Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

The whole relationship between environmental variables and firm performance: Competitive advantage and firm resources as mediator variables

The examination of the possible direct link between environmental protection and firm performance in the literature has generally produced mixed results. The present paper contributes to the literature by using the resource-based view as a mediating process in this relationship. The study specifically tests whether or not the resource-based view of the firm mediates the positive relationships of proactive environmental management and improved environmental performance with competitive advantage, which also has consequences for financial performance. We also check the possible link between the adoption of a pioneering approach and good environmental management practices. Our findings support that early investment timing and intensity in environmental issues impact on the adoption of a proactive environmental management, which in turn helps to improve environmental performance. The findings also show that a firm's resources and competitive advantage act as mediator variables for a positive relationship between environmental protection and financial performance. This contribution is original because the present paper develops a comprehensive whole picture of this path process, which has previously only been partially discussed in the literature. In addition, this study clarifies a relevant point in the literature, namely that the effect of environmental protection on firm performance is not direct and can vary depending on the sector considered. Whereas competitive advantage in relation to costs influences financial performance in the IPPC law sector, the relevant influence in the hotel sector comes from competitive advantage through differentiation.     

Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods

Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a significant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difficulty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specific PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the filters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities.     

Predictive models of turbidity and water depth in the Doñana marshes using Landsat TM and ETM+ images

We have used Landsat-5 TM and Landsat-7 ETM+ images together with simultaneous ground-truth data at sample points in the Doñana marshes to predict water turbidity and depth from band reflectance using Generalized Additive Models. We have point samples for 12 different dates simultaneous with 7 Landsat-5 and 5 Landsat-7 overpasses. The best model for water turbidity in the marsh explained 38% of variance in ground-truth data and included as predictors band 3 (630–690 nm), band 5 (1550–1750 nm) and the ratio between bands 1 (450–520 nm) and 4 (760–900 nm). Water turbidity is easier to predict for water bodies like the Guadalquivir River and artificial ponds that are deep and not affected by bottom soil reflectance and aquatic vegetation. For the latter, a simple model using band 3 reflectance explains 78.6% of the variance. Water depth is easier to predict than turbidity. The best model for water depth in the marsh explains 78% of the variance and includes as predictors band 1, band 5, the ratio between band 2 (520–600 nm) and band 4, and bottom soil reflectance in band 4 in September, when the marsh is dry. The water turbidity and water depth models have been developed in order to reconstruct historical changes in Doñana wetlands during the last 30 years using the Landsat satellite images time series.     

Long-Term Changes in Game Species Over a Long Period of Transformation in the Iberian Mediterranean Landscape

Agricultural change has transformed large areas of traditional farming landscapes, leading to important changes in the species community assemblages in most European countries. We suspect that the drastic changes in land-use that have occurred in Andalusia (southern Spain) over recent decades, may have affected the distribution and abundance of game species in this region. This article compares the distribution of the main game species in Andalusia during the 1960s and 1990s, using data from maps available from the Mainland Spanish Fish, Game and National Parks Service and from recent datasets on hunting yield distributions, respectively. Big-game and small-game species were significantly segregated in southern Spain during the 1990s, as two clearly independent chorotypes (groups of species whose abundances are similarly distributed) were obtained from the classification analysis. In contrast, big-game and small-game species were not significantly segregated several decades ago, when there was only one chorotype consisting of small-game species and wild boar. The other three ungulates did not constitute a significant chorotype, as they showed positive correlations with some species in the group mentioned above. These changes seem to be a consequence of the transformations that have occurred in the Iberian Mediterranean landscape over the last few decades. The abandoning of traditional activities, and the consequent formation of dense scrubland and woodland, has led to an expansion of big-game species, and a decrease of small-game species in mountain areas. Moreover, agricultural intensification has apparently depleted small-game species populations in some agricultural areas. On the other hand, the increasingly intensive hunting management could be artificially boosting this segregation between small-game and big-game species. Our results suggest that the conservation and regeneration of traditional agricultural landscapes (like those predominating in the 1960s) should be a priority for the conservation of small-game species.     

Sediment integrative assessment of the Bay of Cádiz (Spain): An ecotoxicological and chemical approach

This study consisted of the sediment toxicity assessment of the Bay of Cádiz based on two endpoints: growth inhibition for Cylindrotheca closterium (benthic microalgae) and fecundity inhibition for Tisbe battagliai (harpacticoid copepod). A new methodology to eliminate (but not as storage technique) the autochthonous biota present in the sediment samples by immersing them in liquid nitrogen (? 196 °C) was also assessed. Sediment toxicity data showed different toxicity levels for both organisms. In general, T. battagliai was more sensitive; however a good correlation (r = 0.75; p  < 0.05) between sediment toxicity results for both species was found. Data in pore water (pH, redox potential, and toxicity for microalgae and copepod) and sediment (pH, redox potential, organic carbon, and metal concentrations) demonstrated that ultra-freezing did not alter sample characteristics; thus, this technique can be adopted as a pre-treatment in whole-sediment toxicity tests in order to avoid misleading results due to presence of autochthonous biota. Multivariate statistical analysis such as cluster and principal component analysis using chemical and ecotoxicological data were employed. Silt and organic matter percentage and lead concentration were found to be the factors that explain about 77% of sediment toxicity in the Bay of Cádiz. Assay methodology determined in this study for both assayed species is considered adequate to be used in sediment toxicity monitoring programs. Results obtained using both species show that the Bay of Cádiz can be considered a moderately polluted zone.     

