBERT

Description: This paper includes determinations of archeological and geological samples from different sites in central Italy performed at the Ente per le Nuove Tecnologie l'Energia e l'Ambiente (ENEA) Radiocarbon Laboratory. This laboratory has been in operation since 1985 at the ENEA Bologna Research Center.

Description: This is Radiocarbon's annual list of active radiocarbon laboratories and personnel known to us. Conventional beta-counting facilities are listed in Part I, and accelerator mass spectrometry (AMS) facilities are listed in Part II. Laboratory code designations, used to identify published dates, are given to the left of the listing. (See p 515 for a complete list of past and present lab codes.)

Description: Radiocarbon dates on samples aimed to date the settlement of Iceland are given together with comments by the laboratory, since many of the results and descriptions given by Sveinbjörnsdóttir et al. (2004) in Radiocarbon, together with new results, are in error. The intention of this paper is to present correct dates and further relevant information regarding samples used earlier and to discuss possible complications inherent in the method of Sveinbjörnsdóttir et al. (2004). Examples are given of how critical the collection, treatment, and interpretation of samples may be. An age difference between birch charcoal and grains for a site is expected due to various reasons. If the difference amounts up to ∼100 yr, as reported by Sveinbjörnsdóttir et al. (2004), it must only to a small degree be due to biological age. Reference to an excavation report, details regarding stratigraphy, and discussions of the risk for displacement and contamination are missing in their paper. A final evaluation of the time for settlement should not be done until more research is completed and other possible or earlier suggested or even dated sites are discussed. A summary is given of the research on the island and volcanic effects on the 14C activity of the atmospheric CO2, especially over Iceland.

Description: Despite extensive research on political activity on the part of corporations, clear and consistent findings remain elusive. We identify three reasons for this failure. First, most of the empirical literature on corporate political activity simply studies the wrong phenomena by examining political action committees rather than lobbying more generally. Second, the literature studies an excessively narrow sample of organizations that might engage in lobbying, focusing almost always on extremely large corporations, which inevitably attenuates variance on many of the variables hypothesized to influence engagement in political activity. And third, prior work is rarely attentive to the diversity of corporate activities, narrowly conceptualizing vital aspects of the business context that might influence decisions to engage in political activity. Based on this critique, we develop and test new models of corporate political activity, finding that the diversity of the economic context within which firms work and firm size matter a great deal, if in ways somewhat different from those reported in prior work.

Description: This paper explores the East-West dichotomy of outsourcing in the European Union in the context of its 2004 eastward enlargement. The purpose of the study is to shed light on the connection between outsourcing and the causal logic of regional integration. The conventional view is that the transfer of business operations from Western Europe to low-cost locations to the east represents a process of outsourcing West-European jobs which deprives the EU core of growth opportunities to the exclusive benefit of the new members from Eastern Europe. This analysis posits the systemic functions of EU outsourcing as a mechanism of economic homogenization in the regional market along its three principal dimensions: investment, commodity trade, and labor mobility. At the macro-level, outsourcing complements capital movements and trade, and acts as a substitute for labor mobility. Keeping labor mobility “down” is the main value added of EU outsourcing. Empirically, its relevance to the regional market is established in an input-output framework of relationships with indicators of economic convergence (homogenization effects) and labor mobility (substitution effects) in the EU. Positive correlations with indices of business synchronization and weak negative correlations with measures of labor supply and wages suggest that outsourcing fits well both with strategies fostering market integration and those counterbalancing the politically sensitive labor mobility in the EU. There is no significant evidence to suggest that, at the aggregate level, outsourcing has independent substitution effects with regard to unemployment rates and wages in Western Europe. The geographic expansion of EU integration, therefore, is not a proxy for losses of social welfare in the West. The paper concludes that as the cost efficiency and resource allocation functions of outsourcing facilitate the homogenizing dynamics of regional integration, it is likely to become increasingly subsumed under EU-level regulation and monitoring in a trade-off between the regional interest and domestic sectoral concerns.

Description: This study examines the relationships between deregulation, business strategy (low cost, differentiation, and scope), size, and firm performance in the U.S. airline industry based on archival data for the Major, National, and Large Regional air carriers in the U.S. from 1972 to 1995. Cross-sectional time series regression analysis shows that deregulation had a significant impact on the strategic choices made by airlines. Results also support a significant relationship between business strategy and firm performance. Further, the study found that firm size moderates the environment-business strategy relationship and the business strategy-firm performance relationship, thereby supporting the salience of firm size as a contingency variable in strategy studies.

Description: Compensation hypothesis, which has established a link between trade openness of countries and levels of government spending, has been widely accepted in the literature on trade policy and international globalization. However, the nature of the distribution effects produced by trade is likely to determine the existence of more or less redistribution demands from the median voter, and therefore government growth. In this paper I hypothesize that the effects of trade openness on redistribution demands are not homogeneous between countries, and I argue that they depend both on the type-of-factor endowment of the economy and the size of the sectors more likely to be affected by trade. I test this hypothesis with ISSP data for 23 countries, both with a country level and an individual level analysis. The results show that redistribution demands issued from trade openness of the median voter of a country are largely conditional on GDP per capita and size of potential loser sectors such as manufacturing: while trade has a negative effect on pro-redistribution preferences in “poor” and/or in “low manufacturing” countries; it positively affects pro-redistribution preferences in “rich” and/or in “high manufacturing” countries. Additionally, I empirically observe that the size of the loser sector plays a more important mediating role than the type-of-factor endowment of the economy.

Description: Democratic consolidation was the top priority of re-democratized Argentina and Brazil. Regional integration was also part of this goal from two perspectives: from the outside, through a treaty that diminished the scope for political manoeuvring by the military and increased international support for the incumbent administrations, and; from within, through encouragement of a proactive role for business in integration that would give it democratic legitimacy, while, at the same time, exercising democratic practices. Argentine and Brazilian political classes expected to combine these two aspects but soon had to face business reluctance. Government-business relations in the construction of Mercosur reflected government attempts to balance the trade-off between the approaches from without and from within. Although business was largely excluded from the strategic formulation of integration, in a democratic context, governments have to accommodate societal interests. This occurred through a significant overlap between powerful business interests and the executive's plans. The achievement of integration helped consolidate democracy and the choices made by political elites drove forward the democratic process.

Description: This paper focuses on the use of the radiocarbon content of marine shells collected along the Portuguese coast as a proxy for the intensity of coastal upwelling off of Portugal. Differences in the 14C ages of closely associated marine mollusk shells and terrestrial material (charcoal or bones) from several Portuguese archaeological contexts seem to be significant throughout the Holocene. ΔR values range from 940 ± 50 to −160 ± 40 14C yr. Five of these values are significantly higher than the modern value (250 ± 25 14C yr), while the remaining values are lower. The modern value was calculated by measuring the 14C content of live-collected, pre-bomb marine mollusk shells. This value is in accordance with an active upwelling of strong intensity that currently occurs off of Portugal. Some primary observations based on data presented here can be made: i) during the Holocene important changes have occurred in the ocean reservoir effect off the Portuguese coast; ii) these fluctuations may be correlated with regional oceanographic changes, namely with changes in the strength of coastal upwelling; and iii) these changes suggest some sort of variability of the climatic factors forcing coastal upwelling off of Portugal.

Description: Dating ice samples from glaciers via radiocarbon is a challenge that requires systematic investigations. This work describes an approach for extraction and accelerator mass spectrometry (AMS) 14C analysis of the particulate organic carbon (POC) fraction in glacier ice samples. Measurements were performed at VERA (Vienna Environmental Research Accelerator) on ice samples obtained mainly from the non-temperated ablation zone of the Grenzgletscher (Grenz Glacier) system (Monte Rosa Massif, Swiss Alps). The samples were obtained from 2 sampling sites situated roughly on a common flow line. The sample masses used were between 0.3 and 1.4 kg of ice, yielding between 18 and 307 μg of carbon as POC. The carbon contamination introduced during sample processing varied between 5.4 and 33 μg C and originated mainly from the quartz filters and the rinsing liquids used in processing. Minimum sample sizes for successful graphitization of CO2 in our laboratory could be reduced to

Description: In the journal Radiocarbon, Hall et al. (2005:383) claim that 35-CS-9, located in Bandon Ocean Wayside State Park on the southern Oregon coast, is one of the few Oregon coast sites “that includes sediments and artifacts dating to the early Holocene and possibly to the late Pleistocene.” Their claim for an early Holocene or late Pleistocene human occupation rests on a single radiocarbon date of 11,000 ± 140 BP (12,710–12,680 cal BP) taken from charcoal found at least 20 cm below the nearest artifact. Although Hall et al. compile various kinds of geoarchaeological evidence to support this claim, their case is not convincing. While we applaud aspects of their analyses, the inferences they have drawn are not substantiated by the evidence they present. We agree that 35-CS-9 is a significant site but believe claims for the antiquity of its human use have been exaggerated.

Description: This contribution reports the first set of samples and the creation of an internal reference material at the recently opened Radiocarbon Laboratory at the National Autonomous University of Mexico (UNAM). Samples for the initial measurements were selected from archaeological and dating projects on Teotihuacán, one of the largest and best-studied Mesoamerican urban and ceremonial centers. The 14C dates were compared to results obtained by 2 other laboratories in order to assess the results obtained at UNAM and validate the adopted methodology. As part of the quality assurance protocol, an internal reference material was created that consists of charred wood from the Teotihuacán site with a 14C activity in the value range expected for samples from Mesoamerican archaeological sites. Results from 7 analyses have a mean of 1750 ± 16 BP (80.43 ± 0.16 pMC).

Description: Moss et al. (2006) provided comments and criticisms of our recent paper in this journal (Hall et al. 2005). We can appreciate the need for promoting vigorous dialogue among those interested in the research of early sites along the New World Pacific Margin and thus welcome their intervention; however, we are compelled to respond because they raise several points that require clarification and introduce a critical error that must be corrected.

Description: Isotope tracer studies, particularly radiocarbon measurements, play a key role in biological, nutritional, and environmental research. Accelerator mass spectrometry (AMS) is now the most sensitive detection method for 14C, but AMS is not widely used in kinetic studies of humans. Part of the reason is the expense, but costs would decrease if AMS were used more widely. One component in the cost is sample preparation for AMS. Biological and environmental samples are commonly reduced to graphite before they are analyzed by AMS. Improvements and mechanization of this multistep procedure is slowed by a lack of organized educational materials for AMS sample preparation that would allow new investigators to work with the technique without a substantial outlay of time and effort. We present a detailed sample preparation protocol for graphitizing biological samples for AMS and include examples of nutrition studies that have used this procedure.

