Nitro- and oxy-PAHs in grassland soils from decade-long sampling in central Europe.

Long-term exposure to polycyclic aromatic hydrocarbons (PAHs) and their nitrated (NPAHs) and oxygenated (OPAHs) derivatives can cause adverse health effects due to their carcinogenicity, mutagenicity and oxidative potential. The distribution of PAH derivatives in the terrestrial environment has hardly been studied, although several PAH derivatives are ubiquitous in air and long-lived in soil and water. We report the multi-annual variations in the concentrations of NPAHs, OPAHs and PAHs in soils sampled at a semi-urban (Mokrá, Czech Republic) and a regional background site (Kosetice, Czech Republic) in central Europe. The concentrations of the Σ18NPAHs and the Σ11+2OPAHs and O-heterocycles were 0.31 ± 0.23 ng g-1 and 4.03 ± 3.03 ng g-1, respectively, in Kosetice, while slightly higher concentrations of 0.54 ± 0.45 ng g-1 and 5.91 ± 0.45 ng g-1, respectively, were found in soil from Mokrá. Among the 5 NPAHs found in the soils, 1-nitropyrene and less so 6-nitrobenzo(a)pyrene were most abundant. The OPAHs were more evenly distributed. The ratios of the PAH derivatives to their parent PAHs in Kosetice indicate that they were long-range transported to the background site. Our results show that several NPAHs and OPAHs are abundant in soil and that gas-particle partitioning is a major factor influencing the concentration of several semi-volatile NPAHs and OPAHs in the soils. Complete understanding of the long-term variations of NPAH and OPAH concentrations in soil is limited by the lack of kinetic data describing their formation and degradation.

One-year measurements of secondary organic aerosol (SOA) markers in the Paris region (France): Concentrations, gas/particle partitioning and SOA source apportionment.

Twenty-five biogenic and anthropogenic secondary organic aerosol (SOA) markers have been measured over a one-year period in both gaseous and PM10 phases in the Paris region (France). Seasonal and chemical patterns were similar to those previously observed in Europe, but significantly different from the ones observed in America and Asia due to dissimilarities in source precursor emissions. Nitroaromatic compounds showed higher concentrations in winter due to larger emissions of their precursors originating from biomass combustion used for residential heating purposes. Among the biogenic markers, only isoprene SOA marker concentrations increased in summer while pinene SOA markers did not display any clear seasonal trend. The measured SOA markers, usually considered as semi-volatiles, were mainly associated to the particulate phase, except for the nitrophenols and nitroguaiacols, and their gas/particle partitioning (GPP) showed a low temperature and OM concentrations dependency. An evaluation of their GPP with thermodynamic model predictions suggested that apart from equilibrium partitioning between organic phase and air, the GPP of the markers is affected by processes suppressing volatility from a mixed organic and inorganic phase, such as enhanced dissolution in aerosol aqueous phase and non-equilibrium conditions. SOA marker concentrations were used to apportion secondary organic carbon (SOC) sources applying both, an improved version of the SOA-tracer method and positive matrix factorization (PMF) Total SOC estimations agreed very well between both models, except in summer and during a highly processed Springtime PM pollution event in which systematic underestimation by the SOA tracer method was evidenced. As a first approach, the SOA-tracer method could provide a reliable estimation of the average SOC concentrations, but it is limited due to the lack of markers for aged SOA together with missing SOA/SOC conversion fractions for several sources.

On the contribution of biomass burning to POPs (PAHs and PCDDs) in air in Africa.

Forest, savannah, and agricultural fires in the tropics and subtropics are sources for widespread pollution and release many organic substances into the air and soil, including persistent organic pollutants, i.e., polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs). The significance of this source for the exposure of humans and the environment in Africa toward phenanthrene, fluoranthene, pyrene, benzo(a)pyrene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, and octachlorodibenzo-p-dioxin is studied using daily global emissions from vegetation fires observed by satellite and a global multicompartment chemistry-transport model. Near-ground atmospheric concentrations of model-predicted vegetation fire related concentrations of PAHs and PCDDs were in the 10-1000 and 10(-5)-10(-3) pg m(-3) ranges, respectively. Vegetation fires in Africa are found to emit 180 ± 25 kg yr(-1) of PCDD/Fs. By comparison with observations, it is found that fires explain 1-10% of the PCDD (5% of 2,3,7,8- tetrachlorodibenzo-p-dioxin) concentrations in the rural and background atmosphere of sub-Saharan Africa. The contribution of vegetation fires to exposure to PAH is probably >10%, but cannot be quantified due to lack of knowledge with regard to both emission factors and photochemistry. A sensitivity analysis suggests that the heterogeneous reaction of PAHs with ozone is effectively limiting atmospheric lifetime and long-range transport.

