Ozonisation coupled with biological degradation for treatment of phenolic pollutants: a mechanistically based study

Phenolic acids constitute an important group of pollutants which are reluctant to biological treatment. Solutions containing a mixture of cinnamic acid, p-coumaric acid, caffeic acid and ferulic acid were submitted to ozonisation. Then, the changes in biodegradability along the process were studied by means of respirometry. There is an optimum ozone dosage in the interval 3-5 min of treatment which allows to achieve the maximum increase in biodegradability (more than 10 times) and a high efficiency of the ozonisation process (COD decreases to a half of its initial value). Further ozonisation does not help to increase biodegradability and is clearly disadvantageous. Similar results are obtained with actual samples of olive oil wastewaters. This behaviour is explained based on the formation of highly biodegradable benzaldehydes as key ozonisation intermediates, in the early reaction stages.     

A dew point signaller for conservation of works of art

All works of art, from paintings, frescoes, sculptures, to monuments and buildings, are affected by diurnal and seasonal variations of the local microclimate, which induce interactions with the environmental atmosphere. Heat and vapour exchanges cause fluxes of heat and mass between the surface and the atmosphere, and may favour the agressivity of environmental pollutants. Condensation-evaporation cycles are recognized as being very important processes which adversely affect the life-time of the work of art. The need to control the microclimate or to stop condensation processes has been resolved by means of a dew-point signaller especially designed to overcome this problem. This paper discusses the characteristics of this device as well as the environmental philosophy which should be followed when conserving works of art.     

Environmental, land-use and economic implications of Brazilian sugarcane expansion 1996–2006

Governments are promoting biofuels and the resulting changes in land use and crop reallocation to biofuels production have raised concerns about impacts on environment and food security. The promotion of biofuels has also been questioned based on suggested marginal contribution to greenhouse gas emissions reduction, partly due to induced land use change causing greenhouse gas emissions. This study reports how the expansion of sugarcane in Brazil during 1996–2006 affected indicators for environment, land use and economy. The results indicate that sugarcane expansion did not in general contribute to direct deforestation in the traditional agricultural region where most of the expansion took place. The amount of forests on farmland in this area is below the minimum stated in law and the situation did not change over the studied period. Sugarcane expansion resulted in a significant reduction of pastures and cattle heads and higher economic growth than in neighboring areas. It could not be established to what extent the discontinuation of cattle production induced expansion of pastures in other areas, possibly leading to indirect deforestation. However, the results indicate that a possible migration of the cattle production reached further than the neighboring of expansion regions. Occurring at much smaller rates, expansion of sugarcane in regions such as the Amazon and the Northeast region was related to direct deforestation and competition with food crops, and appear not to have induced economic growth. These regions are not expected to experience substantial increases of sugarcane in the near future, but mitigating measures are warranted.     

Local and meso-scale patterns of recruitment and abundance of two intertidal crab species that compete for refuges

Interference competition for limited habitat or refuges is known to produce density-dependent mortality and generate patterns of micro-habitat distribution. While in mobile species the outcome of interference at a local scale can usually be determined from differences in body size and behavior, the population-level consequences of such interactions vary depending on rates of settlement and recruitment at a site, which are not directly correlated to local reproductive success. Previous experimental studies in central Chile demonstrated that interference competition for refuges is the primary factor driving microhabitat segregation between the predatory crabs Acanthocyclus gayi and Acanthocyclus hassleri, with the latter species monopolizing galleries inside mussel beds and excluding A. gayi to rock crevices. Between April 2001 and March 2006 we quantified monthly recruitment rates in artificial collectors at 17 sites over 900 km of the central coast of Chile. Results show that recruitment rates of A. hassleri are almost two orders of magnitude lower than those of A. gayi, and that they are tightly and positively correlated among sites across the region, suggesting that at scales of kilometers larval stages of these species are affected by similar oceanographic processes. Total crab densities per site were also positively correlated between species and strongly associated to mussel cover, with overall low crab densities at all sites where mussel cover was lower than about 60%. At all sites with mussel cover >60%, the ratio of A. gayi to A. hassleri density progressively decreased from recruits (2.6) to juveniles (0.5) to adults (0.04), overcoming initial differences in recruitment rates. The relative success of the inferior competitor at sites with low mussel cover does not appear to provide a potential mechanism favoring regional coexistence through dispersal to other sites (“mass effects”), because their densities were lower than at sites of high mussel cover. Yet, at many sites of low mussel cover the dominant competitor is virtually absent, allowing A. gayi to attain larger population sizes at the scale of the region. Thus, the factors limiting the dominant competitor from successfully utilizing other microhabitats seem to be the most critical factor in promoting both local and regional coexistence between these species.     

