Monitoring of meteorological and hydrological droughts in the Vistula basin (Poland)

The article presents the course of meteorological droughts in Vistula subcatchments in years 1981–2010 and their influence on the occurrence of hydrological droughts. Using the Standardized Precipitation Index (SPI) as an indicator of meteorological drought on the one hand and the Standardized Water-level Index (SWI) and Standardized Runoff Index (SRI) as indicators of hydrological drought on the other, the mutual relationships between precipitation conditions and hydrological conditions were evaluated, as well as the relationships between the two drought types. Studies were conducted for three cumulative periods of these indices, of 12, 24, and 48 months. It was determined that meteorological droughts occurred earliest in the north-western and central part of the basin, and latest in areas lying above 300 m a.s.l. and in the south of Poland. Total duration, depending on the cumulative period, for SPI comprised from 38 to 41% of the analyzed period and for SWI (35–47%) and SRI (24–51%). The strongest relationships were identified in the central part of the Vistula (0.8?<?r?<?0.85), while the weakest relationships were recorded in the foothill region (r?<?0.5). There were also indicated non-climate-related factors influencing those relationships (underground reservoirs, diverse Vistula water resource usage for municipal and industrial intake).     

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

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.     

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.     

PM2.5 and PM10: The influence of sugarcane burning on potential cancer risk

In Brazil, sugarcane fields are often burned to facilitate manual harvesting, and this burning causes environmental pollution from the large amounts of soot released into the atmosphere. This material contains numerous organic compounds such as PAHs. In this study, the concentrations of PAHs in two particulate-matter fractions (PM_2.5 and PM₁₀) in the city of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugarcane plantations) were determined during the sugarcane harvest (HV) and non-harvest (NHV) seasons in 2008 and 2009. The sampling strategy included four campaigns, with 60 samples in the NHV season and 220 samples in the HV season. The PM_2.5 and PM₁₀ fractions were collected using a dichotomous sampler (10 L min^?1, 24 h) with Teflon? filters. The filter sets were extracted (ultrasonic bath with hexane/acetone (1:1 v/v)) and analyzed by HPLC/Fluorescence. The median concentration for total PAHs (PM_2.5 in 2009) was 0.99 ng m^?3 (NHV) and 3.3 ng m^?3 (HV). In the HV season, the total concentration of carcinogenic PAHs (benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene) was 5 times higher than in the NHV season. B(a)P median concentrations were 0.017 ng m^?3 and 0.12 ng m^?3 for the NHV and HV seasons, respectively. The potential cancer risk associated with exposure through inhalation of these compounds was estimated based on the benzo[a]pyrene toxic equivalence (BaP_eq), where the overall toxicity of a PAH mixture is defined by the concentration of each compound multiplied by its relative toxic equivalence factor (TEF). BaP_eq median (2008 and 2009 years) ranged between 0.65 and 1.0 ng m^?3 and 1.2–1.4 ng m^?3 for the NHV and HV seasons, respectively. Considering that the maximum permissible BaP_eq in ambient air is 1 ng m^?3, related to the increased carcinogenic risk, our data suggest that the level of human exposure to PAHs in cities surrounded by sugarcane crops where the burning process is used is cause for concern.     

A simplified approach to the indirect evaluation of the chemical composition of atmospheric aerosols from PM mass concentrations

The present work shows a straightforward procedure to indirectly estimate the chemical composition at a given site only from the determination of the PM concentrations, and the classification of the days according to the main meteorological scenarios. A previous study based on the mean chemical composition associated to the main meteorological scenarios is required.This experiment has been carried out with data from two monitoring sites in the North-Western Mediterranean, one regional and one suburban background. At both sites, one-year datasets on chemical PM₁₀ composition were obtained. Based on these datasets, the mean PM₁₀ compositions according to the most relevant meteorological situations were calculated for both locations. After that, the reconstruction of the chemical composition for all the days with available PM₁₀ concentrations was completed. Subsequently, the estimated PM₁₀ composition was compared with that determined experimentally. The comparison between the rebuilt and the experimental results was very satisfactory in the case of the regional background site, and relatively replaced in the other case. Furthermore, the validation of the method at the regional background site has been conducted from the reconstruction of a 4-year data base, and subsequent comparison with the experimental chemical composition.Our results show that it is possible to attain a good approach to the chemical composition at regional background sites, where local emission sources are negligible. Conversely, when the local sources rise in importance, i.e., at a suburban background site, the approach is suitable only for those components with a more regional origin and/or those from long range transport of air masses.     

An urban emissions inventory for South America and its application in numerical modeling of atmospheric chemical composition at local and regional scales

This work describes the development of an urban vehicle emissions inventory for South America, based on the analysis and aggregation of available inventories for major cities, with emphasis on its application in regional atmospheric chemistry modeling. Due to the limited number of available local inventories, urban emissions were extrapolated based on the correlation between city vehicle density and mobile source emissions of carbon monoxide (CO) and nitrogen oxides (NOx). Emissions were geographically distributed using a methodology that delimits urban areas using high spatial resolution remote sensing products. This numerical algorithm enabled a more precise representation of urban centers. The derived regional inventory was evaluated by analyzing the performance of a chemical weather forecast model in relation to observations of CO, NOx and O₃ in two different urban areas, São Paulo and Belo Horizonte. The gas mixing ratios simulated using the proposed regional inventory show good agreement with observations, consistently representing their hourly and daily variability. These results show that the integration of municipal inventories in a regional emissions map and their precise distribution in fine scale resolutions are important tools in regional atmospheric chemistry modeling.     

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.