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Road dust is an indicator widely used when monitoring contamination and evaluating environmental and health risks in urban ecosystems. We conducted an exhaustive characterization of road dust samples coupling their chemical characteristics and stable isotope compositions (C and N) with the aim of evaluating the levels and spatial distribution of local contamination as well as to identify its main source(s) in the coastal city of Cienfuegos (Cuba). Results indicate that the concentrations of several elements (total nitrogen, S, Ca, V, Cu, Zn, Mo, Sn, Hg, and Pb) exceed the background values reported for both Cuban soils and the upper continental crust (UCC) and showed a high variability among the sampling sites. We show that road dust contamination in Cienfuegos induces high associated ecological risks. Among the studied elements, Cd and Hg are the major contributors to the environmental contamination in the city, mainly along busy roads and downtown. δ13C and δ15N, coupled to a multivariate statistical analysis, help associate the studied elements to several local sources of contamination: mineral matter derived from local soils, cement plant and related activities, road pavement alteration, power plant, road traffic, and resuspension of particulate organic matter (POM). Our results suggest that incorporating the chemical and isotope monitoring of road dust may help implement more effective environmental management measures in order to reduce their adverse impact on ecosystems and human health.

Atmospheric deposition is considered to be the major pathway by which substances from the atmosphere enter to the terrestrial and aquatic ecosystems. This study constitutes the first exhaustive report on trace metal deposition in Cuba and is aimed to determine the monthly atmospheric flux of 47 major and trace elements in a Caribbean coastal site and investigate the main sources contributing to deposition. Bulk deposition (average of 46 018 μg m−2 day−1) and fluxes of studied elements showed a high variability and no seasonality with the dry and wet periods, results that we attributed to the fluctuations of the emissions from their main sources rather than to meteorological factors controlling the deposition processes. However, stronger correlations were found between typical crustal elements, which showed a marked seasonality with the presence of African cloud dust in the Caribbean. Lanthanoids element (Eu anomalies and LaN/LuN ratios) helped us to confirm the seasonal influence of African dust in the geochemical composition of bulk deposition in Cienfuegos. Most of the analysed elements were found in the range of variation of those reported in rural environments around the world but, the elements V, Ni, As and Sb reached higher levels, typically found in urban and industrial areas. The elements Sb, Pb, W, Sn, S, Cu, Mo, Nb and P were moderately enriched (10 100), indicating they were mainly derived from anthropogenic sources. The La/V ratios were found to be exclusively lower than 0.06 suggesting a strong influence of anthropogenic V emissions from industries with oil and/or petroleum-coke combustion processes. However, we found that V have a predominantly natural origin in the studied region which appear to be related with deposition processes dominated by large particles. Finally, Principal Component, Multilinear Regression and Cluster analyses led the identification of 5 main sources contributing to the bulk deposition: crustal matter (39.5%), marine aerosol (38.2%), combustions including the wastes incineration, wood and fossil fuel burning (6.7%), industries (8.7%) and road traffic (1.4%).

In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO 3 − and NH 4 + with stomatal uptake of NH 3 , HNO 3 and NO 2 derived from the DO 3 SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha −1 year −1 ) and at the northeastern sites (17.8 and 12.5 kg N ha −1 year −1 ) than at the central-Spain site (9.4 kg N ha −1 year −1 ). On average, the estimated dry deposition of atmospheric N represented 77% ± 2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ± 2.9 kg N ha −1 year −1 for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ± 0.8 kg N ha −1 year −1 (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO 2 to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10–20 kg N ha −1 year −1 ) was exceeded in three of the four studied forests.

