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.     

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.     

Anoxic-aerobic treatment of the liquid fraction of cattle manure

Cattle manure from a dairy farm was treated in order to reduce its pollution potential. The manure came from a farm with 120 cows kept in stables in a free stall barn. As pretreatment, the manure is usually filtered on the farm using a screw press separator with a 0.5 mm mesh. Approximately 70% of the total filtered volume passes through the screen, thus constituting the liquid fraction. This fraction, with a composition of around 64,500 mg COD/l, 5770 mg total-N/l and 800 mg total-P/l, was subjected to centrifugation followed by a two-step biological treatment (anoxic-aerobic) to reduce organic matter (COD), nitrogen and phosphorus compounds. Centrifugation led to the following removal efficiencies: 35% total solids, 60% COD, 75% total phosphorus and 20% total nitrogen (mainly organic nitrogen). With the subsequent anoxic-aerobic treatment, average removal efficiencies of 85% for COD, 90% for total phosphorus and 75% for total nitrogen were achieved.     

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.     

Prediction models of CO, SPM and SO2 concentrations in the Campo de Gibraltar Region, Spain: a multiple comparison strategy

The 'Campo de Gibraltar' region is a very industrialized area where very few air pollution studies have been carried out. Up to date, no model has been developed in order to predict air pollutant levels in the different towns spread in the region. Carbon monoxide (CO), Sulphur dioxide (SO(2)) and suspended particulate matter (SPM) series have been investigated (years 1999-2000-2001). Multilayer perceptron models (MLPs) with backpropagation learning rule have been used. A resampling strategy with two-fold crossvalidation allowed the statistical comparison of the different models considered in this study. Artificial neural networks (ANN) models were compared with Persistence and ARIMA models and also with models based on standard Multiple Linear Regression (MLR) over test sets with data that had not been used in the training stage. The models based on ANNs showed better capability of generalization than those based on MLR. The designed procedure of random resampling permits an adequate and robust multiple comparison of the tested models. Principal component analysis (PCA) is used to reduce the dimensionality of data and to transform exogenous variables into significant and independent components. Short-term predictions were better than medium-term predictions in the case of CO and SO(2) series. Conversely, medium-term predictions were better in the case of SPM concentrations. The predictions are significantly promising (e.g., d (SPM 24-ahead) = 0.906, d (CO 1-ahead) = 0.891, d (SO2 1-ahead) = 0.851).     

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.     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

Effect of biosolid incorporation to mollisol soils on Cr, Cu, Ni, Pb, and Zn fractionation, and relationship with their bioavailability

Biosolid application to soil may be a supply of nutrients and micronutrients but it may also accumulate toxic compounds which would be absorbed by crops and through them be incorporated to the trophic chain.

The present study deals with the effect of biosolid application on Cr, Cu, Pb, Ni, and Zn in agricultural soils. The procedure used is sequential extraction so that the availability of those metals may be estimated and related to their bioavailability as determined through two indicator plants grown in greenhouse: ryegrass (Lolium perenne L.) and red clover (Trifolium pratense). Results showed that biosolid application to soil increased total Cu and Zn content. Sequential extraction showed that the more labile Zn fractions increased after biosolid application to soil. This was confirmed when assessing the total content of this metal in shoot and root of the plants under study, since a higher content was found in plant tissues, while no significant differences were found for Cu, Cr, Ni, and Pb.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.