Altitude profiles of total chlorinated paraffins in humus and spruce needles from the Alps (MONARPOP)

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. CPs were analyzed in humus and needle samples, which were taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) at sampling sites of 7 different altitude profiles in the Alps. Gas chromatography combined with electron ionization tandem mass spectrometry (EI-MS/MS) was used for the determination of total CPs (sum of short, medium and long chain CPs). CPs were found in all samples; the concentrations varied between 7 and 199 ng g⁻¹ dry weight (dw) and within 26 and 460 ng g⁻¹ dw in humus and needle samples, respectively. A clear vertical tendency within the individual altitude profiles could not be ascertained. Within all altitude profiles, elevated concentrations were observed in humus samples taken between 700 and 900 m and between 1300 and 1500 m. In the needle samples no similar correlation could be observed due to higher variation of the data.     

Occurrence of PAH in the seasonal snowpack of the Eastern Italian Alps

PAH concentrations have been determined in 47 seasonal snowpack samples collected in the Valbelluna valley and in the Bellunesi Dolomites National Park, in the Italian North-Eastern Alps, during the winter of 2005. The ΣPAH concentration in high-altitude alpine sites (above 1700 m) was 32 ± 20 ng/kg while in valley bottom urban areas it was 165 ± 54 ng/kg with maximum values of 290 ng/kg. The GIS mapping technique was employed to produce a PAH spatial distribution. The urbanized Valbelluna valley, and in particular the SW part, had the highest accumulation of all PAH, with values an order of magnitude more than those in rural and alpine areas. This behaviour is consistent with urban air quality data, and is due to geo-morphological and meteorological factors such as the deeper shape of the valley at the position of the town of Feltre and the low altitude of the boundary layer during the winter season.     

Increasing interannual and altitudinal ozone mixing ratios in the Catalan Pyrenees

Interannual, seasonal, daily and altitudinal patterns of tropospheric ozone mixing ratios, as well as ozone phytotoxicity and the relationship with NO_x precursors and meteorological variables were monitored in the Central Catalan Pyrenees (Meranges valley and Forest of Guils) over a period of 5 years (2004–2008). Biweekly measurements using Radiello passive samplers were taken along two altitudinal transects comprised of thirteen stations ranging from 1040 to 2300 m a.s.l. Visual symptoms of ozone damage in Bel-W3 tobacco cultivars were evaluated biweekly for the first three years (2004–2006). High ozone mixing ratios, always above forest and vegetation protection AOT40 thresholds, were monitored every year. In the last 14 years, the AOT40 (Apr–Sept.) has increased significantly by 1047 μg m^?3 h per year. Annual means of ozone mixing ratios ranged between 38 and 67 ppb_v (38 and 74 ppb_v during the warm period) at the highest site (2300 m) and increased at a rate of 5.1 ppb_v year^?1. The ozone mixing ratios were also on average 35–38% greater during the warm period and had a characteristic daily pattern with minimum values in the early morning, a rise during the morning and a decline overnight, that was less marked the higher the altitude. Whereas ozone mixing ratios increased significantly with altitude from 35 ppb_v at 1040 m–56 ppb_v at 2300 m (on average for 2004–2007 period), NO₂ mixing ratios decreased with altitude from 5.5 ppb_v at 1040 m–1 ppb_v at 2300 m. The analysis of meteorological variables and NO_x values suggests that the ozone mainly originated from urban areas and was transported to high-mountain sites, remaining aloft in absence of NO. Ozone damage rates increased with altitude in response to increasing O₃ mixing ratios and a possible increase in O₃ uptake due to more favorable microclimatic conditions found at higher altitude, which confirms Bel-W3 as a suitable biomonitor for ozone concentrations during summer time. Compared to the valley-bottom site the annual means of ozone mixing ratios are 37% larger in the higher sites. Thus the AOT40 for the forest and vegetation protection threshold is greatly exceeded at higher sites. This could have substantial effects on plant life at high altitudes in the Pyrenees.     