The constant increase of anthropogenic emissions of aerosols, usually resulting from a complex mixture from various sources, leads to a deterioration of the ambient air quality. The stable isotope compositions (δ13C and δ15N) of total carbon (TC) and nitrogen (TN) in both PM10 and emissions from potential sources were investigated for first time in a rural and an urban Caribbean costal sites in Cuba to better constrain the origin of the contamination. Emissions from road traffic, power plant and shipping emissions were discriminated by coupling their C and N contents and corresponding isotope signatures. Other sources (soil, road dust and cement plant), in contrast, presented large overlapping ranges for both C and N isotope compositions. δ13CPM10 isotope compositions in the rural (average of −25.4 ± 1.2‰) and urban (average of −24.8 ± 1.2‰) sites were interpreted as a mixture of contributions from two main contributors: i) fossil fuel combustion and ii) cement plant and quarries. Results also showed that this last source is impacting more air quality at the urban site. A strong influence from local wood burning was also identified at the rural site. These conclusions were comforted by a statistical analysis using a conditional bivariate probability function. TN and δ15N values from the urban site demonstrated that nitrogen in PM10 was generated by secondary processes through the formation of (NH4)2SO4. The exchange in the (NH4)2SO4 molecule between gaseous NH3 and particle NH4+ under stoichiometric equilibrium may control the observed 15N enrichment. At low nitrogen concentrations in the aerosols, representing PM10 with both the highest primary N and lowest secondary N proportions, comparison with the δ15N of potential sources indicate that emissions from diesel car and power plant emissions may represent the major vectors of primary nitrogen.

Peri-urban vegetation is generally accepted as a significant remover of atmospheric pollutants, but it could also be threatened by these compounds, with origin in both urban and non-urban areas. To characterize the seasonal and geographical variation of pollutant concentrations and to improve the empirical understanding of the influence of Mediterranean broadleaf evergreen forests on air quality, four forests of Quercus ilex (three peri-urban and one remote) were monitored in different areas in Spain. Concentrations of nitrogen dioxide (NO₂), ammonia (NH₃), nitric acid (HNO₃) and ozone (O₃) were measured during 2 years in open areas and inside the forests and aerosols (PM₁₀) were monitored in open areas during 1 year. Ozone was the only air pollutant expected to have direct phytotoxic effects on vegetation according to current thresholds for the protection of vegetation. The concentrations of N compounds were not high enough to directly affect vegetation but could be contributing through atmospheric N deposition to the eutrophization of these ecosystems. Peri-urban forests of Q. ilex showed a significant below-canopy reduction of gaseous concentrations (particularly NH₃, with a mean reduction of 29-38 %), which indicated the feasibility of these forests to provide an ecosystem service of air quality improvement. Well-designed monitoring programs are needed to further investigate air quality improvement by peri-urban ecosystems while assessing the threat that air pollution can pose to vegetation.

This work provides a comprehensive report on the chemical composition of 47 major and trace elements in Tillandsia recurvata (L.) L. and top soil samples from the cities of Cienfuegos and Santa Clara in Cuba. The main aims were to provide new information on the urban pollution degree in Caribbean urban regions where the availability of data of urban health indicators are very limited and to identify the main pollution sources. The abundance of the analyzed elements at both type of samples were different at each urban regions suggesting the influence of various sources. Top soils were slightly contaminated with Zn, V, Ba, Pb, Ni, Cr, Cu, Co and Hg and seriously contaminated with Ni and Cr in Santa Clara. These and other elements such as Se, S, P, Cd, Mo and Ca where highly enriched in T. recurvata indicating a significant impact of anthropogenic sources in the air quality of both urban areas. Cluster analysis helped us associate most of the elements with an anthropogenic origin with three main pollution sources: road traffic, industrial emissions and oil combustion. The spatial variability was particularly useful to identify some of these sources including the emissions from diesel and fuel oil combustion in power stations, biomass burning and metallurgic industries. The results also showed that V and Ni were strongly associated to the oil combustion and that V/Ni ratio indices in both indicators can be used to trace this type of sources. The results presented in this study confirmed the conclusion that both T. recurvata and top soils can be used as feasible indicators of the health of Caribbean urban ecosystems and the distribution of the main pollution sources that are affecting them.