Description: The accelerator mass spectrometry facility at Seoul National University (SNU-AMS) began functioning in December 1998 and was first reported at the Vienna AMS conference in October 1999 and at the 17th International Radiocarbon Conference in Israel in June 2000. At the Vienna conference, we reported our accelerator system (Kim et al. 2000) and details of the basic sample preparation system (Lee et al. 2000), such as the combustion line to produce CO2; the catalytic reduction line for the graphitization of CO2; and the pretreatment procedures for wood, charcoal, and peat samples. The recent progress of the AMS facility (Kim et al. 2001) and the extension of the sample pretreatment system to iron and bone samples were reported at the 17th International Radiocarbon Conference (Cheoun et al. 2001). In the meantime, extensive testing of accuracy and reproducibility has been carried out, and ∼1000 unknown archaeological and geological samples have been measured every year. In this report, the archaeological, geological, and environmental data carried out in 1999 are presented in terms of yr BP.

Description: Oceanic uptake and transport of bomb radiocarbon as 14CO2 created by atmospheric nuclear weapons testing in the 1950s and 1960s has been a useful diagnostic for determining the carbon transfer between the ocean and atmosphere. In addition, the distribution of 14C in the ocean can be used as a tracer of oceanic circulation. Results obtained on samples collected in the Gulf of Alaska in the summer of 2002 provide a direct comparison with results in the 1970s during GEOSECS and in the early 1990s during WOCE. The open gyre values are 20–40% lower than those documented in 1991 and 1993 (WOCE), although the general trends as a function of latitude are reproduced. Surface values are still significantly higher than pre-bomb levels (∼ −105% or lower). In the central gyre, we observe Δ14C values that are lower in comparison to GEOSECS (stn 218) and WOCE P16/P17 to a density of ∼26.8 σt. This observation is consistent with the overall decrease in surface Δ14C values and reflects the erosion of the bomb-14C transient. We propose that erosion of the bomb-14C transient is accomplished by entrainment of low-14C water via vertical exchange within the Gulf of Alaska and replenishment of surface and subther-mocline waters with waters derived from the far northwest Pacific.

Description: Radiocarbon ages of 8 decadal tree rings and 66 single-yr tree rings have been measured with a highly accurate liquid scintillation counting (LSC) system (0.2% error) after synthesizing 10.5 g of benzene for each α-cellulose sample produced from tree rings of Choukai Jindai cedar in Japan (39°N). The 14C ages were between 2449 and 2539 14C yr BP for the 21 samples. From the wiggle-matching of the data set using the IntCal04 (Reimer et al. 2004) calibration data in OxCal v 3.10 (Bronk Ramsey 2005), the estimated age of the outer edge of the Choukai tree rings was 477.5 BC (±12.5 yr) with a confidence level of 95.5%; hence, the Choukai tree rings range from 2757 to 2437 cal BP. The age indicates an improved eruption date of the Choukai Volcano. The statistical errors at 1 σ are approximately ± 10 and ± 7 14C yr for the 5-yr data and the decadal data from the single-yr measurements, respectively. For the interval between 2580 and 2520 cal BP, it is statistically significant that the Choukai 14C ages are ∼16 14C yr older on average than both the IntCal04 and QL German oak (∼50°N) data sets. The ∼2.0% offset is informative for the study of regional offset in the Far East.

Description: Radiocarbon analysis was performed by liquid scintillation counting (LSC) and accelerator mass spectrometry (AMS) to assess whether the content of biological components in hydrocarbon fuels could be derived. Different fuel mixtures were prepared containing bioethanol, fossil ethanol, and fossil gasoline. The specific 14C activity of these mixtures was obtained from LSC measurements and directly related to the concentration of carbon originating from the bioethanol (biocarbon). The results were checked via standardized carbon dating procedures and AMS. A good linear correlation exists between the fuel mixture's specific 14C activity and the concentration of biocarbon. Also, the biocarbon fraction of the fuel mixture (the ratio biocarbon : total carbon) and the normalized fraction of biocarbon (%M) showed good linear correlation. Therefore, both relations provide a possibility to quantitatively determine a fuel's biocarbon content by 14C analysis. When the sample composition is known (e.g. resolved by gas chromatography-mass spectroscopy [GC-MS] and nuclear magnetic resonance [NMR]), the amount of particular biological components in a fuel sample can be derived subsequently. For mixtures of bioethanol, fossil ethanol, and gasoline with bioethanol contents in the range of 0.5–2% m/m, it was found that errors in the normalized fraction of biocarbon (%M) were in the range of 25–10%, respectively. For samples with a higher bioethanol content (up to pure bioethanol), the errors in %M were

Description: The isotopic composition of ancient wood has the potential to provide information about past environments. We analyzed the δ13C, δ18O, and δ2H of cellulose of conifer trees from several cross-sections at each of 9 sites around the Great Lakes region ranging from ∼4000 to 14,000 cal BP. Isotopic values of Picea, Pinus, and Thuja species seem interchangeable for δ18O and δ2H comparisons, but Thuja appears distinctly different from the other 2 in its δ13C composition. Isotopic results suggest that the 2 sites of near-Younger Dryas age experienced the coldest conditions, although the Gribben Basin site near the Laurentide ice sheet was relatively dry, whereas the Liverpool site 500 km south was moister. The spatial isotopic variability of 3 of the 4 sites of Two Creeks age shows evidence of an elevation effect, perhaps related to sites farther inland from the Lake Michigan shoreline experiencing warmer daytime growing season temperatures. Thus, despite floristic similarity across sites (wood samples at 7 of the sites being Picea), the isotopes appear to reflect environmental differences that might not be readily evident from a purely floristic interpretation of macrofossil or pollen identification.

Description: High freshwater inputs into Scottish sea lochs (fjords) combined with the restricted exchange between sea loch basin water and coastal Atlantic water masses are likely to result in reduced regional marine radiocarbon reservoir ages (R[t]) in these environments. To test this hypothesis, historical, museum-archived shells, collected live on known dates prior to AD 1950 from coastal locations in NW Scotland, were 14C dated to provide a means of determining R(t) and hence the regional deviation (ΔR) from the modeled global surface ocean reservoir age (R). The sea loch data, when combined with 14C dates from the Scottish west coast (Harkness 1983), yield a regional ΔR value of −26 ± 14 yr. The ΔR of sea loch (fjordic) and coastal waters of NW Scotland are statistically different (at a confidence level 〉95%) from the ΔR value of 17 ± 14 yr reported for UK coastal waters (Reimer 2005; data after Harkness 1983) and are in good agreement with the coastal ΔR value of −33 ± 93 yr reported by Reimer et al. (2002). Therefore, it is recommended that a regional ΔR correction of −26 ± 14 yr should be applied to modern (i.e. pre-bomb but not prehistoric) marine 14C dates from the NW coast of Scotland.

Description: Extensive radiocarbon dating of human remains from Neolithic and Bronze Age hunter-gatherer cemeteries in the Cis-Baikal region of Siberia has been undertaken as a part of the multidisciplinary examination of this material conducted by the Baikal Archaeology Project (BAP; http://baikal.arts.ualberta.ca). Due to the large number of analyzed samples, this paper reports the 14C results only in the context of the basic archaeological information about each of the cemeteries. Comprehensive evaluation, analysis, and interpretation of this entire data set will be undertaken in separate publications. In fact, the dates for one such cemetery have already been examined on 2 recent occasions (Weber et al. 2004, 2005).

Description: In this paper, we investigate how to achieve high-accuracy radiocarbon measurements by accelerator mass spectrometry (AMS) and present measurement series (performed on archived CO2) of 14CO2 between 1985 and 1991 for Point Barrow (Alaska) and the South Pole. We report in detail the measurement plan, the error sources, and the calibration scheme that enabled us to reach a combined uncertainty of better than ±3%. The δ13C correction and a suggestion for a span (or 2-point) calibration for the 14C scale are discussed in detail. In addition, we report new, accurate values for the calibration and reference materials Ox2 and IAEA-C6 with respect to Oxl. The atmospheric 14CO2 records (1985–1991) are presented as well and are compared with other existing records for that period. The Point Barrow record agrees very well with the existing Fruholmen (northern Norway) record from the same latitude. The South Pole record shows a small seasonal cycle but with an extreme phase with a maximum on January 1st (±13 days). Together with its generally elevated 14C level compared to the Neumayer record (coastal Antarctica), this makes our South Pole data set a valuable additional source of information for global carbon cycle modeling using 14CO2 as a constraint.

Description: Accurate and reliable dating of paleosols, animal remains, and artifacts is of crucial importance in reconstructing environmental change and understanding the interrelationship between human activities and natural environments. Dating different materials in the same sample can help resolve problems such as soil carbon sources and carbon storage state. Conventional radiocarbon dating of soil (inorganic and organic matter) and accelerator mass spectrometry (AMS) dating of animal remains (fossil bones and teeth) result in different ages for materials from the same sample position in a typical loess section at Xinglong Mountain, Yuzhong County, Gansu Province in NW China. Inorganic matter is ∼3400 yr older than organic matter, 4175 ± 175 cal BP to 3808 ± 90 cal BP. A 1610-yr difference between the 14C ages of fossils (animal bones and teeth) and soil organic matter suggests that a depositional hiatus exists in the studied profile. The varying 14C ages of fossils and soil organic and inorganic matter have important implications for paleoclimate reconstructions from loess sections. It is critical to consider the meaning of the variable 14C ages from different material components from the same sample position in terms of soil organic and inorganic carbon storage, vegetation history reconstruction, archaeology, and the study of ancient civilizations.

Description: We analyzed a sediment core from the equatorial Arabian Sea, chronologically constrained by accurate accelerator mass spectrometry (AMS) radiocarbon dates on selected planktonic foraminiferal species, for paleoproductivity variations corresponding to the variations in the Indian Ocean Equatorial Westerlies (IEW). The IEW in turn are positively correlated to the Southern Oscillation Index (SOI), which is a measure of El Niño, Southwest monsoon (SWM), and east African rainfall (EAR). The productivity data show that Indian and east African rainfalls declined from 35,000 calendar yr BP up to the last glacial maximum (LGM), with the maximum El Niño frequency during the last glacial period. From ∼14,500 to ∼2000 calendar yr BP (i.e. core top), we find strengthening SWM and EAR along with declining El Niño frequency.

Description: Archaeometry is becoming an increasingly important tool in chronological research related to events in the Ancient Near East during the 2nd millennium BCE. This paper is a review of recently published radiometric results in an attempt to establish the probable dating range for one particular event that occurred during the last quarter of that millennium, the end of the Late Bronze Age. The conclusion is that in spite of significant improvements in methodology in recent years, the quantity and quality of radiocarbon data are still insufficient to define the range of that date to much better than a century. It is concluded that the most likely date of the Late Bronze/Iron Age transition (here defined by the arrival of Mycenaean LH IIIC:1b pottery in the Levant) is somewhere in the 8-decade range between ∼1170 to 1100 BCE. A comparative study of archaeological and historical evidence would appear to favor the lower value.

