Chemical and C and N stable isotope compositions of three species of epiphytic Tillandsia in a Caribbean coastal zone: air pollution sources and biomonitoring implications.

We characterized the elemental and C and N stable isotope compositions of Tillandsia fasciculata Sw., Tillandsia balbisiana Schult. & Schult.f. and Tillandsia recurvata (L.) L. samples collected in Cienfuegos (Cuba). Results showed high enrichment factors for S, Hg, Cd, Pb, P, Zn, Cu, Mo, Sb and Ca in all Tillandsia species, indicating inputs from local anthropogenic activities (road traffic, industries and cement production). Carbon concentrations and δ13C varied from 38.3-47.7 % and -20.4 to -13.4 ‰ within the three species, respectively. δ13C showed seasonal dependence with the dry and wet periods and more 13C-depleted values in urban/industrial areas, coherent with the input of anthropogenic emissions. Nitrogen concentrations (0.4-1.3 %) and δ15N values (-9.9-4.4 ‰) exhibit larger variations and are positively correlated in the three species. The most positive δ15N in T. recurvata (-0.2-4.4 ‰) are attributed to contributions from industrial activities and road traffic. In fact, both δ15N and total nitrogen (TN) values increase in sites with higher road traffic and show significant correlations with typical road traffic and industrial tracers. Finally, we calculate an average total nitrogen deposition rate of 4.4 ± 2.3 kg ha-1 a-1 from N content in T. recurvata, similar to the existing values determined in the region by field measurements, but higher than the global terrestrial average.

Carbon and nitrogen isotopes to distinguish sources of sedimentary organic matter in a Caribbean estuary.

Carbon and nitrogen stable isotope compositions (δ13C and δ15N) of organic matter (OM) and total organic carbon to total nitrogen ratio (Corg/TN) in a sediment core collected in Sagua estuary (Cuba), were investigated to elucidate the origin of the Sedimentary OM (SOM) and changes in its main sources, over the last 100 years. Results showed almost constant values in the elemental and isotope composition of SOM from 1908 to 1970 with an abrupt change after 1970. From 1970 to 2005, δ13C increased from -21.2 up to -19.3 ‰, while δ15N declined from 1.5 to values close to 0 ‰. The output of the mass-balance model for the identification of OM sources indicated that δ13C and Corg/TN values are generally influenced by marine Particulate OM (POM) sources. Between 1900 and 1970, the main OM source in sediments was marine POM (>85 %), with freshwater POM contributing ca. 15%. Since 1970, the establishment of the Alacranes Dam determined drastic environmental changes influencing the OM sources in the area. Mixing models pointed to seagrasses (79 %) as the main contributors to SOM in the first period, while since 1973 onward, the contribution of human-derived sources such as fertilizers and urban discharges became greater. This information can provide baseline data for the environmental management of the Sagua watershed.

Levels, spatial distribution, risk assessment, and sources of environmental contamination vectored by road dust in Cienfuegos (Cuba) revealed by chemical and C and N stable isotope compositions.

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.

CFD modelling of air quality in Pamplona City (Spain): Assessment, stations spatial representativeness and health impacts valuation.

A methodology based on CFD-RANS simulations (WA CFD-RANS, Weighted Averaged Computational Fluid Dynamic-Reynolds-Averaged Navier-Stokes simulations) which includes appropriate modifications, has been applied to compute the annual, seasonal, and hourly average concentration of NO2 and NOX throughout the city of Pamplona (Spain) at pedestrian level during 2016. The results have been evaluated using measurements provided both by the city's network of air quality monitoring stations and by a network of mobile microsensors carried around by cyclists during their daily commutes, obtaining a maximum relative error lower than 30% when computing NO2 annual average concentrations. The model has taken into account the actual city layout in three dimensions, as well as the traffic emissions. The resulting air pollution maps provided information critical for studying the traffic-related health effects of NO2 and their associated external costs in the city of Pamplona and the spatial representativeness of the current network of air quality monitoring stations (it has not been carried out for an entire city to date). The developed methodology can be applied to similar cities, providing useful information for the decision-makers.

Multi-element isotopic signature (C, N, Pb, Hg) in epiphytic lichens to discriminate atmospheric contamination as a function of land-use characteristics (Pyrénées-Atlantiques, SW France).

Multi-elemental isotopic approach associated with a land-use characteristic sampling strategy may be relevant for conducting biomonitoring studies to determine the spatial extent of atmospheric contamination sources. In this work, we investigated how the combined isotopic signatures in epiphytic lichens of two major metallic pollutants, lead (206Pb/207Pb) and mercury (δ202Hg, Δ199Hg), together with the isotopic composition of nitrogen and carbon (δ15N, δ13C), can be used to better constrain atmospheric contamination inputs. To this end, an intensive and integrated sampling strategy based on land-use characteristics (Geographic information system, GIS) over a meso-scale area (Pyrénées-Atlantiques, SW France) was applied to more than 90 sampling stations. To depict potential relationships between such multi-elemental isotopic fingerprint and land-use characteristics, multivariate analysis was carried out. Combined Pb and Hg isotopic signatures resolved spatially the contribution of background atmospheric inputs from long range transport, from local legacy contamination (i.e. Pb) or actual industrial inputs (i.e. Pb and Hg from steel industry). Application of clustering multivariate analysis to all studied isotopes provided a new assessment of the region in accordance with the land-use characteristics and anthropogenic pressures.

Carbon and nitrogen isotopes unravels sources of aerosol contamination at Caribbean rural and urban coastal sites.

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 ±â€¯1.2‰) and urban (average of -24.8 ±â€¯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.

Modelling spatial patterns of correlations between concentrations of heavy metals in mosses and atmospheric deposition in 2010 across Europe.