Mercury (Hg) and lead (Pb) isotopic compositions were investigated in mosses and lichens collected in a large mountainous beech forest (Iraty Forest) located on the French-Spanish Pyrenean border. Hg isotopic signature in topsoil samples were also analyzed in selected sampling sites. This is the first work that uses the complementary information of both isotopic systems in two distinct atmospheric bioaccumulators. Mosses and lichens present characteristic accumulation due to their integration times, displaying different information on metal pollution over the area. Hg and Pb concentrations in annual moss shoots represent recent atmospheric accumulation, while whole lichen thalli integrates a process of accumulation over a longer period. Lead isotope ratios in mosses are consistent with reported data corresponding to the actual European atmospheric background (206Pb/207Pb ∼ 1.158), while Hg isotopic composition reflects potential uptake of both dry and wet Hg depositions. For lichens, Pb isotopic composition exhibits the contribution of a longer integration period of both industrial Pb emissions and legacy of leaded gasoline pollution. Hg isotopes in lichens discriminate two main groups: a larger one representing the background atmospheric contribution and a second one corresponding to unexpected higher Hg content. The similarities in odd and even Mass-independent fractionation of Hg isotopes between topsoils and lichens from the larger group, support the idea that foliage uptake is the main input of Hg in soils. The second group of lichens exhibits more negative δ202Hg (down to –4.69‰) suggesting a new source of fractionation in this area, probably related to lichens aging and/or stubble and grass fires due to pastoral activities. This study demonstrates that using both Hg and Pb isotopic signature in lichens and mosses allows to trace atmospheric sources and environmental pathways of these metals in forested ecosystems. This original data set in a remote environment provides also new information on the fate of atmospheric Pb and Hg depositions.

Ammonia (NH3) emissions are linked to eutrophication, plant toxicity and ecosystem shifts from N to P limitation. Bryophytes are key components of terrestrial ecosystems, yet highly sensitive to N deposition. Hence, physiological responses of mosses may be indicative of NH3-related impacts, and thus useful to foresee future ecosystem damages and establish atmospheric Critical Levels (CLEs). In this work, samples of Hypnum cupressiforme Hedw. were seasonally collected along a well-defined NH3 concentration gradient in an oak woodland during a one-year period. We performed a comprehensive evaluation of tissue chemistry, stoichiometry, metabolic enzymes, antioxidant response, membrane damages, photosynthetic pigments, soluble protein content and N and C isotopic fractionation. Our results showed that all the physiological parameters studied (except P, K, Ca and C) responded to the NH3 gradient in predictable ways, although the magnitude and significance of the response were dependent on the sampling season, especially for enzymatic activities and pigments content. Nutritional imbalances, membrane damages and disturbance of cellular C and N metabolism were found as a consequence to NH3 exposure, being more affected the mosses more exposed to the barn atmosphere. These findings suggested significant implications of intensive farming for the correct functioning of oak woodlands and highlighted the importance of seasonal dynamics in the study of key physiological processes related to photosynthesis, mosses nutrition and responses to oxidative stress. Finally, tissue N showed the greatest potential for the identification of NH3-related ecological end points (estimated CLE=3.5μgm-3), whereas highly scattered physiological responses, although highly sensitive, were not suitable to that end.

In this study, PM10 aerosol samples were collected at 4 urban and 1 rural sites in the region of Cienfuegos (Cuba) and analyzed for their chemical compositions (total carbon (TC), total nitrogen (TN), NH4+, Cl−, NO3− and SO42−) and their stable carbon (δ13C) and nitrogen (δ15N), and radioactive (210Pb, 7Be, 137Cs and 40K) isotope systematics, in order to better constrain both their sources of pollution and their atmospheric dynamics. The average PM10 concentrations varied from 21.67 ± 8.54 μg m−3 at the rural site to 39.01 ± 8.23 μg m−3 at an urban site characterized by high road traffic. Chemical compositions showed low variability and similar abundances of the ionic species, but we observed strong correlations between i) NH4+ and SO42− that indicates the formation of secondary ammonium bisulfate (NH4HSO4), and ii) between PM10 and TC highlighting the significant influence of carbonaceous aerosols. We are reporting here the first 210Pb aerosol concentrations in this region and demonstrate that, coupled with the corresponding 7Be concentrations, they allow characterizing the dynamics of the regional continental air masses. δ13C values in PM10 appear to be controlled by i) emissions from different types of combustion sources, including fossil fuel and biomass burning and ii) carbonate inputs from the industrial activities located around the limestone quarries, east of the city. δ15N values presented large isotope variations that can be explained by kinetic processes and the exchange between gas (NH3) and particle (NH4+) phases during the formation of secondary NH4HSO4, a reaction that was enhanced as Cl− concentrations decreased, revealing the preponderant role of local emissions in the budget of the aerosol nitrogen. This study confirms that isotope analysis is reliable for tracing the origin of aerosols and highlight the importance of a multi-isotope approach.