Description: Within the framework of radioecological studies, 90Sr was determined in wheat grains, soil, and deposition samples. The radiochemical purification of 90Y consisted of liquid-liquid extraction by tributyl phosphate (TBP), followed by hydroxide and oxalate precipitations and, if necessary, the removal of thorium by anion exchange chromatography. The procedure proved to be very robust and reliable, having yttrium yields of 92.7 ± 4.6% for 1-kg wheat samples, 90.9 ± 4.2% for 50-g soil samples, and 90.6 ± 3.2% for wet and dry deposition samples. 90Y was determined by Cerenkov counting and proportional counting. By optimizing the Cerenkov counting window, a figure of merit (FOM) of 4750 could be reached using a Quantulus™ 1220 system. Minimum detectable activities were in the range of 10 mBq.

Description: Calibration (using CALIBomb) of radiocarbon measurements made on the enamel of human teeth from people born during the nuclear era typically produce 2 possible age ranges that potentially reflect the period of tooth formation. These ranges correspond to periods before and after the 1963 atmospheric 14C maximum. Further measurements made on the collagen component of the combined dentine and cementum from the roots of the same teeth enable the appropriate age range to be selected. Using this range and the formation times for individual teeth, we estimated the year of birth of the individuals and compared these to the known dates of birth. The results were relatively accurate and confirmed those of a previous study by another research group. The present study demonstrates that it is possible to produce a good estimate of the year of birth from a single tooth.

Description: In recent years, International Political Economy literature on “politics beyond state” has emphasized the role of non-governmental organizations (NGOs) in broader policy processes, both national and international. In addition to their impact on states, NGOs influence the policies of non-state actors such as firms via public and private politics. Dissatisfied with the progress firms have made in response to public regulation, NGOs have sponsored private authority regimes in several issue areas and pushed firms to participate in them. Across the world, the contest between NGOs and firms has provoked substantial behavioral and programmatic change'including widespread participation in these private authority regimes'among firms seeking to escape NGO pressures. Using firm-level data, this paper examines why direct targeting has not led firms in the U.S. forest products sector to participate in an NGO-sponsored private authority regime, the Forest Stewardship Council. This global regime has been adopted widely in Europe, but U.S.-based forestry firms have tended to favor a domestic industry-sponsored regime, the Sustainable Forestry Initiative. Our analysis suggests that the desire of firms to maintain control over their institutional environment in light of hostile relations with NGOs has led US-based firms to favor the Sustainable Forestry Initiative.

Description: In the study of corporate political activity in the United States, scholars have consistently relied on samples comprised entirely or principally of large firms. While scholars have raised the issue of bias in these samples, there have been no systematic examinations of the consequences for causal inference. We address this issue directly by comparing the results of comprehensive models that examine corporate lobbying using both large-firm and randomly-generated samples. We find that while there are some notable differences, they are certainly not so large as to lead us to question fundamentally the results of decades of scholarship. In short, the results generated using a random sample lead to causal inferences largely consistent with those in the theoretical and empirical literature. In particular, firms' resources and interactions with government condition both their decisions to lobby and the level of their activity.

Description: Why do some countries institutionalize a social program compensating the unemployed while others do not? My main argument is that the choice to have an unemployment insurance program is a function of 1) the distribution of unemployment risks within a country and 2) political processes through which demands for insurance are realized. The distribution of industrial-specific risks and workers' employment status are the driving force in shaping workers' demands. In developing countries, these demands are more likely to be realized under democratic regimes. An event history model for 102 developing countries from 1946 to 2000 is used to test the arguments.

Description: This paper examines the motivation and impact of corporate diversification in Chinese listed firms. We find that in local government owned-firms there is a non-linear relationship between the level of firm diversification and state ownership. As state ownership increases from zero, the level of diversification decreases. After state ownership reaches a certain level, the level of diversification increases as state ownership increases. There is no evidence that ownership is related to corporate diversification in non-state-owned firms or central government-owned firms. We also document that diversification is negatively related to firm performance in local government-owned firms. However, there is no evidence that diversification is negatively related to the firm performance in non-state-owned firms or central government-owned firms. Our findings suggest that agency problems are responsible for local government owned-firms taking value-reducing diversification strategies.

Description: We assess the potential damage and smoke production associated with the detonation of small nuclear weapons in modern megacities. While the number of nuclear warheads in the world has fallen by about a factor of three since its peak in 1986, the number of nuclear weapons states is increasing and the potential exists for numerous regional nuclear arms races. Eight countries are known to have nuclear weapons, 2 are constructing them, and an additional 32 nations already have the fissile material needed to build substantial arsenals of low-yield (Hiroshima-sized) explosives. Population and economic activity worldwide are congregated to an increasing extent in megacities, which might be targeted in a nuclear conflict. Our analysis shows that, per kiloton of yield, low yield weapons can produce 100 times as many fatalities and 100 times as much smoke from fires as high-yield weapons, if they are targeted at city centers. A single "small'' nuclear detonation in an urban center could lead to more fatalities, in some cases by orders of magnitude, than have occurred in the major historical conflicts of many countries. We analyze the likely outcome of a regional nuclear exchange involving 100 15-kt explosions (less than 0.1% of the explosive yield of the current global nuclear arsenal). We find that such an exchange could produce direct fatalities comparable to all of those worldwide in World War II, or to those once estimated for a "counterforce'' nuclear war between the superpowers. Megacities exposed to atmospheric fallout of long-lived radionuclides would likely be abandoned indefinitely, with severe national and international implications. Our analysis shows that smoke from urban firestorms in a regional war would rise into the upper troposphere due to pyro-convection. Robock et al. (2006) show that the smoke would subsequently rise deep into the stratosphere due to atmospheric heating, and then might induce significant climatic anomalies on global scales.We also anticipate substantial perturbations of global ozone. While there are many uncertainties in the predictions we make here, the principal unknowns are the type and scale of conflict that might occur. The scope and severity of the hazards identified pose a significant threat to the global community. They deserve careful analysis by governments worldwide advised by a broad section of the world scientific community, as well as widespread public debate.

Description: We briefly present in this short paper a new SIze REsolved Aerosol Model (SIREAM) which simulates the evolution of atmospheric aerosol by solving the General Dynamic Equation (GDE). SIREAM segregates the aerosol size distribution into sections and solves the GDE by splitting coagulation and condensation/evaporation. A moving sectional approach is used to describe the size distribution change due to condensation/evaporation and a hybrid method has been developed to lower the computational burden. SIREAM uses the same physical parameterizations as those used in the Modal Aerosol Model, MAM sartelet05development. It is hosted in the modeling system POLYPHEMUS (Mallet et al., 2006) but can be linked to any other three-dimensional Chemistry-Transport Model.

Description: The results from three 45-year simulations of a coupled chemistry climate model are analysed for solar cycle influences on ozone and temperature. The simulations include UV forcing at the top of the atmosphere, which includes a generic 27-day solar rotation effect as well as the observed monthly values of the solar fluxes. The results are analysed for the 27-day and 11-year cycles in temperature and ozone. In accordance with previous results, the 27-day cycle results are in good qualitative agreement with observations, particularly for ozone. However, the results show significant variations, typically a factor of two or more in sensitivity to solar flux, depending on the solar cycle. We show for the first time good agreement also between the observed 11-year cycle and model results for the ozone vertical profile, which both indicate a minimum in solar response near 20 hPa. In comparison, simulations of the model with fixed solar phase (solar maximum/solar mean) and climatological sea surface temperatures lead to a poor simulation of the solar response in the ozone vertical profile. The results indicate the need for variable phase simulations in solar sensitivity experiments and the role of sea surface temperatures is discussed.

Description: The aerosol chemical mass closure is revisited and a simple and inexpensive methodology is proposed. This methodology relies on data obtained for aerosol mass, and concentration of the major ions and the two main carbon components, the organic carbon (OC) and the black carbon (BC). Atmospheric particles are separated into coarse (AD〉2µm) and fine (AD

Description: Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections.

Description: We describe and begin to evaluate a parameterization to include the vertical transport of hot gases and particles emitted from biomass burning in low resolution atmospheric-chemistry transport models. This sub-grid transport mechanism is simulated by embedding a 1-D cloud-resolving model with appropriate lower boundary conditions in each column of the 3-D host model. Through assimilation of remote sensing fire products, we recognize which columns have fires. Using a land use dataset appropriate fire properties are selected. The host model provides the environmental conditions, allowing the plume rise to be simulated explicitly. The derived height of the plume is then used in the source emission field of the host model to determine the effective injection height, releasing the material emitted during the flaming phase at this height. Model results are compared with CO aircraft profiles from an Amazon basin field campaign and with satellite data, showing the huge impact that this mechanism has on model performance. We also show the relative role of each main vertical transport mechanisms, shallow and deep moist convection and the pyro-convection (dry or moist) induced by vegetation fires, on the distribution of biomass burning CO emissions in the troposphere.

Description: We use a modern climate model and new estimates of smoke generated by fires in contemporary cities to calculate the response of the climate system to a regional nuclear war between emerging third world nuclear powers using 100 Hiroshima-size bombs (less than 0.03% of the explosive yield of the current global nuclear arsenal) on cities in the subtropics. We find significant cooling and reductions of precipitation lasting years, which would impact the global food supply. The climate changes are large and long-lasting because the fuel loadings in modern cities are quite high and the subtropical solar insolation heats the resulting smoke cloud and lofts it into the high stratosphere, where removal mechanisms are slow. While the climate changes are less dramatic than found in previous "nuclear winter'' simulations of a massive nuclear exchange between the superpowers, because less smoke is emitted, the changes are more long-lasting because the older models did not adequately represent the stratospheric plume rise.

Description: Retrieved aerosol optical thickness (AOT) based on data obtained by the Sea viewing Wide Field Sensor (SeaWiFS) is combined with surface wind speed, obtained at the European Centre for Medium-Range Weather Forecasts (ECMWFs), over the North Pacific for September 2001. In this study a cloud screening approach is introduced in an attempt to exclude pixels partly or fully covered by clouds. The relatively broad swath width for which the nadir looking SeaWiFS instrument scanned over the North Pacific means that the AOT can be estimated according to relatively large range of wind speeds for each of the scenes analyzed. The sensitivity in AOT due to sea salt and hygroscopic growth of the marine aerosols has also been investigated. The validation of the results is based on previous parameterization in combination with the environmental quantities wind speed, RH and boundary layer height (BLH), estimated at the ECMWF. In this study a factor of 2 higher mean AOT is obtained for a wind speed up to about 13 m s−1 for September 2001 over remote ocean areas. Furthermore, a factor of 2 higher AOT is more or less supported by the validation of the results. Approximately, 50% of the enhancement seems to be due to hygroscopic growth of the marine aerosols and the remaining part due to increase in the sea salt particle mass concentrations, caused by a wind driven water vapor and sea salt flux, respectively. Reasonable agreement occurs also between satellites retrieved aerosol optical thickness and AOT observed at several AERONET (Aerosol Robotic NETwork) ground-based remote sensing stations. Finally, possible reasons why relatively large standard deviations occur around the mean values of AOT estimated for a single scene are discussed.

