High surface area materials prepared from sewage sludge-based precursors

This paper focuses on physical activation (CO2) and chemical activation (H3PO4, NaOH and KOH) of sewage sludge-based precursors. Our results show that (i) a simple acid washing treatment leads to a significant increase in the adsorption capacity of some precursors; (ii) under the experimental conditions tested, CO2 physical activation and chemical activation with H3PO4 were ineffective for an efficient porosity development and (iii) choosing an appropriate protocol, it is possible to obtain highly porous materials (700-1700 m2 g(-1)) by chemical activation of sludge-based precursors with alkaline hydroxides. The efficiency of the chemical activation with NaOH or KOH is very much influenced by the method used for mixing the activating agent and the precursor. The BET values of the materials obtained when physically mixing ground hydroxides with the precursor almost doubled the values obtained if other mixing methods are employed. Increasing the hydroxide:precursor ratio leads to an enhancement of the adsorption capacity of the adsorbents, with BET values ranging from 689 to 1224 m2 g(-1) for NaOH activation and from 853 to 1686 m2 g(-1) for KOH activation.     

Surveillance programme on dioxin levels in soils in the Campo de Gibraltar (southwest Spain)

The results of an epidemiologic study undertaken by the Spanish Council for Scientific Research (CSIC) after commission by the Spanish Parliament indicated that Huelva and Cádiz were the zones in Andalusia with elevated risk of cancer. A 6% (women) and 10% (men) cancer mortality excess was observed with respect to the other six Andalusian provinces. Huelva and Cádiz are located in the south-western region of Spain, and are characterized by a strong industrial activity concentrated in several industrial sites. This situation led to two environmental surveys in these areas, in which the presence of dioxins was studied among other parameters. A PCDD/F assessment in soils of the Campo de Gibraltar (Cádiz) was carried out from June 2003 to June 2004. A total of 20 samples were collected in this study divided in two sampling campaigns. The first 10 samples were taken in locations affected by high industrial activity zones as well as in landfills (hotspots). The rest of the samples were collected in areas that were not expected to be contaminated, such as agricultural zones and forests. I-TEQ values of the samples ranged from 0.26 to 15.08 ng/kg dm. In all, 85% of the samples were below the limit of 5 ng I-TEQ/kg I-TEQ concentrations of three samples only surpassed this limit. These zones corresponded to a landfill, a quarry used for dumping chemical product containers and a sample from the sewage system of the industrial site. These sites were used neither for agricultural nor for public purposes.     

Antimony content of macrofungi from clean and polluted areas

Species of macrofungi (mushrooms) were collected from clean areas and analyzed for their antimony content. These were compared to species collected from extremely polluted areas in the vicinity of a lead smelter and on mine and slag dumps. Antimony content was determined using long-term instrumental neutron activation analysis (INAA). Ectomycorrhizal and terrestrial saprobic macrofungi were examined. Antimony content of macrofungi from the clean areas was mostly less than 100 μg kg⁻¹ (dry mass). The highest concentrations (units of mg kg⁻¹) were found in various species of the ectomycorrhizal genera Chalciporus and Suillus. Antimony contents of macrofungi growing in the polluted areas were considerably higher. The highest content was found in a single collection of Chalciporus piperatus (1423 mg kg⁻¹).     

Characterization of surface marine sediments from Ría de Arousa estuary according to extractable humic matter content

Surface marine sediments from Ría de Arousa estuary were analyzed for humic and fulvic acids by UV-visible spectrometry and have been characterized using elemental analysis (carbon, hydrogen and nitrogen elemental composition) and spectrometric data (A2/A4 ratio, absorbancies at 270 and 407 nm and E4/E6 ratio, absorbancies at 465 and 665 nm). These variables have been used as discriminating factors to distinguish of marine and terrestrial origin of humic and fulvic acids in Ría de Arousa surface marine sediments. Principal component analysis, PCA, and cluster analysis, CA, have been used as unsupervised pattern recognition procedures. The half-range central value transformation was used as data pre-treatment to homogenize data. After a Varimax rotation, PCA applied to humic acid data has reveled that spectrometric A2/A4 and E4/E6 ratios are the main dominating features in the first principal component (48.6% of total variance), the humic acid content is the feature with the highest weight in the second principal component (22.9% of the total variability) and the carbon elemental composition domain in the third principal component (13.3% of total variance). Results from PCA have revealed that surface sediments collected at inner-left part of the estuary and at the mouth of the river Ulla belong to the same group. Similarly, PCA has shown that surface sediments from the right mouth of the estuary form a compact group. Taking in account the water circulation in Ría de Arousa estuary, these findings mean that the organic matter in surface sediments from the inner-left part of the estuary derived mainly from terrestrial organic matter while the organic matter in surface sediments from the right mouth of the estuary is mainly derived from marine sources. Finally, it must be noticed that any classification of surface sediments was assessed when applying of PCA and CA from fulvic acids data.     