Atmospheric nitrogen deposition is one of the main threats for biodiversity and ecosystem functioning. Measurement techniques like ion-exchange resin collectors (IECs), which are less expensive and time-consuming than conventional methods, are gaining relevance in the study of atmospheric deposition and are recommended to expand monitoring networks. In the present work, bulk and throughfall deposition of inorganic nitrogen were monitored in three different holm oak forests in Spain during two years. The results obtained with IECs were contrasted with a conventional technique using bottle collectors and with a literature review of similar studies. The performance of IECs in comparison with the conventional method was good for measuring bulk deposition of nitrate and acceptable for ammonium and total dissolved inorganic nitrogen. Mean annual bulk deposition of inorganic nitrogen ranged 3.09-5.43 kg N ha(-1) according to IEC methodology, and 2.42-6.83 kg N ha(-1) y(-1) using the conventional method. Intra-annual variability of the net throughfall deposition of nitrogen measured with the conventional method revealed the existence of input pulses of nitrogen into the forest soil after dry periods, presumably originated from the washing of dry deposition accumulated in the canopy. Important methodological recommendations on the IEC method and discussed, compiled and summarized.

To assess the impact of vehicular emissions on a mixed conifer forest, we measured the contents of the trace elements, N, C, and their respective natural isotopes (δ(15)N and δ(13)C), in the epiphytic lichen, L. vulpina. The samples were collected along transects perpendicular to Interstate 80 (I-80) and along a more remote, secondary forest road (R07). Distance to the road verge, trunk cover, and stand basal area were also recorded. Percent N ranged from 1.10% to 2.00% near I-80 and from 0.78% to 1.13% along R07. Concentrations of N, (15)N, Na, As, Pb, and Zn were enhanced in lichen samples near I-80 and were negatively correlated with distance from the road. Trunk cover values differed between roads (p

Altres ajuts: This research was also funded by the project from Autonomous Government of Madrid AGRISOST-CM (P2013/ABI-2717). CIEMAT work in this study was partially supported by an agreement between the Spanish Ministry of Agriculture, Food and Environment and CIEMAT on Critical loads and levels. The utilization of Tres Cantos monitoring site was possible thanks to an agreement between CIEMAT and Ayuntamiento de Madrid. To assess the impact of nitrogen (N) pollutants on forest ecosystems, the role of the interactions in the canopy needs to be understood. A great number of studies have addressed this issue in heavily N-polluted regions in north and central Europe. Much less information is available for the Iberian Peninsula, and yet this region is home to mountain forests and alpine grasslands that may be at risk due to excessive N deposition. To establish the basis for ecology-based policies, there is a need to better understand the forest response to this atmospheric impact. To fill this gap, in this study, we measured N deposition (as bulk, wet, and throughfall fluxes of dissolved inorganic nitrogen) and air N gas concentrations from 2011 to 2013 at four Spanish holm oak (Quercus ilex) forests located in different pollution environments. One site was in an area of intensive agriculture, two sites were influenced by big cities (Madrid and Barcelona, respectively), and one site was in a rural mountain environment 40 km north of Barcelona. Wet deposition ranged between 0.54 and 3.8 kg N ha⁻¹ year⁻¹ for ammonium (NH₄⁺)-N and between 0.65 and 2.1 kg N h⁻¹ year⁻¹ for nitrate (NO₃⁻)-N, with the lowest deposition at the Madrid site for both components. Dry deposition was evaluated with three different approaches: (1) a canopy budget model based in throughfall measurements, (2) a branch washing method, and (3) inferential calculations. Taking the average dry deposition from these methods, dry deposition represented 51-67% (reduced N) and 72-75% (oxidized N) of total N deposition. Canopies retained both NH₄⁺-N and NO₃⁻N, with a higher retention at the agricultural and rural sites (50-60%) than at sites located close to big cities (20-35%, though more uncertainty was found for the site near Madrid), thereby highlighting the role of the forest canopy in processing N pollutant emissions.