Monitoring of persistent organic pollutants in Africa. Part 2: design of a network to monitor the continental and intercontinental background.

A network for the study of long-term trends of the continental background in Africa and the intercontinental background of persistent organic pollutants as resulting from long-range transport of contaminants from European, South Asian, and other potential source regions, as well as by watching supposedly pristine regions, i.e. the Southern Ocean and Antarctica is designed. The results of a pilot phase sampling programme in 2008 and meteorological and climatological information from the period 1961-2007 was used to apply objective criteria for the selection of stations for the monitoring network: out the original 26 stations six have been rejected because of suggested strong local sources of POPs and three others because of local meteorological effects, which may prevent part of the time long-range transported air to reach the sampling site. Representativeness of the meteorological patterns during the pilot phase with respect to climatology was assessed by comparison of the more local airflow situation as given by climatological vs. observed wind roses and by comparison of backward trajectories with the climatological wind (NCEP/NCAR re-analyses). With minor exceptions advection to nine inspected stations was typical for present-day climate during the pilot phase, 2008. Six to nine stations would cover satisfyingly large and densely populated regions of North-eastern, West and East Africa and its neighbouring seas, the Mediterranean, Northern and Equatorial Atlantic Ocean, the Western Indian Ocean and the Southern Ocean. Among the more densely populated areas Southern Cameroon, parts of the Abessinian plateau and most of the Great Lakes area would not be covered. The potential of the network is not hampered by on-going long-term changes of the advection to the selected stations, as these do hardly affect the coverage of target areas.

Evolution of anthropogenic aerosols in the coastal town of Salina Cruz, Mexico: part II particulate phase chemistry.

An analysis of atmospheric gases and particles during periods of land and sea breezes in a coastal city in southwest Mexico indicates limited removal of total particle mass by deposition during periods when the air resides over the ocean. The average PM(2.5) mass concentrations for land and sea breeze samples were 25+/-1.0 and 26+/-1.0 microg m(-3), respectively. The average sum of the ion concentrations (NH(4)(+), SO(4)(2-), NO(3)(-), Na(+), Cl(-)) were 10 and 11.8 microg m(-3) for the samples taken during land and sea breeze periods. The average total carbon concentrations were 6.0 and 5.3 microg m(-3) for land and sea breeze periods. The mass of sulfate in particles of ocean origin, 3.3+/-2.8 microg m(-3), is marginally higher than those originating from the land, 2.0+/-0.8 microg m(-3), presumably as a result of the conversion of SO(2) recirculated from the city. The fraction of sulfate, nitrate and ammonium ions in rainwater samples is almost a factor of two higher than the fraction measured on filtered air samples. The rainwater also contains significant concentrations of elemental and organic carbon. This study, although extending over a period of only 15 days, with limited chemical samples, suggests that recirculation of anthropogenic particles from coastal cities should be taken into consideration when diagnosing and predicting air quality in such regions.

Evolution of anthropogenic aerosols in the coastal town of Salina Cruz, Mexico: part I particle dynamics and land-sea interactions.

Measurements of aerosol particles in a coastal city in southeast Mexico show that the concentrations and optical properties are strongly linked to land and sea breezes. Maximum concentrations of condensation nuclei (CN), black carbon (BC) and particle bound polycyclic aromatic hydrocarbons (PPAH) occur during land breeze periods and decrease with the sea breeze. The concentrations of particles in air from the ocean, however, remain significantly above background, maritime values as a result of the recirculation of anthropogenic emissions. The mass size distribution is dominated by particles larger than 5 microm when wind speeds exceed 4 m s(-1); otherwise, the uptake of water vapor onto unactivated particles is the process that dominates the growth of particles. Precipitation removes particles larger than 5 microm but CN, BC and PPAH concentrations are minimally affected.

On the horizontal homogeneity of mass-related aerosol properties.

We studied the mass-related aerosol properties, simultaneously at two sites at the urban roof top level in the same city. No systematic influence of the wind vector on the difference in the aerosol concentrations between the two locations could be found. These results are compared with results from a second, similar experiment over a larger distance including one urban and one rural site. Surprisingly, we could not detect a tendency which would indicate that sampling air at distance in the order of 1 km would be less affected by the heterogeneity than sampling distanced in the order of 10 km apart. On the contrary, the results suggest that mass-related properties at two sites in the same city are not necessarily more similar than at an urban and a rural site outside the city. These results stress the limited horizontal homogeneity of urban atmospheric aerosol. As a conclusion it is suggested that single-site measurements of mass-related aerosol properties should be considered to be representative for an area smaller than 1 km2 on size.