Description: Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO2), hydrogen sulphide (H2S), hydrogen chloride (HCl) and hydrogen fluoride (HF) concentrations in the volcanic plumes (typically several minutes to a few hours old) were repeatedly determined at distances from the summit vents ranging from 0.1 to ~10 km, and under different environmental conditions. At both volcanoes, acidic gas concentrations were found to decrease exponentially with distance from the summit vents (e.g., SO2 decreases from ~10 000 μg/m3 at 0.1 km from Etna's vents down to ~7 μg/m3 at ~10 km distance), reflecting the atmospheric dilution of the plume within the acid gas-free background troposphere. Conversely, SO2/HCl, SO2/HF, and SO2/H2S ratios in the plume showed no systematic changes with plume aging, and fit source compositions within analytical error. Assuming that SO2 losses by reaction are small during short-range atmospheric transport within quiescent (ash-free) volcanic plumes, our observations suggest that, for these short transport distances, atmospheric reactions for H2S and halogens are also negligible. The one-dimensional model MISTRA was used to simulate quantitatively the evolution of halogen and sulphur compounds in the plume of Mt. Etna. Model predictions support the hypothesis of minor HCl chemical processing during plume transport, at least in cloud-free conditions. Larger variations in the modelled SO2/HCl ratios were predicted under cloudy conditions, due to heterogeneous chlorine cycling in the aerosol phase. The modelled evolution of the SO2/H2S ratios is found to be substantially dependent on whether or not the interactions of H2S with halogens are included in the model. In the former case, H2S is assumed to be oxidized in the atmosphere mainly by OH, which results in minor chemical loss for H2S during plume aging and produces a fair match between modelled and measured SO2/H2S ratios. In the latter case, fast oxidation of H2S by Cl leads to H2S chemical lifetimes in the early plume of a few seconds, and thus SO2 to H2S ratios that increase sharply during plume transport. This disagreement between modelled and observed plume compositions suggests that more in-detail kinetic investigations are required for a proper evaluation of H2S chemical processing in volcanic plumes.

Description: The Active Tracer High-resolution Atmospheric Model (ATHAM) has been adopted to examine the aerosol indirect effect in contrasting clean and polluted cloudy boundary layers during the Second Aerosol Characterization Experiment (ACE-2). Model results are in good agreement with available in-situ observations, which provides confidence in the results of ATHAM. Sensitivity tests have been conducted to examine the response of the cloud fraction (CF), cloud liquid water path (LWP), and cloud optical depth (COD) to changes in aerosols in the clean and polluted cases. It is shown for two cases that CF and LWP would decrease or remain nearly constant with an increase in aerosols, a result which shows that the second aerosol indirect effect is positive or negligibly small in these cases. Further investigation indicates that the background meteorological conditions play a critical role in the response of CF and LWP to aerosols. When large-scale subsidence is weak as in the clean case, the dry overlying air above the cloud is more efficiently entrained into the cloud, and in so doing, removes cloud water more efficiently, and results in lower CF and LWP when aerosol burden increases. However, when the large-scale subsidence is strong as in the polluted case, the growth of the cloud top is suppressed and the entrainment drying makes no significant difference when aerosol burden increases. Therefore, the CF and LWP remain nearly constant. In both the clean and polluted cases, the COD tends to increase with aerosols, and the total aerosol indirect effect (AIE) is negative even when the CF and LWP decrease with an increase in aerosols. Therefore, the first AIE dominates the response of the cloud to aerosols.

Description: We use a global chemical transport model (GEOS-Chem) to evaluate the consistency of satellite measurements of lightning flashes and ozone precursors with in situ measurements of tropical tropospheric ozone. The measurements are tropospheric O3, NO2, and HCHO columns from the GOME satellite instrument, lightning flashes from the OTD and LIS instruments, profiles of O3, CO, and relative humidity from the MOZAIC aircraft program, and profiles of O3 from the SHADOZ ozonesonde network. We interpret these multiple data sources with our model to better understand what controls tropical tropospheric ozone. Tropical tropospheric ozone is mainly affected by lightning and convection in the upper troposphere and by surface emissions in the lower troposphere. Scaling the spatial distribution of lightning in the model to the observed flash counts improves the simulation of O3 in the upper troposphere by 5–20 ppbv versus in situ observations and by 1–4 Dobson Units versus GOME retrievals of tropospheric O3 columns. A lightning source strength of 5±2 Tg N/yr best represents in situ observations from aircraft and ozonesonde. Tropospheric NO2 and HCHO columns from GOME are applied to provide top-down constraints on emission inventories of NOx (biomass burning and soils) and VOCs (biomass burning). The top-down biomass burning inventory is larger by a factor of 2 for HCHO and alkenes, and by 2.6 for NOx over northern equatorial Africa. These emissions increase lower tropospheric O3 by 5–20 ppbv, improving the simulation versus aircraft observations, and by 4 Dobson Units versus GOME observations of tropospheric O3 columns. Emission factors in the a posteriori inventory are more consistent with a recent compilation from in situ measurements. The ozone simulation using two different dynamical schemes (GEOS-3 and GEOS-4) is evaluated versus observations; GEOS-4 better represents O3 observations by 5–15 ppbv due to enhanced convective detrainment in the upper troposphere. Heterogeneous uptake of HNO3 on aerosols reduces simulated O3 by 5–7 ppbv, reducing a model bias versus in situ observations over and downwind of deserts. Exclusion of HO2 uptake on aerosols improves O3 by 5 ppbv in biomass burning regions.

Description: The mechanisms responsible for the extreme dryness of the stratosphere have been debated for decades. A key difficulty has been the lack of models which are able to reproduce the observations. Here we examine results from a new atmospheric chemistry general circulation model (ECHAM5/MESSy1) together with satellite observations. Our model results match observed temperatures in the tropical lower stratosphere and realistically represent recurrent features such as the semi-annual oscillation (SAO) and the quasi-biennual oscillation (QBO), indicating that dynamical and radiation processes are simulated accurately. The model reproduces the very low water vapor mixing ratios (1–2 ppmv) periodically observed at the tropical tropopause near 100 hPa, as well as the characteristic tape recorder signal up to about 10 hPa, providing evidence that the dehydration mechanism is well-captured, albeit that the model underestimates convective overshooting and consequent moistening events. Our results show that the entry of tropospheric air into the stratosphere at low latitudes is forced by large-scale wave dynamics; however, radiative cooling can regionally limit the upwelling or even cause downwelling. In the cold air above cumulonimbus anvils thin cirrus desiccates the air through the sedimentation of ice particles, similar to polar stratospheric clouds. Transport deeper into the stratosphere occurs in regions where radiative heating becomes dominant, to a large extent in the subtropics. During summer the stratosphere is moistened by the monsoon, most strongly over Southeast Asia.

Description: Spores and related chemical compounds from actively spore-discharging Ascomycota (AAM) and actively spore-discharging Basidiomycota (ABM) are primary biogenic components of air particulate matter (characteristic size range 1–10 μm). Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the forcible discharge of fungal spores may account for a large proportion of coarse air particulate matter in tropical rainforest regions during the wet season. For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol, mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively discharged basidiospores (ABS), and that the literature-derived emission ratio of about 5 pg per ABS may be taken as a representative average. ABM emissions may account for most of the atmospheric abundance of mannitol, and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter, but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season, and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol in particulate matter, which is consistent with the above emission ratio and the observed abundance of ABS, we have also calculated a value of ~17 Tg yr−1 as a first estimate for the global average emission rate of ABS over land surfaces. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr−1 of anthropogenic primary organic aerosol; 12–70 Tg yr−1 of secondary organic aerosol) indicate that emissions from actively spore-discharging fungi should be taken into account as a significant source of organic aerosol. Their effects might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

Description: The upwelling planetary wave activity (PW) from the troposphere controls the intensity of the equator to pole transport of stratospheric ozone by the Brewer-Dobson circulation and thereby modulates the total ozone content at mid- and high-latitudes. Rayleigh lidar temperature data obtained from 1981 to 2001 at mid-latitude were used to study the interannual variability of PW activity in winter (October to April). The spectrum of stratospheric temperature fluctuations exhibits 2 peaks corresponding to 2 dominant modes of free travelling Rossby waves known as 16 day- and 12 day-waves. The 12 day-wave activity is shown to be anticorrelated with the equatorial QBO wind at 40 hPa. During the period 1981–2000 the global PW activity shows a negative trend for months October to January and a positive trend in March and April.

Description: The use of SAGE III multiwavelength aerosol extinction coefficient measurements to infer PSC type is contingent on the robustness of both the extinction magnitude and its spectral variation. Past validation with SAGE II and other similar measurements has shown that the SAGE III extinction coefficient measurements are reliable though the comparisons have been greatly weighted toward measurements made at mid-latitudes. Some aerosol comparisons made in the Arctic winter as a part of SOLVE II suggested that SAGE III values, particularly at longer wavelengths, are too small with the implication that both the magnitude and the wavelength dependence are not reliable. Comparisons with POAM III have also suggested a similar discrepancy. Herein, we use SAGE II data as a common standard for comparison of SAGE III and POAM III measurements in the Arctic winters of 2002/2003 through 2004/2005. During the winter, SAGE II measurements are made infrequently at the same latitudes as these instruments. We have mitigated this problem through the use potential vorticity as a spatial coordinate and thus greatly increased the number of coincident events. We find that SAGE II and III extinction coefficient measurements show a high degree of compatibility at both 1020 nm and 450 nm except a 10–20% bias at both wavelengths. In addition, the 452 to 1020 nm extinction ratio shows a consistent bias of ~30% throughout the lower stratosphere. We also find that SAGE II and POAM III are on average consistent though the comparisons show a much higher variability and larger bias than SAGE II/III comparisons. In addition, we find that the two data sets are not well correlated below 18 km. Overall, we find both the extinction values and the spectral dependence from SAGE III are robust and we find no evidence of a significant defect within the Arctic vortex.

Description: In this paper, we study the transport of air mass to San Pietro Capofiume (SPC) in Po Valley, Italy, by means of back trajectory analysis. Our main aim is to investigate whether air masses originate from different regions on nucleation event days and on nonevent days, during three years when nucleation events have been continuously recorded at SPC. The results indicate that nucleation events occur frequently in air masses arriving form Central Europe, whereas event frequency is much lower in air transported from southern directions and from the Atlantic Ocean. We also analyzed the behaviour of meteorological parameters during 96 h transport to SPC, and found that on average, event trajectories undergo stronger subsidence during the last 12 h before the arrival at SPC than nonevent trajectories. This causes a reversal in the temperature and relative humidity (RH) differences between event and nonevent trajectories: between 96 and 12 h back time, temperatures are lower and RH's higher for event than nonevent trajectories and between 12 and 0 h vice versa. Boundary layer mixing is stronger along the event trajectories compared to nonevent trajectories. The absolute humidity (AH) is similar for the event and nonevent trajectories between about 96 h and about 60 h back time, but after that, the event trajectories AH becomes lower due to stronger rain. We also studied transport of SO2 to SPC, and conclude that although sources in Po Valley most probably dominate the measured concentrations, certain Central and Eastern European sources can also have a non-negligible contribution.