PM10 and PM2.5 source apportionment in the Barcelona Metropolitan area, Catalonia, Spain

Levels of total suspended particles, PM10, PM2.5 and PM1 were continuously monitored at an urban kerbside in the Metropolitan area of Barcelona from June 1999 to June 2000. The results show that hourly levels of PM2.5 and PM1 are consistent with the daily cycle of gaseous pollutants emitted by traffic, whereas TSP and PM10 do not follow the same trend, at least in the diurnal period. The PM2.5/PM10 ratio is dependent on the traffic emissions, whereas additional contribution sources for the >10 μm fraction must be taken into account in the diurnal period. Different PM10 and PM2.5 source apportionment techniques were compared. A methodology based on the chemical determination of 83% of both PM10 and PM2.5 masses allowed us to quantify the marine (4% in PM10 and <1% in PM2.5), crustal (26% in PM10 and 8% in PM2.5) and anthropogenic (54% in PM10 and 73% in PM2.5) loads. Peaks of crustal contribution to PM10 (up to 44% of the PM10 mass) were recorded under Saharan air mass intrusions. A different seasonal trend was observed for levels of sulphate and nitrate, probably as a consequence of the different thermodynamic behaviour of these PM species and the higher summer oxidation rate of SO₂.     

A derivation of the statistical characteristics of forest fires

The analysis of large data sets concerning fires in various forested areas of the world has pointed out that burned areas can often be described by different power-law distributions for small, medium and large fires and that a scaling law for the time intervals separating successive fires is fulfilled. The attempts of deriving such statistical laws from purely theoretical arguments have not been fully successful so far, most likely because important physical and/or biological factors controlling forest fires were not taken into account. By contrast, the two-layer spatially extended forest model we propose in this paper encapsulates the main characteristics of vegetational growth and fire ignition and propagation, and supports the empirically discovered statistical laws. Since the model is fully deterministic and spatially homogeneous, the emergence of the power and scaling laws does not seem to necessarily require meteorological randomness and geophysical heterogeneity, although these factors certainly amplify the chaoticity of the fires. Moreover, the analysis suggests that the existence of different power-laws for fires of various scale might be due to the two-layer structure of the forest which allows the formation of different kinds of fires, i.e. surface, crown, and mixed fires.     

Determination of spatially-resolved porosity, tracer distributions and diffusion coefficients in porous media using MRI measurements and numerical simulations

This work is focused on measuring the concentration distribution of a conservative tracer in a homogeneous synthetic porous material and in heterogeneous natural sandstone using MRI techniques, and on the use of spatially resolved porosity data to define spatially variable diffusion coefficients in heterogeneous media. The measurements are made by employing SPRITE, a fast MRI method that yields quantitative, spatially-resolved tracer concentrations in porous media. Diffusion experiments involving the migration of H(2)O into D(2)O-saturated porous media are conducted. One-dimensional spatial distributions of H(2)O-tracer concentrations acquired from experiments with the homogeneous synthetic calcium silicate are fitted with the one-dimensional analytical solution of Fick's second law to confirm that the experimental method provides results that are consistent with expectations for Fickian diffusion in porous media. The MRI-measured concentration profiles match well with the solution for Fick's second law and provide a pore-water diffusion coefficient of 1.75×10(-9)m(2)s(-1). The experimental approach was then extended to evaluate diffusion in a heterogeneous natural sandstone in three dimensions. The relatively high hydraulic conductivity of the sandstone, and the contrast in fluid density between the H(2)O tracer and the D(2)O pore fluid, lead to solute transport by a combination of diffusion and density-driven advection. The MRI measurements of spatially distributed tracer concentration, combined with numerical simulations allow for the identification of the respective influences of advection and diffusion. The experimental data are interpreted with the aid of MIN3P-D - a multicomponent reactive transport code that includes the coupled processes of diffusion and density-driven advection. The model defines local diffusion coefficients as a function of spatially resolved porosity measurements. The D(e) values calculated for the heterogeneous sandstone and used to simulate diffusive and advective transport range from 5.4×10(-12) to 1.0×10(-10)m(2)s(-1). These methods have broad applicability to studies of contaminant migration in geological materials.     