Synoptic weather patterns and their relationship to high ozone concentrations in the Taichung Basin

Frequent high ozone days (defined as daily maximum ozone concentration ⩾80 ppb) during recent years in the Taichung Basin have caused much concern. High ozone days occur mainly during autumn and spring. Statistically, there is no clear linear relationship between a single meteorological variable and ozone concentration. In this study, data from 1996–2000 has shown that high ozone concentrations occur during two types of synoptic weather patterns. The first type is a continental cyclone emanating from mainland China, the southern part of it swept towards Taiwan by easterly winds. The second pattern is a tropical depression moving northwards toward the region, the northern part of it affecting Taiwan via easterly winds. Both types cover Taiwan with easterly winds, which are blocked by the Central Mountain Ranges (altitude of 2000–3000 m). The ranges create lee cyclogenesis to the west, which is unfavorable for pollutant dispersion and leads to serious air pollution episodes.The statistical results of the synoptic weather patterns in relation to ozone concentrations are based on the 5 yr data (1996–2000). This was obtained from a network of air-pollution monitoring sites in the study area, while the vertical data come from two 3-day tethersonde experimental campaigns conducted during March and October 2000, measuring air pressure, air temperature, relative humidity, wind speed and direction, non-methane hydrocarbons, NO_x and O₃.     

Soil type affects migration pattern of airborne Pb and Cd under a spruce-beech forest of the UN-ECE integrated monitoring site Zöbelboden, Austria

Anthropogenic trace element emissions have declined. However, top soils all over the world remain enriched in trace elements. We investigated Pb and Cd migration in forest soils of a remote monitoring site in the Austrian limestone Alps between 1992 and 2004. Large spatial variability masked temporal changes in the mineral soil of Lithic Leptosols (Skeltic), whereas a significant reduction of Pb concentrations in their forest floors occurred. Reductions of concentrations in the less heterogeneous Cambisols (Chromic) were significant. In contrast, virtually no migration of Pb and Cd were found in Stagnosols due to their impeded drainage. Very low element concentrations (<1 μg l⁻¹) in field-collected soil solutions using tension lysimeters (0.2 μm nylon filters) imply that migration largely occurred by preferential flow as particulate-bound species during intensive rainfall events. Our results indicate that the extent of Pb and Cd migration in soils is largely influenced by soil type.     

Characteristics of springtime profiles and sources of ozone in the low troposphere over northern Taiwan

To quantify the possible sources of the high ambient ozone concentration in the low troposphere over Taiwan, ozone sounding data from a two-year intensive field measurement program conducted in April and early May of 2004 and 2005 in northern Taiwan has been examined. We found that the vertical ozone distributions and occurrence of enhanced ozone in the lower troposphere (below 6 km) mainly resulted from (1)Type NE: the long-range transport of ozone controlled by the prevailing northeasterly winds below 2 km, (2)Type LO: the local photochemical ozone production process, and (3)Type SW: the strong southwest/westerly winds aloft (2–6 km). In the boundary layer (BL), where Asian continental outflow prevails, the average profile for type NE is characterized by a peak ozone concentration of nearly 65 ppb at about 1500 m altitude. For type LO, high ozone concentration with an average ozone concentration greater than 80 ppb was also found in the BL in the case of stagnant atmospheric and sunny weather conditions dominated. For type SW, significant ozone enhancement with average ozone concentration of 70–85 ppb was found at around 4 km altitude. It is about 10 ppb greater than that of the types NE and LO at the same troposphere layer owing to the contribution of the biomass burning over Indochina. Due to Taiwan's unique geographic location, the complex interaction of these ozone features in the BL and aloft, especially features associated with northeasterly and south/southwesterly winds, have resulted in complex characteristics of ozone distributions in the lower troposphere over northern Taiwan.     

Seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk from a high altitude pasture in the Italian Alps

The seasonal and spatial variability of polychlorinated biphenyls (PCBs) in vegetation and cow milk was studied in a high altitude pasture in the Alps (1900 m a.s.l.). PCB contamination in vegetation shows a concentration peak in June, which is mainly interpreted as the consequence of a temporary PCB enrichment of the air layer above the ground due to net emission fluxes from the soil. A three compartment dynamic model was developed to test this hypothesis. The North/South enrichment factor in the vegetation was 1.5-1.6 for penta- and hexa-substituted congeners and 1.7 for hepta- and octa-PCBs, according to the effect of temperature on compounds having higher K_oa values. Milk concentrations followed the vegetation seasonal trend. The congener abundance in milk is in agreement with the biotransformation susceptibility, absorption efficiency and residence time of the different congeners in dairy cows.     

Mesoscale modelling of vertical atmospheric transport in the Alps associated with the advection of a tropopause fold – a winter ozone episode

The role of vertical atmospheric transport (VAT) for a winter ozone episode (January 1988) in the Alps, observed both on the mountain crest (3580 m asl) and in the lee of the Alps (209 m asl), is investigated. Numerical simulations were carried out with a doubly nested mesoscale model (14 km horizontal resolution), characterised by a refined orography scheme. A comparison between the modelled vertical profiles with features observed in the aerological soundings over Payerne indicated that the model is able to reproduce the fold in the Alps down to 650 hPa. Frictional processes are found to be responsible for the fragmentation of the lower parts of the fold when it is advected over the mountains, thus enhancing ozone concentrations at the mountain crest with likely cross-tropopause mixing. Vertically propagating gravity waves and strong mesoscale vertical winds (nordfoehn) are responsible for the further downward transport of ozone-rich air to the lower troposphere. This mechanism leads to ozone concentrations up to 70 ppb(v) in the leeside. The study is important because tropospheric ozone trends in the lee of the Alps have been inferred, in the past, from ozone peaks associated with such nordfoehn conditions. It is now shown that nordfoehn may entrain air which has been recently exchanged across the tropopause.     

Variability of total ozone over India and its adjoining regions during 1997–2008

Total Ozone Concentration (TOC) data over nineteen stations around India (fifteen stations) and its adjoining regions (three stations in Pakistan and one station in Bangladesh) are investigated in the present analysis. The overpass satellite data for these nineteen stations, distributed in the latitude range from 8.48°N to 35.83°N and altitude range from 6 m to 2718 m are available from FTP Site. TOC data pertaining to the last twelve years from 1997 to 2008 were obtained from two different instruments: Total Ozone Mapping Spectrometer (TOMS) and Ozone Monitoring Instrument (OMI) on Earth Probe and AURA satellites respectively. The analysis is divided into two phases, each of six years duration; from 1997 to 2002 and from 2003 to 2008. Seasonal average values of TOC are calculated for the two phases and compared to study the spatial distribution (latitude, longitude and station altitude) and the trends of TOC variation. In general a decreasing tendency in ozone concentration was found everywhere. The average yearly rate of the TOC decrease was ?0.363 DU over the entire region during the period 1997–2008. The trends in the TOC distribution and its decrease with latitude were found parabolic, with a deep near 14.7°N and 12.1°N for the two phases respectively. The decrease was maximum at lower latitude (?1.87%) and minimum (?0.25%) at higher latitude. Weak oscillatory trends in the TOC distribution and its decrease with longitude were found. A deep in the longitudinal variation was observed in each phase, at 77.4°E during 1997–2002 and at 78.2°E during 2003–2008. The minimum centre of the ozone distribution is therefore shifted from 14.7°N, 77.4°E to 12.1°N, 78.2°E over the last twelve years, and in general a meridional line near 78°E appears to divide symmetrically the TOC distribution over this region. Strong oscillatory trends in the seasonal average of TOC distribution and its decrease with station altitude are observed during the two phases. The inversion of high correlation coefficients between the seasonal average TOC and station altitude in the range 6 m to 2718 m indicate the existence of four transition layers aloft, near 200, 740, 1670, and 2400 m in the lower troposphere. Emission of precursor pollutants together with complex wind pattern around the marine boundary appears to have strong potentials to modulate tropospheric ozone and the observed spatial distribution of TOC may be expected.     