Description: Reactive halogens are responsible for boundary-layer ozone depletion and mercury deposition in Polar Regions during springtime. To investigate the source of reactive halogens in the air arriving at Barrow, Alaska, we measured BrO, a marker of reactive halogen chemistry, and correlated its abundance with airmass histories derived from meteorological back trajectories and remotely sensed sea ice properties. The BrO is found to be positively correlated to first-year sea-ice contact (R2=0.55), and weakly negatively correlated to potential frost flower (PFF) contact (R2=0.04). These data indicate that snow contaminated with sea salts on first-year sea ice is a more probable bromine source than are frost flowers. Recent climate-driven changes in Arctic sea ice are likely to alter frost flower and first year sea ice prevalence, suggesting a significant change in reactive halogen abundance, which will alter the chemistry of the overlying Arctic atmosphere.

Description: Systematic analyses of interannual and seasonal variations of tropospheric NO2 vertical column densities (VCDs) based on GOME satellite data and the regional scale chemical transport model (CTM), Community Multi-scale Air Quality (CMAQ), are presented over eastern Asia between 1996 and June 2003. A newly developed year-by-year emission inventory (REAS) was used in CMAQ. The horizontal distribution of annual averaged GOME NO2 VCDs generally agrees well with the CMAQ results. However, CMAQ/REAS results underestimate the GOME retrievals with factors of 2–4 over polluted industrial regions such as Central East China (CEC), a major part of Korea, Hong Kong, and central and western Japan. For the Japan region, GOME and CMAQ NO2 data show good agreement with respect to interannual variation and show no clear increasing trend. For CEC, GOME and CMAQ NO2 data show good agreement and indicate a very rapid increasing trend from 2000. Analyses of the seasonal cycle of NO2 VCDs show that GOME data have systematically larger dips than CMAQ NO2 during February–April and September–November. Sensitivity experiments with fixed emission intensity reveal that the detection of emission trends from satellite in fall or winter have a larger error caused by the variability of meteorology. Examination during summer time and annual averaged NO2 VCDs are robust with respect to variability of meteorology and are therefore more suitable for analyses of emission trends. Analysis of recent trends of annual emissions in China shows that the increasing trends of 1996–1998 and 2000–2002 for GOME and CMAQ/REAS show good agreement, but the rate of increase by GOME is approximately 10–11% yr−1 after 2000; it is slightly steeper than CMAQ/REAS (8–9% yr−1). The greatest difference was apparent between the years 1998 and 2000: CMAQ/REAS only shows a few percentage points of increase, whereas GOME gives a greater than 8% yr−1 increase. The exact reason remains unclear, but the most likely explanation is that the emission trend based on the Chinese emission related statistics underestimates the rapid growth of emissions.

Description: The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic products of ozonolysis in increasing the oxidative capacity of the troposphere, are also discussed.

Description: The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations and accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.

Description: In order to improve the representation of the shortwave radiative transfer in the MAECHAM5 general circulation model, the spectral resolution of the shortwave radiation parameterization used in the model has been increased and extended in the UV-B and UV-C bands. The upgraded shortwave parameterization is first validated offline with a 4 stream discrete-ordinate line-by-line model. Thereafter, two 20-years simulations with the MAECHAM5 middle atmosphere general circulation model are performed to evaluate the temperature changes and the dynamical feedbacks arising from the newly introduced parameterization. The offline clear-sky comparison of the standard and upgraded parameterizations with the discrete ordinate model shows considerable improvement for the upgraded parameterization in terms of shortwave fluxes and heating rates. In the simulation with the upgraded ratiation parameterization, we report a significant warming of almost the entire atmosphere, largest at 1 hPa at the stratopause, and stronger zonal mean zonal winds in the middle atmosphere. The warming at the summer stratopause alleviates the cold bias present in the model when the standard radiation scheme is used. The stronger zonal mean zonal winds induce a dynamical feedback that results in a dynamical warming (cooling) of the polar winter (summer) mesosphere, caused by an increased downward (upward) circulation in the winter (summer) hemisphere. In the troposphere, the changes in the spectral resolution and the associated changes in the cloud optical parameters introduce a relatively small warming and, consistenly, a moisteneing. The warming occurs mostly in the upper troposphere and can contribute to a possible improvement of the model temperature climatology.

Description: This study investigates the connections between atmospheric sulphuric acid and new particle formation during QUEST III and BACCI/QUEST IV campaigns. The campaigns have been conducted in Heidelberg (2004) and Hyytiälä (2005), the first representing a polluted site surrounded by deciduous forest, and the second a rural site in a boreal forest environment. We have studied the role of sulphuric acid in particle formation and growth by determining 1) the power-law dependencies between sulphuric acid ([H2SO4]), and particle concentrations (N3–6) or formation rates at 1 nm and 3 nm (J1 and J3; 2) the time delays between [H2SO4] and N3–6 or J3, and the growth rates for 1–3 nm particles; 3) the empirical nucleation coefficients A and K in relations J1=A[H2SO4] and J1=K[H2SO4]2, respectively; 4) theoretical predictions for J1 and J3 for the days when no significant particle formation is observed, based on the observed sulphuric acid concentrations and condensation sinks. In both environments, N3–6 or J3 and [H2SO4] were linked via a power-law relation with exponents typically ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation have the potential to explain the observed particle formation. However, some differences between the sites existed: The 1–3 nm growth rates were slightly higher and the nucleation coefficients about an order of magnitude greater in Heidelberg than in Hyytiälä conditions. The time lags between J3 and [H2SO4] were consistently lower than the corresponding delays between N3–6 and [H2SO4]. The exponents in the J3∝[H2SO4]nJ3-connection were consistently higher than or equal to the exponents in the relation N3–6∝[H2SO4]nN36. In the J1 values, no significant differences were found between the observed rates on particle formation event days and the predictions on non-event days. The J3 values predicted by the cluster activation or kinetic nucleation hypotheses, on the other hand, were considerably lower on non-event days than the rates observed on particle formation event days. This study provides clear evidence implying that the main process limiting the observable particle formation is the competition between the growth of the freshly formed particles and their loss by scavenging, rather than the initial particle production by nucleation of sulphuric acid. In general, it can be concluded that the simple models based on sulphuric acid concentrations and particle formation by cluster activation or kinetic nucleation can predict the occurence of atmospheric particle formation and growth well, if the particle scavenging is accurately accounted for.

Description: Atmospheric cloud condensation nuclei (CCN) concentrations are a key uncertainty in the assessment of the effect of anthropogenic aerosols on clouds and climate. The ability of new ultrafine particles to grow to become CCN varies throughout the atmosphere and must be understood in order to understand CCN formation. We have developed the Probability of Ultrafine particle Growth (PUG) model to answer questions regarding which growth and sink mechanisms control this growth, how the growth varies between different parts of the atmosphere and how uncertainties with respect to the magnitude and size distribution of ultrafine emissions translates into uncertainty in CCN generation. It was found in most cases that condensation is the dominant growth mechanism and coagulation with larger particles is the dominant sink mechanism for ultrafine particles. In this work we found that the probability of a new ultrafine particle generating a CCN varies from 90% in different parts of the atmosphere, though in the boundary layer a large fraction of ultrafine particles have a probability between 5% and 40%. Some regions, such as the tropical free troposphere, are areas with high probabilities; however, variability within regions makes it difficult to predict which regions of the atmosphere are most efficient for generating CCN from ultrafine particles. For a given mass of primary ultrafine aerosol, an uncertainty of a factor of two in the modal diameter can lead to an uncertainty in the number of CCN generated as high as a factor for eight. It was found that no single moment of the primary aerosol size distribution, such as total mass or number, is a robust predictor of the number of CCN ultimately generated. Therefore, a complete description of the size distribution is generally required for global aerosol microphysics models.

Description: Long-range atmospheric transport to Svalbard has been studied with a compilation of 4 years of daily trajectories to determine how the atmospheric flow patterns influence the observed methane (CH4) at Mt. Zeppelin station (475 m.a.s.l.) in Ny-Ålesund (78°54' N, 11°53' E). The flow patterns were determined through cluster analysis of 5-day back-trajectories arriving at Ny-Ålesund twice a day (00:00 and 12:00 UTC) for the period 2000–2003. Eight cluster patterns were obtained and used in the analysis of the continuous methane measurements at Mt. Zeppelin station. The analysis shows a shift in frequencies eastward into the Arctic compared to identical studies of transport for 1992–2001. Higher concentrations of methane are mainly seen in clusters with transport from Europe and Russia in contrast to air following transport pathways within the Arctic Basin. The vertical motion of the trajectories has been investigated and shows that it has an effect on the methane concentration at the Mt. Zeppelin station. This is consistent with previous similar studies of CO2 and of other anthropogenic species. Seasonal variation in trajectory frequency can be seen, like for instance more trajectories from Europe and Siberia during winter, and short trajectories from the Arctic region in summer. The identified seasonal and indications of decadal shifts in transport pathways translate into shifts in source areas sampled by a single station. To determine shifts in regional source (and sink) strengths it is necessary to correct for transport pathway shifts when interpreting time series data.

Description: An intercomparison of three Fourier transform spectrometers (FTSs) with significantly different resolutions is presented. The highest-resolution instrument has a maximum optical path difference of 250 cm, and the two lower-resolution instruments have maximum optical path differences of 50 cm and 25 cm. The results indicate that the two lower-resolution instruments can retrieve total column amounts of O3, HCl, N2O and CH4 using the SFIT2 retrieval code with percent differences from the high-resolution instrument generally better than 3%, with respect to the high-resolution FTS. Total column amounts of the stratospheric species (O3 and HCl) have larger differences than those of the tropospheric species (N2O and CH4). Instrument line shape (ILS) information is found to be of critical importance when retrieving total columns of stratospheric gases from the lower-resolution instruments. Including the ILS information in the retrievals significantly reduces the difference in total column amounts between the three instruments. The remaining errors for stratospheric species total column amounts can be attributed to the lower sensitivity of the lower-resolution FTSs to the stratosphere.

Description: There is increasing evidence that there exist interstellar-terrestrial relations and that the heliosphere's effectivity to serve as a protecting shield for the Earth, specifically against cosmic rays, is varying in time. Nonetheless, a debate is going on whether, amongst other drivers, the Sun or the cosmic rays are influencing the terrestrial climate, particularly on periods of hundred years and shorter. As the modelling of the transport of cosmic rays in the heliosphere has evolved from pure test particle simulations to far more consistent treatments, one can explain various correlations within the framework of physical models and one can make quantitative predictions regarding terrestrial indicators of interstellar-terrestrial relations. This level of understanding and modelling allows to identify a criterion with which one can discriminate between solar and cosmic ray forcing on a period of several decades. We define such a criterion and discuss related existing observations.