Determining seasonal greenhouse gas emissions from ground-level area sources in a dairy operation in central Texas

Greenhouse gas (GHG) emissions from agricultural production operations are recognized as an important air quality issue. A new technique following the U.S. Environmental Protection Agency Method TO-14A was used to measure GHG emissions from ground-level area sources (GLAS) in a free-stall dairy operation in central Texas. The objective of this study was to quantify and report GHG emission rates (ERs) from the dairy during the summer and winter using this protocol. A weeklong sampling was performed during each season. A total of 75 and 66 chromatograms of air samples were acquired from six delineated GLAS (loafing pen, walkway, barn, silage pile, settling basin, and lagoon) of the same dairy during summer and winter, respectively. Three primary GHGs--methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O)--were identified from the dairy operation during the sampling periods. The estimated overall ERs for CH4, CO2, and N2O during the summer for this dairy were 274, 6005, and 7.96 g head(-1)day(-1), respectively. During the winter, the estimated overall CH4, CO2, and N2O ERs were 52, 7471, and 3.59 g head(-1)day(-1), respectively. The overall CH4 and N2O ERs during the summer were approximately 5.3 and 2.2 times higher than those in the winter for the free-stall dairy. These seasonal variations were likely due to fluctuations in ambient temperature, dairy manure loading rates, and manure microbial activity of GLAS. The annualized ERs for CH4, CO2, and N2O for this dairy were estimated to be 181, 6612, and 6.13 g head(-1)day(-1), respectively. Total GHG emissions calculated for this dairy with 500 cows were 2250 t of carbon dioxide equivalent (CO2e) per year.     

Preliminary risk analysis for LNG tankers approaching a maritime terminal

LNG ships may represent a remarkable risk source, especially when approaching a land terminal, not only due to the possible occurrence of maritime accident, but also since they may represent a suitable target for terrorist attacks. A preliminary risk analysis for LNG ships approaching the Panigaglia terminal is carried out: based on literature data and on the characteristics of the location, a spill originated from a sea accident can be excluded; on the contrary, intentional damages may cause the release of a large amount of LNG, giving rise to a pool fire. Consequence analysis shows that dangerous thermal effects are expected within a radius of 700–1500 m; in the location under exam, the impact on resident population will be negligible, for the most probable attack site, and marginal for an occasionally used anchorage, which should be no longer allowed.     

Source apportionment of urban fine and ultra-fine particle number concentration in a Western Mediterranean city

Extensive measurements on particle number concentration and size distribution (13–800 nm), together with detailed chemical composition of PM_2.5 have constituted the main inputs of the database used for a source apportionment analysis. Data were collected at an urban background site in Barcelona, Western Mediterranean.The source identification analysis helped us to distinguish five emission sources (vehicle exhausts, mineral dust, sea spray, industrial source and fuel-oil combustion) and two atmospheric processes (photochemical induced nucleation and regional/urban background particles derived from coagulation and condensation processes). After that, a multilinear regression analysis was applied in order to quantify the contribution of each factor.This study reveals that vehicle exhausts contribute dominantly to the number concentration in all the particle sizes (52–86%), but especially in the range 30–200 nm. This work also points out the importance of the regional and/or urban formed aerosols (secondary inorganic particles) on the total number concentration (around 25% of the total number), with a higher impact on the accumulation mode. The photo-chemically induced nucleation of aerosols only represents a small proportion of the total number as an annual mean (3%), but is very relevant when considering only the nucleation mode (13–20 nm) fraction (23%). The other sources recognized registered sporadic contributions to the total number, coinciding with specific meteorological scenarios.This study discloses the main sources and features affecting and controlling the fine and ultra-fine aerosols in a typical city in the Western Mediterranean coast. Whereas the road traffic appears to be the most important source of sub-micrometric aerosols, other sources may not be negligible under specific meteorological conditions.