Wet N deposition comprises oxidised (nitrate) and reduced (ammonium) N forms in proportions that vary spatially with source and topography. Field evidence of long-term N form effects on semi-natural ecosystems and how these are modified by phosphorus and potassium availability are lacking. This study describes cover changes for some key peatland species and litter chemistry from Sphagnum capillifolium, Calluna and Eriophorum vaginatum, and peat in response to 9 years of N treatment. Ammonium and nitrate as NH4Cl or NaNO3 were provided to replicate plots in rainwater spray at +8 (low) or +56 (high) kg N ha−1 year, with and without PK via an automated system coupled to site meteorological conditions. Reduced N caused greater N accumulation in all key species than oxidised N, especially at higher doses, but cover declined more, though not significantly so, with oxidised than reduced N at the high N dose. Overall the detrimental effects of high N on Sphagnum and Calluna cover were significant but small. By comparison PK inclusion with 56 kg N ha−1 year as oxidised N, not reduced N, had devastating effects on cover, causing both S. capillifolium and Calluna to decrease 3–5-fold, facilitating invasion and expansion of nitrophiles, non-characteristic bog plants e.g. Epilobium angustifolium, Epilobium palustre, Juncus effusus, Digitalis purpurea and Dryopteris dilatata. N form appears to be significant for peatlands because of its effects on pH. The significance of changes in plant cover for peat chemistry and decomposition for biogeochemistry is discussed.

PM10 and PM2.5 levels, concentrations of major components, trace elements, pH, conductivity and source apportionment were evaluated from samples collected during 2009 at three different locations (rural, urban and urban-traffic) in Navarra (North of Spain). Mean particulate matter concentrations were below the annual limit value for PM10 and annual target value for PM2.5 established by the European Directive 2008/50/EC and similar to those recorded at other locations in the North of Spain. The major components of PM10 in the three sampling stations were, by order of importance, OC + EC, NO3- and non-marine sulphate (nmSO42-), whereas the major components of PM2.5 were OC + EC, nmSO42- and NO3-. ΔpH values indicated that PM2.5 samples were more acidic than PM10 ones. The 90–96% of total trace elements contribution in PM2.5 and PM10 were described by P, Ti, Cr, Mn, Ni, Cu, Zn, Sr, Sn, Ba and Pb. Concentrations of those elements were lower than values obtained in Pamplona in 2002–2004 and similar to those found in other sub-urban and urban Spanish cities. PMF model identified 5 principle sources for PM10 and PM2.5 in Iturrama and Plaza de la Cruz (crustal, secondary sulphate, secondary nitrate, traffic and sea-salt aerosols) and 4 sources for PM10 in Bertiz (crustal, secondary sulphate, secondary nitrate and sea-salt).

This study was carried out in order to assess both the deposition of heavy metal and nitrogen in a mountain ecosystem with low levels of metal deposition and its possible interactions with factors such as lithology and topography. For this purpose, samples of Hypnum cupressiforme Hedw. and topsoils were collected in a forest catchment within Bertiz Natural Park, an International Cooperative Programme on Integrated Monitoring site. Trace metals levels in mosses can be considered low compared with values reported elsewhere in Europe, and the dust soil mineral particles seemed to be the main source of these values. Only Cd and Hg presented external inputs, probably with an anthropic origin, for mosses according to the enrichment factor values, whereas historical pollution-related deposition in soils was determined for Pb, Cu, and Ni, attending to their total/extractable ratio.