Presence of plutonium contamination in soils from Palomares (Spain)

More than 30 years after the occurrence of an aircraft accident which involved the detonation of two nuclear weapons in the surrounding area of the village of Palomares (Spain), the affected terrestrial area has been investigated for remaining transuranic contamination. Evidence from the presence of this contamination was initially found through the analysis of the 241Am inventories in superficial soil samples collected in the region, and was confirmed through the analysis of the (239+240)Pu inventories and their associated 238Pu/(239+240)Pu activity ratios in the same samples. However, it was also observed that a considerable fraction of the remaining contamination in the area was present in particulate form, i.e. as "hot particles". The work performed in our laboratory for identification, isolation and characterisation of these "hot particles" as well as some conclusions obtained from these analyses are outlined in this paper.     

Presence of surfactants and their degradation intermediates in sediment cores and grabs from the Cadiz Bay area

The occurrence and distribution of the major surfactants--LAS, AES, APEOs and AEOs--and their degradation intermediates--SPCs, AP and APECs--in a marine-estuarine environment at Spain are presented. Results show that their concentration in surface sediments is clearly correlated with their usage and the existence of wastewater discharges. The degradation processes appear to lead to the formation of SPCs in the case of LAS, and to the shortening of the average ethoxylated chain length in the case of NPEOs, AEOs and AES. Vertical profiles for AEOs and AES are reported for the first time and present the highest values nearest the surface, followed by a sharp decrease with depth for all surfactants, as well as the appearance of degradation intermediates in deeper sedimentary layers. Shorter LAS homologues and SPCs tend to be present in pore water while strongly non-polar intermediates like NP are firmly attached to the sediments.     

Effect of acid rain on building material of the El Tajín archaeological zone in Veracruz, Mexico

Three limestone slabs (approx. 20 cm2 each) were extracted from the El Tajin archaeological zone in Veracruz, Mexico. X-ray diffraction analysis revealed three components: calcite (81.2%), quartz (17.9%) and feldspar (0.9%). Calcite content by x-ray diffraction analysis was slightly higher than that determined by chemical reaction between the limestone sample and nitric acid. The latter analysis, carried out in triplicate, yielded a calcite content of 77.1%. Mean water absorption, density and porosity of the limestone samples were also determined. Dissolution of limestone samples was investigated using an experimental rainfall simulation chamber, in which the stone samples were irrigated with artificial rain matching the pH and the ionic composition with 40 rainfall samples collected at El Tajin from August 18, 2002, to April 9, 2003. According to calcium and bicarbonate net concentrations found in the effluent of the chamber, a chemical mechanism by which limestone at El Tajin is dissolved by acid rain is proposed. A model used to investigate the air transport pathways corresponding to precipitation events at El Tajin shows that air parcels come mainly from the Gulf of Mexico, although no directional preference is evident for acidic vs. non-acidic events.     

Use of the genus Artemia in ecotoxicity testing

Information related to varied uses of several species of the genus Artemia (commonly known as brine shrimp), is dispersed among literature from several scientific areas, such as Ecology, Physiology, Ecotoxicology, Aquaculture and Genetics. The present paper reviews information related to Artemia that may be considered relevant for ecotoxicity testing. Integration of different areas of scientific knowledge concerning biology, life cycle and environmental needs of Artemia is of crucial importance when considering the interpretation of results drawn from tests involving this genus. Furthermore, this paper provides suggestions to overcome problems related to toxicity assessment with the use of Artemia as test organism in bioassays, under the scope of estuarine, marine and hypersaline environments. Aspects related to variability in results, adoptable toxicity end-points, culture conditions, characteristics of species and strains, influence of geographical origins over physiological features and responses to exposure to chemical agents are considered.     

Using sediment quality guidelines for dredged material management in commercial ports from Spain

Dredged material contamination was assessed in different commercial ports from Spain: Port of Cádiz and Huelva, South West; Bilbao and Pasajes, North; Cartagena and Barcelona, East; Coru?a, North West. Sediment from different locations of these ports was sampled and was characterized following the Spanish recommendations for dredged material management. This characterization included grain size distribution, organic matter content and concentration of the chemical compounds included in the list of pollutants and hazardous substances (As, Cd, Cu, Cr, Hg, Ni, Pb and Zn; PCB congeners IUPAC number 28, 52, 101, 118, 138, 153 and 180; PAHs were also analyzed). The results were compared to the limit values of Spanish Action Levels that define the different categories for assessment and management. A set of empirically derived sediment quality guidelines (SQG) was used to assess the possible toxicity of the dredged materials and to improve the use of the chemical approach to characterize dredged material for its management.     

Multi-technique characterization of a nuclear bomb particle from the Palomares accident

A January 1966 accident dispersed Pu and other nuclear bomb materials in the vicinity of Palomares, a village in southeastern Spain. Radioactive particles were identified in a soil sample collected in 1998 and analytical results obtained from one of the isolated particles are presented here. Isolation of the particle was performed using gamma-ray spectrometry and imaging plates. Scanning electron microscopy with X-ray microanalysis revealed the presence of U and Pu as well as Pb and Fe in the particle of approximately 10microm diameter. Radioisotopes of U, Pu, and Am were quantified using radiometric methods, inductively coupled plasma mass spectrometry and secondary ion mass spectrometry. The elevated (235)U/(238)U atom ratio indicates enriched U, and the Pu atom ratios are consistent with weapons-grade material. This work demonstrates that the analysis of individual particles provides information not available through bulk sample analysis.