Description: Because of its ubiquitous release on land and well-characterized atmospheric loss, radon-222 has been very useful for deducing fluxes of greenhouse gases such as CO2, CH4, and N2O. It is shown here that the radon-tracer method, used in previous studies to calculate regional-scale greenhouse gas fluxes, returns a weighted-average flux (the flux field F weighted by the sensitivity of the measurements to that flux field, f) rather than an evenly-weighted spatial average flux. A synthetic data study using a Lagrangian particle dispersion model and modeled CO2 fluxes suggests that the discrepancy between the sensitivity-weighted average flux and evenly-weighted spatial average flux can be significant in the case of CO2, due to covariance between F and f for biospheric CO2 fluxes during the growing season and also for anthropogenic CO2 fluxes in general. A technique is presented to correct the radon-tracer derived fluxes to yield an estimate of evenly-weighted spatial average CO2 fluxes. A new method is also introduced for correcting the CO2 flux estimates for the effects of radon-222 radioactive decay in the radon-tracer method.

Description: The role of the retention coefficient (i.e. the fraction of a dissolved trace gas which is retained in hydrometeors during freezing) for the scavenging and redistribution of highly soluble trace gases by deep convective cloud systems is investigated using a modified version of the Weather Research and Forecasting (WRF) model. Results from cloud system resolving model runs (in which deep convection is initiated by small random perturbations in association with so-called "large scale forcings (LSF)") for a tropical oceanic (TOGA COARE) and a mid-latitude continental case (ARM) are compared to two runs in which bubbles are used to initiate deep convection (STERAO, ARM). In the LSF runs scavenging is found to almost entirely prevent a highly soluble tracer initially located in the lowest 1.5 km of the troposphere from reaching the upper troposphere, independent of the retention coefficient. The release of gases from freezing hydrometeors leads to mixing ratio increases in the upper troposphere comparable to those calculated for insoluble trace gases only in runs in which bubbles are used to initiate deep convection. This result indicates that previous cloud resolving model studies using bubbles to initiate deep convection may possibly have over-estimated the influence of the retention coefficient on the vertical transport of highly soluble tracers. The retention coefficient is, however, found to play an important role for the scavenging and redistribution of highly soluble trace gases with a (chemical) source in the free troposphere and also for trace gases for which even relatively inefficient transport may be important.

Description: This paper gives an overview of the MIPAS Level 1B (L1B) processor whose main objective is to calibrate atmospheric measurements radiometrically, spectrally and geo-located. It presents also the results of instrument characterization done during the first years in-flight. MIPAS has shown very good performance and stability.

Description: We present the adjoint of the global chemical transport model GEOS-Chem, focusing on the chemical and thermodynamic relationships between sulfate – ammonium – nitrate aerosols and their gas-phase precursors. The adjoint model is constructed from a combination of manually and automatically derived discrete adjoint algorithms and numerical solutions to continuous adjoint equations. Explicit inclusion of the processes that govern secondary formation of inorganic aerosol is shown to afford efficient calculation of model sensitivities such as the dependence of sulfate and nitrate aerosol concentrations on emissions of SOx, NOx, and NH3. The adjoint model is extensively validated by comparing adjoint to finite difference sensitivities, which are shown to agree within acceptable tolerances; most sets of comparisons have a nearly 1:1 correlation and R2〉0.9. We explore the robustness of these results, noting how insufficient observations or nonlinearities in the advection routine can degrade the adjoint model performance. The potential for inverse modeling using the adjoint of GEOS-Chem is assessed in a data assimilation framework through a series of tests using simulated observations, demonstrating the feasibility of exploiting gas- and aerosol-phase measurements for optimizing emission inventories of aerosol precursors.

Description: Principal component analysis provides a fast and robust method to reduce the data dimensionality of an aerosol size distribution data set. Here we describe a methodology for applying principal component analysis to aerosol size distribution measurements. We illustrate the method by applying it to data obtained during five field studies. Most variations in the sub-micrometer aerosol size distribution over periods of weeks can be described using 5 components. Using 6 to 8 components preserves virtually all the information in the original data. A key aspect of our approach is the introduction of a new method to weight the data; this preserves the orthogonality of the components while taking the measurement uncertainties into account. We also describe a new method for identifying the approximate number of aerosol components needed to represent the measurement quantitatively. Applying Varimax rotation to the resultant components decomposes a distribution into independent monomodal distributions. Normalizing the components provides physical meaning to the component scores. The method is relatively simply, computationally fast, and numerically robust. The resulting data simplification provides an efficient method of representing complex data sets and should greatly assist in the analysis of size distribution data.

Description: We have estimated impacts of alternative aviation routings on the radiative forcing. Changes in ozone and OH have been estimated in four Chemistry Transport Models (CTMs) participating in the TRADEOFF project. Radiative forcings due to ozone and methane have been calculated accordingly. In addition radiative forcing due to CO2 is estimated based on fuel consumption. Three alternative routing cases are investigated; one scenario assuming additional polar routes and two scenarios assuming aircraft cruising at higher (+2000 ft) and lower (−6000 ft) altitudes. Results from the base case in year 2000 are included as a reference. Taking first a steady state backward looking approach, adding the changes in the forcing from ozone, CO2 and CH4, the ranges of the models used in this work are −0.8 to −1.8 and 0.3 to 0.6 m Wm−2 in the lower (−6000 ft) and higher (+2000 ft) cruise levels, respectively. In relative terms, flying 6000ft lower reduces the forcing by 5–10% compared to the current flight pattern, whereas flying higher, while saving fuel and presumably flying time, increases the forcing by about 2–3%. Taking next a forward looking approach we have estimated the integrated forcing (m Wm−2 yr) over 20 and 100 years time horizons. The relative contributions from each of the three climate gases are somewhat different from the backward looking approach. The differences are moderate adopting 100 year time horizon, whereas under the 20 year horizon CO2 naturally becomes less important relatively. Thus the forcing agents impact climate differently on various time scales. Also, we have found significant differences between the models for ozone and methane. We conclude that we are not yet at a point where we can include non-CO2 effects of aviation in emission trading schemes. Nevertheless, the rerouting cases that have been studied here yield relatively small changes in the radiative forcing due to the radiatively active gases.

Description: The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. The concentrations of the hydroxyl radical, the hydroperoxy radical and the sum of peroxy radicals, were measured between 25 July and 31 August using laser-induced fluorescence at low pressure and the peroxy radical chemical amplifier techniques. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. OH initiation was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main initiation route for HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.

Description: New atmospheric particles with diameters of 3–10 nm and their subsequent growth to cloud condensation nucleus have been observed at various places in the European boundary layer. These events have been observed simultaneously within wide geographical areas (over 1000 km) in connection to specific weather systems, the cold air behind cyclones. Here we show that atmospheric aerosol formation (i.e. nucleation and initial growth) is favoured by the outbreak of cold Arctic air over northern Europe. Aerosol formation was about twice as common in Arctic air as in sub-Polar air, and even more so compared to other air masses. The most important general factor favouring aerosol formation in Arctic air and marine air was weaker competing condensational sink (CS) for the precursor gases (less pre-existing aerosols), while high CS prevented aerosol formation in heated sub-Polar air and mid-latitude air. High SO2 levels favoured nucleation in continental air and high UV-B radiation in sub-tropical air. The critical factor that determined if aerosol formation would start on a day with Arctic air was the UV-B radiation. The same applied to sub-Polar air and continental air, while increased SO2 concentration could trigger formation in heated sub-Polar and mid-latitude air, and reduced CS could cause formation in mid-latitude, marine or mixed/transient air. We speculate that strong emissions of volatile organic compounds from the Boreal forest and strong boundary layer dynamics may have caused aerosol formation in sub-Polar air masses and air in transition from a marine to a continental character. The monthly frequency of Arctic air masses and the probability for photo-chemically driven aerosol formation explains the observed annual cycle in monthly particle formation frequency as well as much of the inter annual variability. The same cyclones that transport cold, clean air from the Arctic to Europe will also transport warm polluted air in the other direction, which help cause the Arctic Haze phenomena. The cyclones have a key role for the atmospheric aerosol life cycle in mid to high latitudes. Due to the observed growth to the size of CCN in one to two days, there is a potential feed back from the effects on the CCN population and cloud albedo even within the same weather system, but also on the climatic time scale.

Description: It is important to obtain the year-to-year trend of stratospheric minor species in the context of global changes. An important example is the trend in global ozone depletion. The purpose of this paper is to report the accuracy and precision of measurements of stratospheric chemical species that are made at our Poker Flat site in Alaska (65° N, 147° W). Since 1999, minor atmospheric molecules have been observed using a Fourier-Transform solar-absorption infrared Spectrometer (FTS) at Poker Flat. Vertical profiles of the abundances of ozone, HNO3, HCl, and HF for the period from 2001 to 2003 were retrieved from the FTS spectra by using Rodgers' formulation of the Optimal Estimation Method (OEM). The accuracy and precision of the retrievals were estimated by formal error analysis. Errors for the total column were estimated to be 5.3%, 3.4%, 5.9%, and 5.3% for ozone, HNO3, HCl, and HF, respectively. The ozone vertical profiles were in good agreement with profiles derived from collocated ozonesonde measurements that were smoothed with averaging kernel functions that had been obtained with the retrieval procedure used in the analysis of spectra from the ground-based FTS (gb-FTS). The O3, HCl, and HF columns that were retrieved from the FTS measurements were consistent with Earth Probe/Total Ozone Mapping Spectrometer (TOMS) and HALogen Occultation Experiment (HALOE) data over Alaska within the error limits of all the respective datasets. This is the first report from the Poker Flat FTS observation site on a number of stratospheric gas profiles including a comprehensive error analysis.

Description: The volatility of sub-micrometer atmospheric aerosol particles was studied in a rural background environment in Finland using a combination of a heating tube and a scanning mobility particle sizer. The analysis focused on nano-particles formed from nucleation bursts which were subsequently observed during their growth in the diameter range between 5 and 60 nm. During the 6 days of new particle formation shown in detail, the concentrations of newly formed particles increased up to 10 000 cm−3. The number of nucleation mode particles measured after volatilization in the heating tube at 280°C was up to 90% of the total number under ambient conditions. Taking into account the absolute accuracy of the size distribution measurements, all ambient particles found in the rural atmosphere could have a non-volatile core after volatilization at 280°C. As the regional new particle formation events developed over time as a result of further vapor condensation, the newly formed particles grew at an average growth rate of 2.4±0.3 nm h−1. Importantly, the non-volatile cores of nucleation mode particles were also observed to grow over time, however, at a lower average growth rate of 0.6±0.3 nm h−1. One implication of the volatility analysis is that the newly formed particles, which have reached ambient diameters of 15 nm, are unlikely to consist of sulfuric acid, ammonium sulfate, and water alone. A relatively constant ratio between the growth rate of the ambient particles as well as their non-volatile cores indicates that non-volatile matter is formed only gradually in the growing particles. The non-volatile fraction of the particles showed some correlation with the ambient temperature. The composition and formation mechanism of this non-volatile material in nucleation mode particles are, to date, not known.