Ground-level dynamics of O3, NO x and benzene, toluene, ethylbenzene and xylenes were characterised at rural sites in the medium Ebro River Basin (Northern Spain) from April to September (2003–2007) and by means of automated and passive monitoring. The study registered high O3 levels within the area, which were influenced by traffic emissions, and a monthly evolution of these levels consistent with the occurrence of a broad summer maximum, typical of polluted areas. The mean ozone concentration registered in the studied area by means of passive sampling was 87 ± 12 μg m−3. The 2008/50/EC objective value for the protection of vegetation was widely exceeded during this study (AOT40 = 57,147 ± 14,114 μg m−3 h), suggesting that current ambient levels may pose a risk for crops and vegetation in this important agroindustrial region.

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was performed in the North of Navarra (Spain) in 2006. The levels of V, Cr, Mn, Ni, Cu, Zn, As, Zr, Cd, Hg and Pb, and the total nitrogen content were determined in the samples by means of ICP-MS, CV-AA, and the Kjeldahl method. PCA analysis showed a differentiation between lithogenic (V, Cr, Mn, Ni, As and Zr) and anthropogenic elements (Mn, Cu, Zn, Cd, Hg and Pb). Spatial distribution maps were drawn using the kriging method, in order to identify the most affected areas and the main pollution sources. A similar spatial distribution was observed for the elements belonging to each group separated by the PCA, showing an important contribution from metal industries located in the Basque Country, as well as influence of long-range transboundary pollution processes. Background levels were also determined for the study area, along with the contamination factor for the different elements analysed. Mosses seemed to be good biomonitors of N deposition in areas of accumulation.

Indoor and outdoor concentrations of volatile organic compounds (VOCs) were measured in 30 pubs and cafes (13 smoking, 13 non-smoking and 4 mixed atmospheres) in Pamplona city, Spain. The samples were obtained using a sampling pocket pump connected to stainless steel tubes filled with Tenax TA, and subsequently analysed by means of GC–MS coupled to a thermal desorption unit. The levels registered were found to be generally higher indoors. Smoking, cleaning products and the entrance of outdoor pollutants were identified as the main sources of these compounds, the later being especially relevant in non-smoking areas. BTEX concentrations were higher during the winter months and higher in smoking areas also.

Fagus sylvatica L. is the most representative tree species in forests of Navarre (Northern Spain), in the boundary between the Euro-Siberian and Mediterranean regions. In this paper we assess the nutritional status of 30 beech forest stands selected in this area which belong to three vegetation series: Saxifrago hirsutae – Fageto sylvaticae S., Scillo lilio-hyacinthi – Fageto sylvaticae S. and Carici sylvaticae – Fageto sylvaticae S. We also determine the foliar content of sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), nitrogen (N) phosphorus (P) and sulphur (S) for these stands. Additionally, the crown condition was also assessed. Average stand values for Ca, Na, Mg and K foliar content were found to be above the reference values in many of the stands. Consequently, macronutrient ratios for these elements (N/Ca, K/Ca, Ca/Mg and K/Mg) were either above or below the range considered to be suitable for the harmonious growth of beech trees, but no evidence was found that this had a deleterious effect on the health status of the beech trees. Results showed that crown condition in these stands was good, with an average 12.2% of trees considered as damaged compared to an EU 22.8% for the same period. No symptoms of N-saturation were found; on the contrary, N is believed to still be a limiting factor for tree growth in the area.

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was conducted in the surroundings of two steel plants located in the North of Spain. Levels of V, Cr, Ni, Cu, Zn, As, Cd, Hg, Pb and N were determined. Very high concentrations in the areas of study were detected when compared to nearby unaffected regions. Similar trends were observed for all the elements in the differently orientated transects, showing an appreciable influence of the NW prevailing winds of the region in the dispersion of pollutants, as well as a clear decreasing gradient in the concentrations of metals in mosses within a distance of 1500 meters from the facilities. A differentiation between the elements emitted by the chimney as result of the industrial activity (V, Cr, Ni, Cu and As) and those with a high presence in steel slag deposits (Zn, Cd, Hg and Pb) was observed. The range of contamination was also established by means of the Contamination Factor, indicating a category 4 out of 6 categories, which shows the high levels reported in the areas of study. A different dynamic was registered for nitrogen regarding the rest of the heavy metals analysed except for Hg, probably due to the elevated volatility and mobility of both elements, as well as their high persistence in the atmosphere.

Ambient concentrations of volatile organic compounds (VOC) and nitrogen dioxide (NO2) were measured by means of passive sampling at 40 sampling points in a medium-size city in Northern Spain, from June 2006 to June 2007. VOC and NO2 samplers were analysed by thermal desorption followed by gas chromatography/mass-selective detector and by visible spectrophotometry, respectively. Mean concentrations of benzene, toluene, ethylbenzene, xylenes, propylbenzene, trimethylbenzenes, and NO(2) were 2.84, 13.26, 2.15, 6.01, 0.59, 1.32 and 23.17 microg m(-3) respectively, and found to be highly correlated. Their spatial distribution showed high differences in small distances and pointed to traffic as the main emission source of these compounds. The lowest levels of VOC and NO2 occurred during summer, owing to the increase in solar radiation and to lower traffic densities. Mean concentrations of benzene and NO2 exceeded the European limits at some of the monitored points.

This study examines the exposure level of passengers and drivers to VOC in public buses in a medium-size metropolitan area (Northern Spain). In-vehicle monitoring was performed on different routes, on peak and non-peak hours, during January and February 2007. A total of 112 air samples were collected onto adsorbent tubes and analysed by thermal desorption (TD) and gas chromatography/mass selective detector (GC/MSD) technique. Statistical differences were found among route to route concentrations, with those routes with major prevalence in the commercial area of the city displaying higher values; differences between peak and non-peak hours were also observed. A decrease in VOC concentrations was also registered during the weekend. BTEX ratios were estimated and found to be related to traffic emissions and similar for all the surveyed routes. Correlations confirmed traffic as the main emission source for BTEX and trimethylbenzene, their concentrations being highly associated to changes in meteorological conditions.

Ambient concentrations of volatile organic compounds (VOCs) were measured at 40 rural sampling points in Navarre (northern Spain). Air samples were collected by means of sorbent passive sampling and analyzed by thermal desorption (TD) and gas chromatography/mass-selective detector (GC/MSD). A total of 140 VOCs were identified during the study, which was carried out between May to October 2004 for a total of a 10 biweekly sampling campaigns. Concentrations of benzene, toluene, ethylbenzene, m / p -xylenes, o -xylene (BTEX) and 1,3,5-trimethylbenzene were determined in order to investigate their temporal and spatial distributions. Geostatistical analysis pointed to traffic as the main emission source of these compounds. Supporting this idea, BTEX and nitrogen oxides concentrations were found to be highly significantly correlated ( r = 0.495, P = 0.001), whereas a strong negative correlation between BTEX and ozone was also observed ( r = − 0.355, P = 0.025). The concentrations for the BTEX group were similar to the values that have been previously reported for other rural areas.

In grassland systems, cattle and sheep urine patches are recognized as nitrous oxide (N2O) emission hot spots due to the high urinary nitrogen (N) concentrations. Hippuric acid (HA) is one of the constituents of ruminant urine that has been reported as a natural inhibitor of soil N2O emissions. The aim of this study was to examine the potential for elevated ruminant urine HA concentrations to reduce N2O emissions, in situ, on an acidic heavy clay soil under poorly drained conditions (WFPS > 85%). A randomized complete block design experiment with three replications and four treatments was conducted using the closed-static-flux chamber methodology. The four treatments were applied inside the chambers: control with no artificial urine application (C), control artificial urine (U), and enriched artificial urine containing two rates of HA (55.8 and 90 mM, U+HA1, U+HA2). Soil inorganic-N, soil dissolved organic carbon (DOC), soil pH as well as N2O and methane (CH4) fluxes were monitored over a 79-day period. Although N2O emissions were not affected by the HA enriched urine treatments, U+HA2 positively affected the retention of N as NH4+ until day 3, when the soil pH dropped to values