Mapping of tritium emissions using absorption vapour samplers

Püspökszilágy Radioactive Waste Treatment and Disposal Facility (RWTDF) is a typical near-surface engineered repository designated to store low- and intermediate-level wastes from various institutes, research facilities and hospitals in Hungary. Two automatic combined ¹⁴C–tritium sampling units installed at the facility sample the air 2 m above surface. The one installed near the vaults detects tritium (T) activities two orders of magnitude higher than the far reference sampling unit. To localize the T emissions, 19 small absorption vapour samplers filled with silica gel were settled onto the ground surface. After the saturation of the silica gel, the water was recovered and its T concentration was measured with a low-background liquid scintillation counter. The absorption vapour samplers are cheap, simple and easy-to-use. We present the samplers and the T distribution map constructed from the data, which helps to localize the T emission.     

Numerical simulations on the influence of matrix diffusion to carbon sequestration in double porosity fissured aquifers

The double porosity model for fissured rocks, such as limestones and dolomites, has some features that may be relevant for carbon sequestration. Numerical simulations were conducted to study the influence of matrix diffusion on the trapping mechanisms relevant for the long-term fate of CO₂ injected in fissured rocks. The simulations show that, due to molecular diffusion of CO₂ into the rock matrix, dissolution trapping and hydrodynamic trapping are more effective in double porosity aquifers than in an equivalent porous media. Mineral trapping, although assessed indirectly, is also probably more relevant in double porosity aquifers due to the larger contact surface and longer contact time between dissolved CO₂ and rock minerals. However, stratigraphic/structural trapping is less efficient in double porosity media, because at short times CO₂ is stored only in the fissures, requiring large aquifer volumes and increasing the risk associated to the occurrence of imperfections in the cap-rock through which leakage can occur. This increased risk is also a reality when considering storage in aquifers with a regional flow gradient, since the CO₂ free-phase will move faster due to the higher flow velocities in fissured media and discharge zones may be reached sooner.     

Bench-scale composting of source-separated human faeces for sanitation

In urine-diverting toilets, urine and faeces are collected separately so that nutrient content can be recycled unmixed. Faeces should be sanitized before use in agriculture fields due to the presence of possible enteric pathogens. Composting of human faeces with food waste was evaluated as a possible method for this treatment. Temperatures were monitored in three 78-L wooden compost reactors fed with faeces-to-food waste substrates (F:FW) in wet weight ratios of 1:0, 3:1 and 1:1, which were observed for approximately 20 days. To achieve temperatures higher than 15 degrees C above ambient, insulation was required for the reactors. Use of 25-mm thick styrofoam insulation around the entire exterior of the compost reactors and turning of the compost twice a week resulted in sanitizing temperatures (>or=50 degrees C) to be maintained for 8 days in the F:FW=1:1 compost and for 4 days in the F:FW=3:1 compost. In these composts, a reduction of >3 log(10) for E. coli and >4 log(10) for Enterococcus spp. was achieved. The F:FW=1:0 compost, which did not maintain >or=50 degrees C for a sufficiently long period, was not sanitized, as the counts of E. coli and Enterococcus spp. increased between days 11 and 15. This research provides useful information on the design and operation of family-size compost units for the treatment of source-separated faeces and starchy food residues, most likely available amongst the less affluent rural/urban society in Uganda.     

Dynamics of leaf litter and soil respiration in a complex multistrata agroforestry system,Pernambuco, Brazil

High litter inputs in agroforestry systems contribute to soil microbial activity, soil fertility and productivity. Considering that the cycling of organic matter is essential to the maintenance of physical–chemical and microbiological properties of the soil, the aims of this work were to estimate the production, accumulation and decomposition of litter, and assess soil microbial respiration in a complex multistrata agroforestry system located in the north-east of Brazil. This agroforestry system has three strata formed by forest and fruit trees and species of multiple uses. During 3 years (2011–2013), leaf litter was sampled monthly to account for litterfall and quarterly to account for litter accumulation. The rates of litter decomposition were estimated using the ratio produced-to-accumulated litter, and the correlation between litter fall and rainfall was calculated. Precipitation data were provided by the water and climate agency of Pernambuco (APAC). Soil samples (0–15 cm) were also taken quarterly, simultaneously with the litter accumulation samples, and soil microbial respiration was assessed using the capture, by a KOH solution, of the evolved CO₂. The annual production of leaf litter was stable in the 3 years of study in this agroforestry system, and the monthly input of litter to the soil was influenced by rainfall, being higher in the dry seasons. The accumulated litter on the ground was constant, as was microbial activity (respiration) through time. The estimated litter decomposition rates were 1.49 (first year), 1.33 (second year) and 1.42 (third year), being considered rapid rates of decomposition. This guarantees (to the farmer) that this system is capable of maintaining soil fertility and eliminates the need for chemical fertilizers.