Description: The temperature dependence of secondary organic aerosol (SOA) formation from ozonolysis of β-pinene was studied in a flow reactor at 263–303 K and 1007 hPa. The observed SOA yields were of similar magnitude as predicted by a two-product model based on detailed gas phase chemistry (Jenkin, 2004), reaching maximum values of 0.22–0.39 at high particle mass concentrations. However, the measurement data exhibited significant deviations (up to 50%) from the predicted linear dependence on inverse temperature. When fitting the measurement data with a two-product model, we found that both the partitioning coefficients (Kom,i) and the stoichiometric yields (αi) of the low-volatile and semi-volatile species vary with temperature. The results indicate that not only the reaction product vapour pressures but also the relative contributions of different gas-phase or multiphase reaction channels are dependent on temperature. We suggest that the modelling of secondary organic aerosol formation in the atmosphere needs to take into account the effects of temperature on the pathways and kinetics of the involved chemical reactions as well as on the gas-particle partitioning of the reaction products.

Description: Absolute principal component analysis can be applied, with suitable modifications, to atmospheric aerosol size distribution measurements. This method quickly and conveniently reduces the dimensionality of a data set. The resulting representation of the data is much simpler, but preserves virtually all the information present in the original measurements. Here we demonstrate how to combine the simplified size distribution data with trace gas measurements and meteorological data to determine the origins of the measured particulate matter using absolute principal component analysis. We have applied the analysis to four different sets of field measurements that were conducted at three sites in southern Ontario. Several common factors were observed at all the sites; these were identified as photochemically produced secondary aerosol particles, regional pollutants (including accumulation mode aerosol particles), and trace gas variations associated with boundary layer dynamics. Each site also exhibited a factor associated specifically with that site: local industrial emissions in Hamilton (urban site), processed nucleation mode particles at Simcoe (polluted rural site), and transported fine particles at Egbert (downwind from Toronto).

Description: Boundary layer concenrations of several volatile organic compounds (VOC) were measured during two campaigns in springs of 2003 and 2006. Measurements were conducted over boreal forests near SMEAR II measurement station in Hyytiälä, Southern Finland. In 2003 the measuremens were performed using light aircraft and in 2006 using hot air ballon. Isoprene concentrarions were low, usually below detection limit. This is explained by low biogenic production due to cold weather. Monoterpenes were observed frequently. Average total monoterpene concentration in the boundary layer was 33 pptv. Many anthropogenic compounds e.g. benzene, xylene and toluene, were observed in high amounts. Ecosystem scale surface emissions were estimated using simple mixed box budget methodology. Total monoterpene fluxes varied up to 80 μg m−2 h−1, α-pinene contributing typically more than two thirds of that. Highest fluxes of anthropogenic compounds were those of p/m xylene.

Description: The performance of a new chemical ionization reaction time-of-flight mass spectrometer (CIR-TOF-MS) utilising the environment chamber SAPHIR (Simulation of Atmospheric Photochemistry In a large Reaction Chamber – Forschungzentrum Jülich, Germany) is described. The work took place as part of the ACCENT (Atmospheric Composition and Change the European NeTwork for excellence) supported oxygenated volatile organic compound (OVOC) measurement intercomparison during January 2005. The experiment entailed the measurement of 14 different atmospherically significant OVOCs at various mixing ratios in the approximate range 10.0–0.6 ppbV. The CIR-TOF-MS operated throughout the exercise with the hydronium ion (H3O+) as the primary chemical ionization (CI) reagent in order to facilitate proton transfer to the analyte OVOCs. The results show the CIR time-of-flight mass spectrometer is capable of detecting a wide range of atmospheric OVOCs down to sub-ppbV mixing ratios with high accuracy and precision. It is demonstrated that the technique has rapid multi-channel response at the required sensitivity, accuracy and precision for atmospheric OVOC measurements.

Description: A fire storm that occured on 28 May 2001 devastated the town of Chisholm, ~150 km north of Edmonton, Alberta, induced a violent fire-invigorated cumulonimbus cloud. This pyro-cumulonimbus (pyro-Cb) had overshooting tops of 2.5–3 km above the tropopause, and injected massive amounts of smoke into the lower stratosphere. Fortunately, this event occurred under good coverage of radar, rain gauge, lightning and satellite measurements, which allowed in-depth documentation of the event. The combination of heat and smoke created a cloud with extremely small drops, which ascended rapidly in violent updrafts. There appeared to be little freezing up to the homogeneous freezing isotherm level of –38°C. A cloud with such small and short-lived highly supercooled drops is incapable of producing precipitation except for few large graupel and hail, which produced the observed radar echoes and charged the cloud with positive lightning. The small cloud drops froze homogeneously to equally small ice particles, for which there is no mechanism to aggregate into precipitation particles that hence remain in the anvil. The small precipitation efficiency implies that only a small fraction of the smoke is scavenged, so that most of it is exhausted through the anvil to the upper troposphere and lower stratosphere. Comparisons with other cases suggest that a pyro-Cb does not have to be as violent as the Chisholm case to have strongly suppressed precipitation. However, this level of convective vigor is necessary to create the overshooting updraft that injects the smoke into the lower stratosphere.

Description: The results of a comparison exercise of radiative transfer models (RTM) of various international research groups for Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) viewing geometry are presented. In contrast to previous comparison exercises, box-air-mass-factors (box-AMFs) for various atmospheric height layers were modelled, which describe the sensitivity of the measurements as a function of altitude. In addition, radiances were calculated allowing the identification of potential errors, which might be overlooked if only AMFs are compared. Accurate modelling of radiances is also a prerequisite for the correct interpretation of satellite observations, for which the received radiance can strongly vary across the large ground pixels, and might be also important for the retrieval of aerosol properties as a future application of MAX-DOAS. The comparison exercises included different wavelengths and atmospheric scenarios (with and without aerosols). The results were systematically investigated with respect to their dependence on the telescope's elevation angle and the azimuth angle. For both dependencies, a strong and systematic influence of aerosol scattering was found indicating that from MAX-DOAS observations also information on atmospheric aerosols can be retrieved. During the various iterations of the exercises, the results from all models showed a substantial convergence, and the final data sets agreed for most cases within about 5%. Larger deviations were found for cases with low atmospheric optical depth, for which the photon path lengths along the line of sight of the instrument can become very large. The differences occurred between models including full spherical geometry and those using only plane parallel approximation indicating that the correct treatment of the Earth's sphericity becomes indispensable. The modelled box-AMFs constitute an universal data base for the calculation of arbitrary (total) AMFs by simple convolution with a given trace gas concentration profile. Together with the modelled radiances and the specified settings for the various exercises, they can serve as test cases for future RTM developments.

Description: Odin-SMR is a limb-sounder operating in the 500 region with the capability of performing measurements down to altitudes of about 10 with relatively low influence of ice clouds. Until now spectra from tropospheric tangent altitudes have been disregarded due to inadequate handling of scattering. A first method to extract upper tropospheric quantities has now been developed, yielding the humidity in two layers around 200 and 130 and information on cloud ice content above 200. The main concern for these retrievals is the calibration performance. A careful analysis indicates a systematic calibration error of about 1 K, but also a random component that differs between the two bands. The random calibration uncertainty results in retrieval errors of 10–60% depending on humidity and band. Presently this prohibits use of single retrievals, but averages can be presented with good accuracy. The fixed calibration error can largely be removed, leaving the spectroscopic uncertainties to dominate the humidity retrieval accuracy, estimated to be around 20%. First results are presented that are in agreement with seasonal structure obtained from other satellite measurements. An encouraging comparison between MOZAIC data and measurements for the 200 layer gives further confidence in the capability of Odin-SMR to measure humidity in the upper tropical troposphere.

Description: We present the first detailed microphysical simulations which are performed online within the framework of a global 3-D chemical transport model (CTM) with full chemistry. The model describes the formation and evolution of four types of polar stratospheric cloud (PSC) particles. Aerosol freezing and other relevant microphysical processes are treated in a full explicit way. Each particle type is described by a binned size distribution for the number density and chemical composition. This set-up allows for an accurate treatment of sedimentation and for detailed calculation of surface area densities and optical properties. Simulations are presented for the Antarctic winter of 2003 and comparisons are made to a diverse set of satellite observations (optical and chemical measurements of POAM III and MIPAS) to illustrate the capabilities of the model. This study shows that a combined resolution approach where microphysical processes are simulated in coarse-grained conditions gives good results for PSC formation and its large-scale effect on the chemical environment through processes such as denitrification, dehydration and ozone loss. It is also shown that the influence of microphysical parameters can be measured directly from these processes.

Description: We report in situ and remote observations proving occasional occurrence of solid particles in the tropical lowest stratosphere, far away from deep convective events. The particles were found during field campaigns in Southeast Brazil (49.03 W 22.36 S). They occur in the altitude range from 17.5 to 20.8 km, at temperatures up to at least 10 K above the expected frost point temperature. While stability of ice particles at these altitudes is unexpected from a theoretical point of view, it is argued that these observations are indications of tropospheric air masses penetrating into the stratosphere during convective overshoots. It is concluded that the intrusion of tropospheric air must have carried a large amount of water with it, which effectively hydrated the lowest stratosphere, and consequently suppressed sublimation. This conclusion is further supported by a separate water vapor mixing ratio profile obtained at the same observation site.

Description: More than three years of measurements of aerosol size-distribution and different gas and meteorological parameters made in Po Valley, Italy were analysed for this study to examine which of the meteorological and trace gas variables effect on the emergence of nucleation events. As the analysis method, we used discriminant analysis with non-parametric Epanechnikov kernel, included in non-parametric density estimation method. The best classification result in our data was reached with the combination of relative humidity, ozone concentration and a third degree polynomial of radiation. RH appeared to have a preventing effect on the new particle formation whereas the effects of O3 and radiation were more conductive. The concentration of SO2 and NO2 also appeared to have significant effect on the emergence of nucleation events but because of the great amount of missing observations, we had to exclude them from the final analysis.

Description: Aerosol spectral measurements by sunphotometers can be characterized by three independent pieces of information: 1) the optical thickness (AOT), a measure of the column aerosol concentration, 2) the optical thickness average spectral dependence, given by the Angstrom exponent (α), and 3) the spectral curvature of α (δα). We propose a simple graphical method to visually convert (α, δα) to the contribution of fine aerosol to the AOT and the size of the fine aerosols. This information can be used to track mixtures of pollution aerosol with dust, to distinguish aerosol growth from cloud contamination and to observe aerosol humidification. The graphical method is applied to the analysis of yearly records at 8 sites in 3 continents, characterized by different levels of pollution, biomass burning and mineral dust concentrations. Results depict the dominance of fine mode aerosols in driving the AOT at polluted sites. In stable meteorological conditions, we see an increase in the size of the fine aerosol as the pollution stagnates and increases in optical thickness. Coexistence of coarse and fine particles is evidenced at the polluted sites downwind of arid regions.