Himalayan alpine ecohydrology: An urgent scientific concern in a changing climate

Climate change is projected to have important impacts on snow and vegetation distribution in global mountains. Despite this, the coupling of ecological shifts and hydrological processes within alpine zones has not attracted significant scientific attention. As the largest and one of the most climatically sensitive mountain systems, we argue that Himalayan alpine ecohydrological processes require urgent scientific attention because up to 1.6 billion people rely on water supplies from the mountains. We review studies from global mountain systems to highlight the importance of considering ecohydrological impacts within Himalayan alpine zones (4100–6000 m.a.s.l), explaining mechanisms for interactions between snow and dwarf plants. Our findings highlight the paucity of monitoring stations within Himalayan alpine systems. We suggest that it is likely that alpine ecological shifts will impact hydrological processes, but we found that specific mechanisms and functional relationships are missing for Himalayan systems, so the strength and direction of ecohydrological relationships is currently unknown. We advocate for more purposeful and widespread monitoring efforts below glaciers and above the treeline, calling for new experiments to query the role of small plants within the Himalayan alpine hydrological system. We outline the need for community engagement with alpine ecohydrological experiments, and we explain how new snow and vegetation products derived from remote sensing observations have the potential to improve scientific understanding of the interacting effects of warming and ecohydrological factors in this sensitive region.     

Atmospherically deposited major and trace elements in the winter snowpack along a gradient of altitude in the Central Pyrenees: The seasonal record of long-range fluxes over SW Europe

The chemistry of high mountain snowpacks is a result of the long-range atmospheric transport and deposition of elements. Pyrenean snowpacks contain information about the fluxes of elements over SW Europe in winter. Here we analysed Al, Ti, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb in the 2004–05 winter snowpack in the Central Pyrenees, at an altitude range of 1820–3200 m a.s.l. Ni, As, Se and Cd were not detected in most cases. The concentrations of the remaining elements were comparable to those found in other high mountain areas in Europe and North America considered representative of regional background of atmospheric deposition in populated areas. In contrast, our measurements were higher than those of polar areas, which represent the global background. Single measurements of concentrations and snow accumulation were subject to considerable spatial variability, which may be attributable to strong wind drift and other post-depositional processes. The major ions chemistry of the snow indicated three possible origins for the solutes: terrigenous dust, sea salt spray and polluting S and N aerosols. We found no association between Cu, Zn and Pb and any of these possible sources. This observation therefore indicates that these elements were not preferentially bound to any particular kind of aerosol. Snow collected at altitudes of up to 2050 m a.s.l. presented higher concentrations of several elements than snow above this altitude, thereby indicating a local influence. Snow collected above 2300 m a.s.l. was therefore more representative of broad regional inputs. At these higher altitudes, snow was not enriched in Al, Ti, Mn, Fe or As compared with the composition of the upper continental crust and the local lithology, and these elements (except Mn) appeared almost exclusively in the particulate fraction. This observation indicates that Al, Ti, Mn, Fe and As were present mainly as part of dust particles of terrigenous origin. In contrast, Cu, Zn, and Pb presented medium to high enrichment factors and showed a higher proportion of soluble forms, thereby indicating their polluting character.     

Ozone production from Grenoble city during the August 2003 heat wave

The heat wave from 1 to 16 August 2003 is considered in the city of Grenoble (French Alps). The modelling system (PREVALP) is based on several models operating on nested domains: MM5 for dynamics, CHIMERE for chemistry (18 km and 6 km grid size) and METPHOMOD for both dynamics and chemistry (2 km grid size). The analysis of the results shows that during the heat wave, the mixing layer is thicker, up to 3500 m agl, hence inducing transport of ozone to high altitude. Two regimes were diagnosed: (1) a freely developing convective layer, (2) a layer trapped under south wind which makes ozone precursors accumulate in the city. Local ozone production is estimated to be 40% of the plume maximum in case (2) and only 30% in case (1). Sensitivity analysis by step increase for temperature at the boundary of the inner domain shows the non-linearity of the response; in this case most of the effect comes from chemistry. By changing biogenic emission significant changes are observed in restricted areas.     

