Influence of boundary conditions on CMAQ simulations over the Iberian Peninsula

The influence of chemical boundary conditions (BC) on the response of the Community Multiscale Air Quality (CMAQ) model over the Iberian Peninsula was investigated in this study. Three strategies to supply boundary conditions in the context of the Integrated Assessment Modelling System for the Iberian Peninsula (SIMCA) were tested. Alternative methods consist in providing BC from (1) fixed, time-independent, concentration profiles, (2) concentrations predicted in a CMAQ mother domain (48 km, 1 h resolution) and (3) concentration values from the GEOS-Chem chemical-transport global model (2 × 2.5°, 3 h resolution). High resolution (3 km) simulated concentrations of the main pollutants (NO₂, NO, SO₂, O₃, PM₁₀ and PM_2.5) were compared through a comprehensive statistical analysis including observational data from 165 monitoring stations all over the Iberian Peninsula. It was found that model sensitivity to BC for nitrogen and sulphur oxides was limited, being restricted to the vicinity of model boundaries. However, significant domain-wide differences were found when modelling ozone and PM depending on the BC provided to run the tests. Although model performance was affected by spatial and seasonal factors, the results indicate that model-derived, dynamic BC improved CMAQ predictions when compared to those based on static concentrations prescribed in the boundaries. Aggregated statistics suggest that the GEOS-Chem produced the best results for O₃ and PM_2.5 while NO₂ and PM₁₀ were slightly better predicted under the CMAQ nesting approach. Besides the statistical evaluation some other relevant issues in the context of Integrated Assessment Modelling (IAM) are discussed to gain a better insight into the suitability of the methods analyzed and limitations of downscaling methods. Despite being useful to get a better understanding of the role of BC in SIMCA, this study contributed to highlight model deficiencies and therefore to point out future research needs to improve IAM activities in the Iberian Peninsula.     

Polycyclic aromatic hydrocarbons in air on small spatial and temporal scales – II. Mass size distributions and gas-particle partitioning

Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling).In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1–1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge–Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log K_p = m log p_L⁰ + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Variable emissions of microbial volatile organic compounds (MVOCs) from root-associated fungi isolated from Scots pine

Soils emit a large variety of volatile organic compounds. In natural ecosystems, measurements of microbial volatile organic compound (MVOC) exchange rates between soil and atmosphere are difficult due to e.g. the spatial heterogeneity of the belowground organisms, and due to the many potential sources for the same compounds. We measured in laboratory conditions the MVOC emission rates and spectra of eight typical fungi occurring in boreal forest soils. The studied species are decomposers (Gymnopilus penetrans, Ophiostoma abietinum), ectomycorrhizal (Cenococcum geophilum, Piloderma olivaceum, Suillus variegatus, Tomentellopsis submollis) and endophytic fungi (Meliniomyces variabilis, Phialocephala fortinii). The MVOC emissions contained altogether 21 known and 6 unidentified compounds whose emission rates were >0.1 μg g(DW)^?1 h^?1. The most abundant compounds were the short-chain carbonyl compounds (acetone and acetaldehyde). The greatest carbonyl emissions were measured from P. olivaceum (1.9 mg acetone g(DW)^?1 h^?1) and P. fortinii (0.114 mg acetaldehyde g(DW)^?1 h^?1). Terpenoid emissions (isoprene, mono- and sesquiterpenes) were detected from some fungal cultures, but in relatively small amounts. We conclude that soil micro-organisms can potentially be responsible for significant emissions of volatiles, especially short-chain oxygenated compounds, to the below-canopy atmosphere.     

Influence of roads and inhabited areas on metal concentrations in terrestrial mosses

The guidelines regarding sampling terrestrial mosses for biomonitoring the atmospheric contamination in a region specifically recommend that sampling close to focal points of contamination (i.e. roads, populated areas, etc.) should be avoided for satisfactory characterization of general patterns of contamination. However, these recommendations cannot always be followed in many parts of the world with dense, highly dispersed populations. The aim of the present study was to determine how the distances between sampling sites (SS) and contamination foci such as roads, isolated houses and urban nuclei affect regular, large-scale sampling networks. Metal concentrations obtained in biennial sampling surveys carried out between 2000 and 2006 in Galicia (NW Spain) were used, and the relative proportions of the concentrations corresponding to small-scale and large-scale processes were calculated. The possible relationship between the mean concentrations corresponding to small-scale processes in the different sampling surveys and the distances from SS to roads, buildings and urban nuclei was established by a GIS. Outliers in the data were identified at many of the SS and frequency statistics revealed the absence of any relationship between the distance to these foci and the concentrations of metals in the moss. The method also revealed many instances of the influence of one or more small-scale contamination foci such as airports and railways (often not considered in the sampling recommendations) on SS. Relocation of such SS would improve the representativeness of the sampling grid.     

