Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

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.     

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).     

Assessing coastal waters of American Samoa: territory-wide water quality data provide a critical “big-picture” view for this tropical archipelago

The coastal waters of American Samoa’s five high islands (Tutuila, Aunu’u, Ofu, Olosega, and Ta’u) were surveyed in 2004 using a probabilistic design. Water quality data were collected from the near-shore coastal habitat, defined as all near-shore coastal waters including embayments, extending out to 1/4 mile off-shore. Hydrography and water column samples were collected, and water quality data were compared to the Territorial water quality standards for pH, dissolved oxygen (DO), Enterococcus, chlorophyll a, water clarity, total nitrogen, and total phosphorus. All station measurements for pH, DO, and Enterococcus satisfied the local water quality standards, although some fraction of the Territory could not be assessed for either DO or Enterococcus. With respect to chlorophyll a, 66 ± 18% of Territory coastal waters complied with the standard, while 34 ± 18% failed to comply with the standard. For water clarity, 54 ± 18% of the Territorial waters complied with the standard while 42 ± 7% failed to comply. Territorial waters satisfied the standards for total nitrogen and phosphorus 72 ± 17% and 92 ± 10%, respectively. These data provide the first “big-picture” view of water quality in the near shore region around the high islands of American Samoa. While the picture is encouraging, these data suggest emerging water quality concerns.     

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.     

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.     

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.