PCDD/F and PCB in spruce forests of the Alps

PCDD/F and PCB concentrations in remote mountainous spruce stands of the Central European Alps show strong geographic variation. Independent of the matrix (0.5 year old needles, humus or mineral soil), the highest pollutant levels were always found at the lateral zones of the mountain range. High levels coincided with strong precipitation, particularly along the northern margin of the study region. The most volatile PCB congener propagated farther into the colder, drier central Alps than the heavier species. Matrices with different accumulation history (needles and humus) repeatedly reflected different spatial immission patterns. Consistent with its much longer exposure, pollutant levels in humus exceeded those of needles by up to two orders of magnitude. Needle contamination varied with altitude but the vertical trends were highly variable between transsects and changed between years, too.     

Wintering French Mallard and Teal Are Heavier and in Better Body Condition than 30?Years Ago: Effects of a Changing Environment?

Animal populations are exposed to large-scale anthropogenic impact from e.g. climate change, habitat alteration and supplemental stocking. All of these may affect body condition in wintering dabbling ducks, which in turn may affect an individual’s survival and reproductive success. The aim of this study was to assess whether there have been morphometric changes in Mallard (Anas platyrhynchos) and Teal (Anas crecca) over the last 30 years at a major wintering site. Body mass and condition increased from the 1950s–1960s to the 2000s in both species. The increase in body mass amounted to as much as 11.7%, with no corresponding change in body size. Improved body condition was maintained from early to mid-winter, but then converged with historical values for late winter. Our interpretation is that increasingly benign ambient winter conditions permit ducks to maintain better energetic “safety margins” throughout winter, and that converging spring departure values may be related to evolutionary flight energetic optima. The observed changes are consistent with large-scale climate amelioration and local/regional habitat improvement (both anthropogenic).     

Atmospheric heavy metals in high altitude surface snows from Mont Blanc,French Alps

We present here the results of the analysis of various surface snow samples collected in the massif of Mont Blanc, French Alps, at three locations whose altitude ranges from 3560 to 4785 m a. s l. These samples were collected using ultra-clean techniques similar to the ones developed for Greenland and Antarctic studies. They were analysed for Pb, Cd, Cu, Zn, Ag, Na, Mg, K, Ca, Fe, Al and Mn by Graphite Furnace Atomic Absorption in clean room conditions. Measured concentrations are very low, then confirming the extreme purity of high altitude snow in the Alps. Principal components factor analysis of the data suggest a crustal source for Na, Mg, K, Ca, Fe, Mn and Al; heavy metals Pb, Cd, Cu, Zn and Ag are found on the other hand to be derived from one or several sources independent of the crustal source. Measured concentrations in snow appear to be closely related to thos̀e previously published by other authors for local aerosols.     

Altitude dependence of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface soil from Tibetan Plateau, China

Remote mountain areas besides high latitude regions are beginning to receive increased attention in studying the transport and behavior of persistent organic pollutants (POPs). In the present work, surface soil samples were collected from the Tibetan Plateau, the highest plateau in the world which includes the northern slope of Mt. Qomolangma, to investigate the levels and trends of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) along the altitudinal gradient. The average PCB and PBDE concentrations were 185.6 ng kg⁻¹ dry weight (dw) (range 47.1–422.6 ng kg⁻¹ dw) and 11.1 ng kg⁻¹ dw (range 4.3–34.9 ng kg⁻¹ dw), respectively. Regression analysis between the log-transformed TOC-normalized concentrations and the altitudes of the sampling sites showed two opposite trends with regard to altitude dependence: negative relationship with altitude below about 4500 m followed by a positive altitude dependence above this point. Considering minimum anthropogenic activities and very sparse precipitation in the north of Himalayas, the trends above 4500 m imply that the significant altitude dependence of these two groups of POPs were irrespective of pollution sources, but could be predicted by the global distillation effect involving cold condensation in high altitude mountain areas. Increasing levels of heavier congeners were found in higher altitude sites, although the lighter congeners were the main contributors to the total amount, suggesting that less volatile congeners seem to become enriched easier than those more volatile at higher altitudes in this region.     