Overview of strontium-89,90 deposition measurements in Finland 1963-2005

In Finland the deposition of strontium-89 (⁹⁰Sr) and strontium-90 (⁹⁰Sr) has been monitored since the early 1960s. The measured cumulative ⁹⁰Sr deposition in 1963-2005 is on average 1200 Bq m⁻², of which 150 Bq m⁻² originates from the Chernobyl accident. Adding to this the deposition in 1945-1962 produces a value of 2040 Bq m⁻² for the cumulative deposition in Finland. The nuclear explosion-derived deposition up to 1985 obtained in this study, 1850 Bq m⁻², is in good agreement with the zonal ⁹⁰Sr deposition of 1740 Bq m⁻² in the 60°N-70°N latitude band estimated by UNSCEAR. The regional deposition patterns of ⁸⁹Sr and ⁹⁰Sr following the Chernobyl accident resemble those of the refractory nuclides such as ^239,240Pu and ⁹⁵Zr. The total deposition of Chernobyl-derived ⁹⁰Sr in Finland was about 5.3 × 10¹³ Bq. This activity corresponds to 0.027% of the reactor core inventory and 0.66% of the atmospheric emissions from the accident. The corresponding figures for ⁸⁹Sr are 4.5 × 10¹⁴ Bq, 0.023% and 0.56%, respectively.     

The distribution of Cs, K, Rb and Cs in plants in a Sphagnum-dominated peatland in eastern central Sweden

We record the distribution of ¹³⁷Cs, K, Rb and Cs within individual Sphagnum plants (down to 20 cm depth) as well as ¹³⁷Cs in vascular plants growing on a peatland in eastern central Sweden. In Calluna vulgaris¹³⁷Cs was mainly located within the green parts, whereas Andromeda polifolia, Eriophorum vaginatum and Vaccinium oxycoccos showed higher ¹³⁷Cs activity in roots. Carex rostrata and Menyanthes trifoliata showed variable distribution of ¹³⁷Cs within the plants. The patterns of ¹³⁷Cs activity concentration distribution as well as K, Rb and Cs concentrations within individual Sphagnum plants were rather similar and were usually highest in the capitula and/or in the subapical segments and lowest in the lower dead segments, which suggests continuous relocation of those elements to the actively growing apical part. The ¹³⁷Cs and K showed relatively weak correlations, especially in capitula and living green segments (0-10 cm) of the plant (r = 0.50). The strongest correlations were revealed between ¹³⁷Cs and Rb (r = 0.89), and between ¹³⁷Cs and stable Cs (r = 0.84). This suggests similarities between ¹³⁷Cs and Rb in uptake and relocation within the Sphagnum, but that ¹³⁷Cs differs from K.     

Patagonian Fjord Ecosystems in Southern Chile as a Highly Vulnerable Region: Problems and Needs

Southern Chile encompasses one of the most extensive fjord regions of the world, the Patagonia, currently exposed to natural and anthropogenic perturbations. These fjord ecosystems provide important services to humans, which have not been adequately measured and valued. As a consequence, ecosystem services are commonly ignored in public policy design and in the evaluation of development projects. Here we tackle questions that are highly relevant for the nation’s development, namely (1) understanding fjord functioning, and (2) developing management strategies based on ecosystem services, in order to secure simultaneous and adequate use of these ecosystems which area influenced by ecological (e.g., biogeochemical) and productive (e.g., aquaculture, fisheries) processes. We also seek to strengthen the analysis of fjord ecosystem value from the economical (including coastal zoning), socio-cultural, institutional, and governmental points of view. In addition, the investigation of current and future effects of climate change on this large region offers a unique opportunity to understand the social and economic consequences of a global phenomenon at local to regional scales. Biogeochemical and socio-economic models will be used to simulate future scenarios under a gamut of management options.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs).