Organic speciation of atmospheric particles in Alvão Natural Park (Portugal)

PM₁₀ continental rural background aerosols were collected during a summer field campaign (August–September 2006) at Lamas de Ôlo in the upper zone of the Alvão Natural Park, a mountain region of northern Portugal. In addition to the determination of the carbonaceous content by a thermal–optical method, the organic speciation of aerosols was performed by gas chromatography–mass spectrometry in an effort to evaluate photo-oxidation products of biogenic volatile organic compounds and other markers for source characterization. The detailed analysis revealed relatively high concentrations of polyols and short-chain dicarboxylic, tricarboxylic, hydroxycarboxylic, and oxocarboxylic acids, many of which are thought to be indicators of secondary aerosol formation, accounting for about 70% of global chromatographically resolved mass. Major photo-oxidation products of α- and β-pinene have been detected. The tracers for the photo-oxidation of isoprene comprise two diastereoisomeric 2-methyltetrols, C₅-alkene triols, and 2-methylglyceric acid, which have only recently been elucidated. In addition, the occurrence of levoglucosan and other biomass combustion tracers indicates that the site was affected by wildfires. This source contributed to more than 80% of the organic carbon mass during a period of strong forest fire influence.     

Risk of boron and heavy metal pollution from agro-industrial wastes applied for plant nutrition

In this study, the effects of various agro-industrial wastes were investigated when applied to soil alone or in combination with chemical fertilizers, regarding the risks of boron and heavy metal pollution of soils and plants. Nine combinations of production residues from various agro-industries, urban wastes, and mineral fertilizers were applied to potatoes in a field experiment. The content of available boron in the soil differed significantly (p < 0.05) among the applications. Generally, B values were found to be slightly higher when soapstock, prina, and blood were used alone or in combination. Although total Co, Cd, and Pb contents of soils showed no significant differences between the applications, Cr content differed significantly (p < 0.05). No pollution risk was observed in soil in respect to total Co, Cd, Pb, and Cr contents. The amount of boron and heavy metals in leaves showed no significant differences among the applications. Cobalt, Cd, and Pb in leaves were at normal levels whereas Cr was slightly above normal but well under the critical level. Boron was low in tubers and varied significantly between applications such as Co and Cd. The Co content of tubers was high, Cd and Cr contents were below average, and Pb content was between the given values. Some significant correlations were found between soil characteristics and the boron and heavy metal content of soil, leaves, and tubers.     

Trace metal concentrations in tissues of two tinamou species in mining areas of Bolivia and their potential as environmental sentinels

Mining has a long history in the Bolivian Andes and has left many tailing piles, from which trace metals may reach surface waters, soils, and biota. The potential of tinamous (Birds: Tinamidae) as sentinels has never been tested before, although their biological and ecological characteristics mean they could well be appropriate bioindicators. We captured 13 and nine individuals of the Ornate Tinamou (Nothoprocta ornata) from two polluted sites (P1 and P2) and 10 and five from control unpolluted sites (NP1 and NP2) and used, for comparative purposes, four specimens bred in captivity. We also captured six specimens of Darwin’s Nothura (Nothura darwinii) from the polluted site, P2. We determined the concentration of As, Cd, Pb, and Sb in feathers, liver, and kidney and conducted histological analyses of liver and kidney. For the Ornate Tinamou, a site effect was found for all trace metals in all tissues, with the highest concentrations at polluted sites. At the P2 site, no differences between the two tinamou species were detected except in some cases where Darwin’s Nothura shows near-double concentrations. In some cases, mean and/or individual values of trace metal concentrations reached toxicity levels at the polluted sites. Thesaurismosis in proximal convoluted renal tubules, probably related to Cd exposure, was observed in 30% of the samples from the P1 site. Significant correlations were observed between all tissues for all trace metals and also for all trace metals in each tissue. Because the species studied are ubiquitous and relatively abundant, we recommend monitoring programs based on feather analysis.     

Effect of humic deposit (leonardite) on degradation of semi-volatile and heavy hydrocarbons and soil quality in crude-oil-contaminated soil

In order to investigate the bioremedial potential of humic deposit (leonardite), the effects of the treatments of leonardite and a commercial bioaugmentation agent on the degradation of a variety of petroleum hydrocarbons (C13–C31) and soil enzyme activities (urease acid-alkaline phosphatase and dehydrogenase) were tested within a soil incubation experiment lasting 120 days. Experimentally crude-oil-contaminated soil (2.5%) was regulated to a C:N:P ratio (100:15:1; Oilcon), amended with 5% of leonardite and regulated to the same C:N:P ratio (Oilcon-L) or mixed with a commercial bioaugmentation product (Oilcon-B), respectively. In the short period of incubation (60 days), Oilcon and Oilcon-B treatments showed higher hydrocarbon degradations, whereas Oilcon-L showed higher hydrocarbon degradation over Oilcon and Oilcon-B treatments in the long-term (120 days). Applying contaminated soil with leonardite increased urease (LSD, 4.978, *P?<?0.05) and dehydrogenase (LSD, 0.660, *P?<?0.05) activities. However, acid and alkaline phosphatase activities showed no certain inclination between different treatments. Dehydrogenase seemed to be more related to hydrocarbon degradation process. Overall results showed that leonardite enhanced biodegradation of petroleum hydrocarbons and also stimulated soil ecological quality measured as soil enzyme activities.     

Performance evaluation of two commercial chemiluminescence NOx analysers according to European Standard EN 14211

According to Directive 2008/50/EC, all equipment used for NO(x) fixed measurements must comply with the reference method or equivalent by 11 June 2013. Up to that date, non-type-approved equipment can continue to be used in air monitoring networks and will probably also be used in air pollution studies even after that date. In this context, it is advisable to know how these "old" measuring instruments respond to the requirements of European Standard EN 14211: 2005: Ambient Air Quality--Standard method for the measurement of the concentration of nitrogen dioxide and nitrogen monoxide by chemiluminescence. In this work, we carry out a thorough performance evaluation of two commercial NO(x) analysers, both purchased before 2010, according to the mentioned Standard. Results show that water vapour interference is one of the most important disconformities with this Standard. The expanded uncertainty estimation of both analysers was below the quality objective of the above-mentioned Directive (15%); however, this calculation was performed by applying some modifications to the proposed model of Standard EN 14211. These modifications are also discussed in the paper.     

Monitoring water quality in reservoirs for human supply through multi-biomarker evaluation in tropical fish

Paraíba do Sul River is located at a very densely inhabited region of Brazil crossing the three most industrialized states of the country (S?o Paulo, Minas Gerais and Rio de Janeiro states). As a result, industrial and farming residues as well as urban sewage are frequently disposed without appropriate treatment. The current study aimed at investigating the water quality in three reservoirs along the Paraíba do Sul River (Ilha dos Pombos, Santa Cecília and Santa Branca), through physiological, morphological, biochemical, and genetic biomarkers. The bioindicator chosen was the catfish Pimelodus maculatus, sampled during the dry (June 2008) and rainy (February 2009) seasons. Also, some water physicochemical parameters were analyzed from the sampling sites, but displayed no alterations according to the Brazilian Agency for Water Quality Legislation. Branchial carbonic anhydrase activity was inhibited in the dry season, while renal carbonic anhydrase activity was inhibited in the rainy season in the Santa Branca reservoir, indicating disturbance of osmoregulatory and acid-base regulation processes. Histopathological alterations were observed in the gills (neoplasic and tissue hyperplasia processes) and liver (necrosis), indicating serious damage to the functional integrity of these organs. A high incidence of melanomacrophage centers was observed in the liver, suggesting an intense immune response in all reservoirs. Acetylcholinesterase and catalase activity showed also differences corroborating some morphological results. Likewise, the induction of the micronucleus and DNA damage indicate genotoxicity, but mainly in the Santa Branca reservoir. Thus, the health status of P. maculatus warrants caution in the use of the water from the 3 reservoirs for direct human consumption, particularly after the accidental spill of endosulfan in November 2008, three months before the rainy season sampling.     

Workplace aerosol mass concentration measurement using optical particle counters

Direct-reading aerosol measurement usually uses the optical properties of airborne particles to detect and measure particle concentration. In the case of occupational hygiene, mass concentration measurement is often required. Two aerosol monitoring methods are based on the principle of light scattering: optical particle counting (OPC) and photometry. The former analyses the light scattered by a single particle, the latter by a cloud of particles. Both methods need calibration to transform the quantity of scattered light detected into particle concentration. Photometers are simpler to use and can be directly calibrated to measure mass concentration. However, their response varies not only with aerosol concentration but also with particle size distribution, which frequently contributes to biased measurement. Optical particle counters directly measure the particle number concentration and particle size that allows assessment of the particle mass provided the particles are spherical and of known density. An integrating algorithm is used to calculate the mass concentration of any conventional health-related aerosol fraction. The concentrations calculated thus have been compared with simultaneous measurements by conventional gravimetric sampling to check the possibility of field OPC calibration with real workplace aerosols with a view to further monitoring particle mass concentration. Aerosol concentrations were measured in the food industry using the OPC GRIMM? 1.108 and the CIP 10-Inhalable and CIP 10-Respirable (ARELCO?) aerosol samplers while meat sausages were being brushed and coated with calcium carbonate. Previously, the original OPC inlet had been adapted to sample inhalable aerosol. A mixed aerosol of calcium carbonate and fungi spores was present in the workplace. The OPC particle-size distribution and an estimated average particle density of both aerosol components were used to calculate the mass concentration. The inhalable and respirable aerosol fractions calculated from the OPC data are closely correlated with the results of the particle size-selective sampling using the CIP 10. Furthermore, the OPC data allow calculation of the thoracic fraction of workplace aerosol (not measured by sampling), which is interesting in the presence of allergenic particles like fungi spores. The results also show that the modified COP inlet adequately samples inhalable aerosol in the range of workplace particle-size distribution.     

Monitoring of ozone effects on the vitality and increment of Norway spruce and European beech in the Central European forests

The ozone effect on Norway spruce (Picea abies (L) Karst.) and European beech (Fagus sylvatica L.) was studied on 48 monitoring plots in 2005-2008. These plots represent two major forest tree species stands of different ages in eight regions of the Czech Republic. The forest conditions were represented by defoliation and the annual radial increment of individual trees. The ozone exposure was assessed by using modeled values of mean annual O(3) concentration and the AOT40 index. The malondialdehyde (MDA) content of the foliage was analysed and used as an indicator of oxidative stress. The correlation analysis showed a significant relation of Norway spruce defoliation to the AOT40 exposure index, and European beech defoliation to the MDA level. The radial increment response to ozone was significant only for the European beech: (a) the correlation analysis showed its decrease with increasing AOT40; (b) the regression model showed its decrease with increasing mean annual ozone concentration only at lower altitudes (<700 m a.s.l.).     

Apportionment of the airborne PM10 in Spain. Episodes of potential negative impact for human health

The particulate matter with an aerodynamic diameter less than or equal to 10 and 2.5 microns respectively (PM10 and PM2.5) constitutes one of the main air pollutants, which is currently regulated in Europe through Directive 2008/50/EC due to its proven harmful effects on human health. In this paper, the airborne PM10 samples collected in Zaragoza city during 2001-2009 were apportioned by statistical tools based on principal component analysis with absolute principal component scores (PCA-APCS). PM10 samples were characterized regarding their concentrations of polycyclic aromatic hydrocarbons (PAH) and water-soluble ions. PAH were analyzed by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) and ions were analyzed by ion chromatography. A total of five factors were identified by PCA-APCS corresponding to different anthropogenic and natural sources. This work was focused on analyzing in more detail those samples involving higher negative impact on human health, in particular, PM10 samples exceeding the daily PM10 limit value of 50 μg m(-3) according to Directive 2008/50/EC and samples with concentrations of benzo[a]pyrene (BaP) higher than the upper assessment threshold (BaP > 0.6 ng m(-3)) established by the Directive 2004/107/EC. Most of the exceedances of the daily PM10 limit value were associated with direct and indirect North-African long-range transport. During these exceedances, it was observed that anthropogenic pollution sources slightly decreased with regard to the natural sources. This indicated that episodes of high PM10 could have a natural origin associated with long-range transport from the African continent. On the contrary, those exceedances with regional contribution and samples with BaP concentrations higher than 0.6 ng m(-3) showed an important contribution of anthropogenic pollution sources increasing their negative impact on human health.