BACKGROUND: This paper aims to investigate the correlations between the concentrations of nine heavy metals in moss and atmospheric deposition within ecological land classes covering Europe. Additionally, it is examined to what extent the statistical relations are affected by the land use around the moss sampling sites. Based on moss data collected in 2010/2011 throughout Europe and data on total atmospheric deposition modelled by two chemical transport models (EMEP MSC-E, LOTOS-EUROS), correlation coefficients between concentrations of heavy metals in moss and in modelled atmospheric deposition were specified for spatial subsamples defined by ecological land classes of Europe (ELCE) as a spatial reference system. Linear discriminant analysis (LDA) and logistic regression (LR) were then used to separate moss sampling sites regarding their contribution to the strength of correlation considering the areal percentage of urban, agricultural and forestry land use around the sampling location. After verification LDA models by LR, LDA models were used to transform spatial information on the land use to maps of potential correlation levels, applicable for future network planning in the European Moss Survey. RESULTS: Correlations between concentrations of heavy metals in moss and in modelled atmospheric deposition were found to be specific for elements and ELCE units. Land use around the sampling sites mainly influences the correlation level. Small radiuses around the sampling sites examined (5 km) are more relevant for Cd, Cu, Ni, and Zn, while the areal percentage of urban and agricultural land use within large radiuses (75-100 km) is more relevant for As, Cr, Hg, Pb, and V. Most valid LDA models pattern with error rates of < 40% were found for As, Cr, Cu, Hg, Pb, and V. Land use-dependent predictions of spatial patterns split up Europe into investigation areas revealing potentially high (= above-average) or low (= below-average) correlation coefficients. CONCLUSIONS: LDA is an eligible method identifying and ranking boundary conditions of correlations between atmospheric deposition and respective concentrations of heavy metals in moss and related mapping considering the influence of the land use around moss sampling sites.

Quantitative study on nitrogen deposition and canopy retention in Mediterranean evergreen forests.

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 ha-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.

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems.

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990-2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990-2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990-2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.

Relevance of canopy drip for the accumulation of nitrogen in moss used as biomonitors for atmospheric nitrogen deposition in Europe.

High atmospheric deposition of nitrogen (N) impacts functions and structures of N limited ecosystems. Due to filtering and related canopy drip effects forests are particularly exposed to N deposition. Up to now, this was proved by many studies using technical deposition samplers but there are only some few studies analysing the canopy drip effect on the accumulation of N in moss and related small scale atmospheric deposition patterns. Therefore, we investigated N deposition and related accumulation of N in forests and in (neighbouring) open fields by use of moss sampled across seven European countries. Sampling and chemical analyses were conducted according to the experimental protocol of the European Moss Survey. The ratios between the measured N content in moss sampled inside and outside of forests were computed and used to calculate estimates for non-sampled sites. Potentially influencing environmental factors were integrated in order to detect their relationships to the N content in moss. The overall average N content measured in moss was 20.0mgg(-1) inside and 11.9mgg(-1) outside of forests with highest N values in Germany inside of forests. Explaining more than 70% of the variance, the multivariate analyses confirmed that the sampling site category (site with/without canopy drip) showed the strongest correlation with the N content in moss. Spatial variances due to enhanced dry deposition in vegetation stands should be considered in future monitoring and modelling of atmospheric N deposition.

Mosses as an integrating tool for monitoring PAH atmospheric deposition: comparison with total deposition and evaluation of bioconcentration factors. A year-long case-study.

Polycyclic aromatic hydrocarbon (PAH) atmospheric deposition was evaluated at a remote site in Northern Spain using moss biomonitoring with Hylocomium splendens (Hedw.) Schimp., and by measuring the total deposition fluxes of PAHs. The year-long study allowed seasonal variations of PAH content in mosses to be observed, and these followed a similar trend to those of PAH fluxes in total deposition. Generally, atmospheric deposition of PAHs is greater in winter than in summer, due to more PAH emissions from domestic heating, less photoreactivity of the compounds, and intense leaching of the atmosphere by wet deposition. However, fractionation of these molecules between the environmental compartments occurs: PAH fluxes in total deposition and PAH concentrations in mosses are correlated with their solubility (r=0.852, p<0.01) and lipophilic properties (KOW, r=0.768, p<0.01), respectively. This annual study therefore showed that atmospheric PAH fluxes can be estimated with moss biomonitoring data if the bioconcentration or 'enriching' factors are known.

Nitrogen and carbon contents and δ(15) N and δ(13) C signatures in six bryophyte species: assessment of long-term deposition changes (1980-2010) in Spanish beech forests.

In this study we used recent (2010) and herbarium material (1980) of six bryophyte species to assess long-term atmospheric deposition in natural forested areas in northern Spain. For this purpose, tissue nitrogen and carbon content, as well as δ(13) C and δ(15) N signatures of samples of Hypnum cupressiforme, Polytrichastrum formosum, Leucobryum juniperoideum, Rhytidiadelphus loreus, Homalothecium lutescens and Diplophyllum albicans were analysed and comparisons made between years and species. In addition, the usefulness of each of the six species was evaluated. The range of values observed was similar to that in other studies carried out in rural areas. Significantly lower values were found in 2010 for N (H. cupressiforme), δ(15) N (R. loreus and D. albicans), C (R. loreus) and δ(13) C (all except L. juniperoideum). Our natural areas are thus now less influenced by atmospheric pollutants than they were, most probably due to changes in some traditional local activities. Differences were observed between species for all the four parameters studied, so different species must not be analysed together. Finally, R. loreus and H. lutescens seem to be good bioindicators, sensitive even with a few samples, although further studies are needed to corroborate their usefulness.