Description: The properties of atmospheric aerosol particles in Marseille and Athens were investigated. The studies were performed in Marseille, France during July 2002 and in Athens Greece during June 2003. The aerosol size distribution and the formation and growth rates of newly formed particles were characterized using Differential Mobility Particle Sizers. Hygroscopic properties were observed using a Hygroscopic Tandem Differential Mobility Analyzer setup. During both campaigns, the observations were performed at suburban, almost rural sites, and the sites can be considered to show general regional background behavior depending on the wind direction. At both sites there were clear pattern for both aerosol number concentration and hygroscopic properties. Nucleation mode number concentration increased during the morning hours indicating new particle formation, which was observed during more than 30% of the days. The observed formation rate was typically more than 1 cm−3 s−1, and the growth rate was between 1.2–9.9 nm h−1. Based on hygroscopicity measurements in Athens, the nucleation mode size increase was due to condensation of both water insoluble and water soluble material. However, during a period of less anthropogenic influence, the growth was to a larger extent due to water insoluble components. When urban pollution was more pronounced, growth due to condensation of water soluble material dominated.

Description: A statistical synthesis of marine aerosol measurements from experiments in four different oceans is used to evaluate a global aerosol microphysics model (GLOMAP). We compare the model against observed size resolved particle concentrations, probability distributions, and the temporal persistence of different size particles. We attempt to explain the observed size distributions in terms of sulfate and sea spray and quantify the possible contributions of anthropogenic sulfate and carbonaceous material to the number and mass distribution. The model predicts a bimodal size distribution that agrees well with observations as a grand average over all regions, but there are large regional differences. Notably, observed Aitken mode number concentrations are more than a factor 10 higher than in the model for the N Atlantic but a factor 7 lower than the model in the NW Pacific. We also find that modelled Aitken mode and accumulation mode geometric mean diameters are generally smaller in the model by 10–30%. Comparison with observed free tropospheric Aitken mode distributions suggests that the model underpredicts growth of these particles during descent to the MBL. Recent observations of a substantial organic component of free tropospheric aerosol could explain this discrepancy. We find that anthropogenic continental material makes a substantial contribution to N Atlantic marine boundary layer (MBL) aerosol, with typically 60–90% of sulfate across the particle size range coming from anthropogenic sources, even if we analyse air that has spent an average of 〉120 h away from land. However, anthropogenic primary black carbon and organic carbon particles do not explain the large discrepancies in Aitken mode number. Several explanations for the discrepancy are suggested. The lack of lower atmospheric particle formation in the model may explain low N Atlantic particle concentrations. However, the observed and modelled particle persistence at Cape Grim in the Southern Ocean, does not reveal a diurnal cycle consistent with a photochemically driven local particle source. We also show that a physically based cloud drop activation scheme is needed to explain the observed change in accumulation mode geometric mean diameter with particle number.

Description: In this study, we evaluate the ability of the BRAMS mesoscale model compared to ECMWF global analysis to simulate the observed vertical variations of water vapour in the tropical upper troposphere and lower stratosphere (UTLS). The observations are balloon-borne measurements of water vapour mixing ratio and temperature from micro-SDLA (Tunable Diode Laser Spectrometer) instrument. Data from two balloon flights performed during the 2004 HIBISCUS field campaign are used to compare with the mesoscale simulations and to ECMWF analysis. The mesoscale model performs significantly better than ECMWF analysis for water vapour in the upper troposphere and similarly or slightly worse for temperature. The improvement provided by the mesoscale model for water vapour comes mainly from (i) the enhanced vertical resolution in the UTLS (250 m for BRAMS and ~1 km for ECMWF model) and (ii) the more detailed microphysical parameterization providing ice supersaturations as in the observations. The ECMWF vertical resolution (~1 km) is too coarse to capture the observed fine scale vertical variations of water vapour in the UTLS. In near saturated or supersaturated layers, the mesoscale model relative humidity with respect to ice saturation is close to observations provided that the temperature profile is realistic. For temperature, ECMWF analysis gives good results partly thanks to data assimilation. The analysis of the mesoscale model results showed that in undersaturated layers, the water vapour profile depends mainly on the dynamics. In saturated/supersaturated layers, microphysical processes play an important role and have to be taken into account on top of the dynamical processes to understand the water vapour profiles. In the lower stratosphere, the ECMWF model and the BRAMS model give very similar water vapour profiles that are significantly dryer than micro-SDLA measurements. This similarity comes from the fact that BRAMS is initialised using ECMWF analysis and that no mesoscale process acts in the stratosphere leading to no modification of the BRAMS results with respect to ECMWF analysis.

Description: We present a simple method to perform degradation correction to Global Ozone Monitoring Experiment (GOME) reflectance spectra by comparing the average reflectance for 60° N–60° S with that at the beginning of GOME observations after removing the dependences on solar zenith angle and seasonal variation. The results indicate positive degradation of up to ~15–25% in the wavelength range 289–370 nm during 2000–2002; the degradation also exhibits significant dependence on wavelength and view zenith angle. These results are consistent with previous studies using radiative transfer models and ozone observations or climatology. The degradation causes retrieval biases of up to ~3% (10 DU, 1 DU=2.69×1016 molecules cm−2), 30% (10 DU), 10%, and 40% in total column ozone, tropospheric column ozone, stratospheric ozone and tropospheric ozone, respectively, from our GOME ozone profile retrieval algorithm. The application of this degradation correction generally improves the retrievals relative to Dobson and ozonesonde measurements during 2000–2003 and improves the retrieval consistency during 1996–2003.

Description: The authors introduce the radiative transfer model CLOUD for reflection, transmission, and absorption characteristics of terrestrial clouds and discuss the accuracy of the approximations used within the model. A Fortran implementation of CLOUD is available for download. This model is fast, accurate, and capable of calculating multiple raditiative transfer characteristics of cloudy media including the spherical and plane albedo, reflection and transmission functions, absorptance as well as global and diffuse transmittance. The approximations are based on the asymptotic solutions of the radiative transfer equations. While the analytic part of the solutions is treated in the code in an approximate way, the correspondent reflection function (RF) of a semi-infinite water cloud R∞ is calculated using numerical solutions of the radiative transfer equations in the assumption of Deirmendjian's cloud C1 model. In the case of ice clouds, the fractal ice crystal model is used. The resulting values of R∞ with respect to the viewing geometry are stored in a look-up table (LUT).

Description: The Lagrangian transport model COMET has been developed to evaluate emission estimates based on atmospheric concentration observations. This paper describes the model and its application in modelling the methane concentrations at the European stations Cabauw and Macehead. The COMET model captures in most cases both synoptic and diurnal variations of the concentrations as a function of time and in absolute size quite well. The explained variability by COMET of the mixed layer concentration for Cabauw varies from 50% to 84%; for all hourly observations in 2002 the explained variability is 71% with a RMSE of 112 ppb. The explained variability for Macehead is 48%. The most important model parameters were tested for their influence on model performance, but in general the model is not very sensitive to variations within acceptable limits. For a regionally and locally polluted continental site the COMET model shows only a small bias and a moderate random error, and therefore is considered to capture the influence of the sources on the concentration variations quite well. It is therefore concluded that inverse methods and more specifically the COMET model is suitable to be applied in deriving independent estimates of greenhouse gas emissions using Source-Receptor relationships.

Description: A light aircraft was equipped with a bank of Condensation Particle Counters (CPCs) (50% cut from 3–5.4–9.6 nm) and a nano-Scanning Mobility Particle Sizer (nSMPS) and deployed along the west coast of Ireland, in the vicinity of Mace Head. The objective of the exercise was to provide high resolution micro-physical measurements of the coastal nucleation mode in order to map the spatial extent of new particle production regions and to evaluate the evolution, and associated growth rates of the coastal nucleation-mode aerosol plume. Results indicate that coastal new particle production is occurring over most areas along the land-sea interface with peak concentrations at the coastal plume-head in excess of 106 cm−3. Pseudo-Lagrangian studies of the coastal plume evolution illustrated significant growth of new particles to sizes in excess of 8 nm approximately 10 km downwind of the source region. Close to the plume head (

Description: MonteCarlo simulations have been performed to evaluate the importance of multiple scattering effects in co- and cross-polar radar returns for 94GHz radars in Cloudsat and airborne configurations. Thousands of vertically structured profiles derived from some different cloud resolving models are used as a test-bed. Mie theory is used to derive the single scattering properties of the atmospheric hydrometeors. Multiple scattering effects in the cross polar channel (reflectivity enhancement) are particularly elusive, especially in airborne configuration. They can be quite consistent in satellite configurations, like Cloudsat, especially in regions of high attenuation and in the presence of highly forward scattering layers associated with snow and graupel particles. When the cross polar returns are analysed, high LDR values appear both in space and in airborne configurations. The LDR signatures are footprints of multiple scattering effects since they cannot be explained by single scattering computations, even including non-spherical particles. We see these signatures confirmed by some experimental data collected during the Wakasa Bay experiment. Multiple scattering effects can be important for Clousat applications like rainfall and snowfall retrievals since single scattering based algorithms will be otherwise burdened by positive biases.

Description: Contrary to tropospheric CO2 whose oxygen isotopic composition follows a standard mass dependent relationship, i.e. δ17O~0.5 δ18O, stratospheric CO2 is preferentially enriched in 17O, leading to a strikingly different relation with δ17O~1.7δ18O. The isotope anomaly is likely inherited from O3 via photolytically produced O(1D) that undergoes isotope exchange with CO2 and the anomaly may well serve as a tracer of stratospheric chemistry if details of the exchange mechanism are understood. We have studied the photochemical isotope equilibrium in UV-irradiated O2-CO2 and O3-CO2 mixtures to quantify the transfer of the anomaly from O3 to CO2 at room temperature. By following the time evolution of the oxygen isotopic compositions of CO2 and O2 under varying initial isotopic compositions of both, O2/O3 and CO2, the isotope equilibria between the two reservoirs were determined. A very strong dependence of the isotope equilibrium on the O2/CO2-ratio was established. Equilibrium enrichments of 17O and 18O in CO2 relative to O2 diminish with increasing CO2 content, and this reduction in the equilibrium enrichments does not follow a standard mass dependent relation. When molecular oxygen exceeds the amount of CO2 by a factor of about 20, 17O and 18O in equilibrated CO2 are enriched by (142±4) and (146±4), respectively, at room temperature and at a pressure of 225 hPa, independent of the initial isotopic compositions of CO2 and O2 or O3. From these findings we derive a simple and general relation between the starting isotopic compositions and amounts of O2 and CO2 and the observed slope in a three oxygen isotope diagram. Predictions from this relation are compared with published laboratory and atmospheric data.