Forest ecosystems and the changing patterns of nitrogen input and acid deposition today and in the future based on a scenario.

A global assessment of the impact of the anthropogenic perturbation of the nitrogen and sulfur cycles on forest ecosystems is carried out for both the present-day [1980-1990] and for a projection into the future [2040-2050] under a scenario of economic development which represents a medium path of development according to expert guess [IPCC IS92a]. Results show that forest soils will receive considerably increasing loads of nitrogen and acid deposition and that deposition patterns are likely to change. The regions which are most prone to depletion of soils buffering capacity and supercritical nitrogen deposition are identified in the subtropical and tropical regions of South America and Southeast Asia apart from the well known 'hotspots' North-Eastern America and Central Europe. The forest areas likely to meet these two risks are still a minor fraction of the global forest ecosystems, though. But the bias between eutrophication and acidification will become greater and an enhanced growth triggered by the fertilizing effects of increasing nitrogen input cannot be balanced by the forest soils nutrient pools. Results show increasing loads into forest ecosystems which are likely to account for 46% higher acid loads and 36% higher nitrogen loads in relation to the 1980-1990 situation. Global background deposition of up to 5 kg N ha-1 a-1 will be exceeded at more than 25% of global forest ecosystems and at more than 50% of forest ecosystems on acid sensitive soils. More than 33% of forest ecosystems on acid sensitive soils will receive acid loads which exceeds their buffering capacity. About 25% of forest areas with exceeded acid loads will receive critical nitrogen loads.

Low-molecular weight dicarboxylic acids and glyoxylic acid: seasonal and air mass characteristics.

Low-molecular weight dicarboxylic acids are important constituents ofthe organic fraction of atmospheric particulate matter in remote and polluted regions. The knowledge on their sources is sparse, however, and organic aerosols in general need to be better characterized. Observations of C2-C5 alpha,omega-dicarboxylic acids (DCAs oxalic, malonic, succinic, and glutaric acid) and C2 oxomonocarboxylic acid (glyoxylic acid) from rural and urban sites in different seasons in Germany are reported using filter sampling and ion chromatography. The C2-C5 DCAs accounted for (by average) 0.07-0.51 microg m(-3) at the various sites corresponding to 3.4-23 mg g(-1) of total suspended particulate matter and glyoxylic acid for < 0.18-0.28 mg g(-1). Both, the transport of air masses over the continent and the summer season favored the occurrence of the acids. Secondary photochemical formation dominated the sources. It was found that for central Europe the anthropogenic emissions are more important than the biogenic emissions for all the acids determined and most important for oxalic acid. The biogenic precursors play a signifcant role for malonic acid. The influence of the marine sources was detectable for malonic and glutaric acid.

Sensitive method for the determination of different S(IV) species in cloud and fog water.

Suppressed ion chromatography has been applied to the determination of S(IV) species in cloud and fog water in the range 0.012-2.4 mg S(IV)-S/L. The samples have been preserved prior to storage and S(IV) species have been determined as hydroxy methanesulfonate (HMS) together with the low molecular weight carboxylic acid anions, formate and acetate. Samples have been divided and treated differently such that total S(IV) as well as the non-oxidizable fraction of S(IV) (as given by the reactivity with H(2)O(2), added in surplus) could be determined. The difference between the two corresponds to the S(IV) fraction subjected to oxididation, which is of paramount interest in cloud and fogwater chemistry.

Greenhouse effect of NOX.

Through various processes the nitrogen oxides (NOX) interact with trace gases in the troposphere and stratosphere which do absorb in the spectral range relevant to the greenhouse effect (infrared wavelengths). The net effect is an enhancement of the greenhouse effect. The catalytic role of NOX in the production of tropospheric ozone provides the most prominent contribution. The global waming potential is estimated as GWP (NOX = 30 - 33 and 7 - 10 for the respective time horizons of 20 and 100 years, and is thereby comparable to that of methane. NOX emissions in rural areas of anthropogenically influenced regions, or those in the vicinity of the txopopause caused by air traffic, cause the greenhouse effectivity to be substantially more intense. We estimate an additional 5-23 % for Germany's contribution to the anthropogenic greenhouse effect as a result of the indirect greenhouse effects stemming from NOX. Furthermore, a small and still inaccurately defined amount of the deposited NOX which has primarily been converted into nitrates is again released from the soil into the atmosphere in the form of the long-lived greenhouse gas nitrous oxide (N2O). Thus, anthropogenically induced NOX emissions contribute to enhanced greenhouse effect and to stratospheric ozone depletion in the time scale of more than a century.