Middle and lower troposphere aerosol characteristics and ozone concentrations over northwestern Greece during STAAARTE 1997

Accumulation aerosol particle distributions were measured on 14 June 1997 during two research flights over northwestern Greece, including the greater Thessaloniki area (GTA). At flight altitudes of about 5000 m (<550 mb), accumulation mode number particle size distributions appeared to be unimodal with a maximum in the first bin of the measured number size distribution with a mid-point of 0.11 μm. At lower altitudes and over the GTA, accumulation mode particle size distributions were bimodal with a first mode peak at 0.125 μm and a second mode peak at 0.275 μm. The second mode was more pronounced in areas of higher relative humidity, thus indicating the presence of deliquescent aerosols, but also in areas where high O₃ concentrations were measured. Ozone concentrations ranged between 25 and 60 ppb at high altitudes east of GTA and between 50 and 110 ppb over the city of Thessaloniki with the maximum measured at an altitude of about 500 m. This is consistent with the local topographical and meteorological conditions, mainly due to the nocturnal inversion and the development of local circulation flows (land and sea breeze) over the city.     

Ozone assessment in the southern part of the Alps

In this paper ozone measurements carried out at six alpine and prealpine sites, located in the Italian region of Central Alps are shown. The stations are placed at altitudes between 800 and 1900 m a.s.l., far away from local sources of pollution. Ozone concentrations appear to be quite uniform, with summer mean values varying from 40 to 47 ppb and winter ones from 19 to 35 ppb. The number of hours exceeding the 75 and 100 ppb WHO thresholds and the AOT40 (Average Over Threshold 40 ppb of ozone) are evaluated for the growing season. The temporal variability of weekly ozone cycle at alpine stations provides useful informations to assess an emission control strategy.     

Vertical distribution of organochlorine pesticides in humus along Alpine altitudinal profiles in relation to ambiental parameters

In forest soils along vertical profiles located in different parts of the Alps, concentrations of persistent organic pollutants (POPs), namely organochlorine pesticides (OCPs) like dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), heptachlor, aldrin, dieldrin and mirex, were measured. Though local characteristics of the sites are influenced by numerous factors like orographic and meteorological parameters, forest stand characteristics and humus parameters, we ascertained a marked vertical increase of concentrations of some organochlorine compounds in the soil. On the basis of climatological values of each site, we found that the contamination increase with altitude can be ascribed to a certain ‘cold condensation effect’. In addition, the perennial atmospheric deposition of POPs is controlled by precipitation. Other key parameters explaining the accumulation of POPs are the soil organic carbon stocks, the turnover times, the re-volatilisation and degradation processes, which vary with altitude.     

An unusual springtime ozone episode at high elevation in the Swiss Alps: contributions both from cross-tropopause exchange and from the boundary layer

An unusually “smooth” springtime ozone episode (maximum 97 ppb(v)) at the Jungfraujoch Observatory (3580 m asl) in the Swiss Alps is described. Analysis of meteorological variables is combined with back-trajectory analysis, and numerical simulations from a mesoscale model nested within a limited area model to examine the origin of the episode. Cross-tropopause exchange on the western flank of an upper trough, deep convection in a Gulf of Genoa cyclone, and the northwards advection of boundary-layer air (with possible in situ photochemistry) all combined to produce the highest ozone concentration of the year (1987) at the mountain site.