Critical analysis of the waste management performance of two uranium production units in Brazil--part II: Caetite production center

This paper discusses the environmental waste management of the Heap-Leach Uranium Production Facility of Caetité located in a semi-arid region in Brazil. A comparison is made with the first uranium production site of the country located in Poços de Caldas. It is demonstrated that differences in the operational process along with different environmental conditions can lead to different impacts. In the present case groundwater is the potential most sensitive environmental medium despite the well-established consensus in the literature that radon and aerosol emissions may turn-out to be the most relevant environmental aspects of an installation located at this type of region. Most of the ²²⁶Ra content in the ore remains in the leached ore that is deposited with the waste rock. A lack in appropriate prediction of the hydrological balance has been causing unanticipated emissions of liquid effluents into the environment. Chemical treatment of this effluent may be needed. Contamination of groundwater in the short term by the waste ponds is not to be expected but it can be a relevant issue in the long term. As a consequence, careful closure schemes will need to be put in place. Finally, the overall costs with remediation in the Caetité production center are lower than those observed at the Poços de Caldas mining site.     

Application of fluorescence in situ hybridization technique to detect simazine-degrading bacteria in soil samples

We propose a new approach to evaluate the natural attenuation capacity of soil by using fluorescence in situ hybridization (FISH). A specific oligonucleotide probe AtzB1 was designed based on the sequence data of the atzB gene involved in the hydrolytic deamination of s-triazines; this gene, located in a multiple copy plasmid was detected by the optimized FISH protocol. Two agricultural soils (Lodi and Henares) with a history of simazine treatments, and two natural soils (Soto and Monza), without previous exposure to simazine, were studied. AtzB1 probe-target cells were found only in the agricultural soils and, in a greater percentage, in the Lodi soil, compared to the Henares one. Moreover, the greatest percentage of AtzB1 probe-target cells in Lodi was accompanied by a greater mineralization rate, compared to the Henares soil. The FISH method used in this study was suitable for the detection of simazine-degrading bacteria and could be a useful indicator of the potential of soil bioremediation.     

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.     

Biochemical mechanisms of resistance in Daphnia magna exposed to the insecticide fenitrothion

Resistance to fenitrothion and enzyme activities associated with the toxicity and metabolism of organophosphorus insecticides were measured in three genetically unique Daphnia magna clones collected from rice fields of Delta del Ebro (NE Spain) during the growing season and a lab sensitive clone. The studied clones showed up to sixfold differences in resistance to fenitrothion. The lack of correlation between in vitro sensitivity of acetylcholinesterase (AChE) to fenitrooxon and resistance to fenitrothion indicated that insensitivity of AChE to the most active oxon metabolite was not involved in the observed differences in resistance. Inhibition of mixed- function oxidases (MFOs) by piperonyl butoxide (PBO) increased the tolerance to fenitrothion by almost 20-fold in all clones without altering their relative ranking of resistance. Conversely, when exposed to fenitrooxon, the studied clones showed similar levels of tolerance, thus indicating that clonal differences in the conversion of fenitrothion to fenitrooxon by MFOs were involved in the observed resistance patterns. Despite that resistant clones showed over 1.5 higher activities of carboxilesterase (CbE) than sensitive ones, toxicity tests with 2-(O-cresyl)-4H-1,3,2-benzodioxaphosphorin-2 oxide, which is a specific inhibitor of these enzymes, evidenced that this system only contributed marginally to the observed clonal differences in tolerance. Glutathione-S-transferases activity (GST) varied across clones but not under exposure to fenitrothion, and was only related with tolerance levels in the field clones. In summary, our results indicate that MFO mediated differences on the bio-activation of the phosphorotionate OP pesticide to its active oxon metabolite contributed mostly in explaining the observed moderate levels of resistance, whereas the activities of CbE and GST had only a marginal role.     

Sub-soil contamination due to oil spills in six oil-pipeline pumping stations in northern Mexico

Mexico has a very important oil industry, comprehending the exploration, production, transformation, storage and distribution of crude oil and its fractions. Petroleos Mexicanos (PEMEX) is a state-owned monopoly in charge of these activities. Oil and oil-products transport is an extremely crucial operation for the cycle production-transformation-distribution. Pipeline system transport crude oil and sub-products along the country (including liquids, gases and mixtures). It has been reported that more than 30% of the oil ducts in Mexico have been operating for over 30 years, although their lifetime has been calculated in 25-30 years. This work is aimed at characterizing a zone around six oil-pipeline pumping stations located at northern Mexico. The specific places to evaluate soil contamination were (1) the distribution head of the Gomez Palacio (GOPA) pumping station; (2) the north side of the old ditch, the API oil separator and the wastewater zones of the Jimenez (JIM) pumping station; (3) the pumping stations of Ceballos (CE), Peronal (PER), Simon Bolivar (SIBO), and Mayran (MAY). The study comprehended sampling of the areas, delimitation of contamination in the vertical and horizontal extension, analysis of the sampled soils, regarding TPH and, in some cases, the 16 PAHs considered as a priority by USEPA, calculation of areas and volumes contaminated (according to the Mexican legislation, specifically NOM-EM-138-ECOL-2002) and, finally, a proposal for the best remediation techniques suitable for the encountered contamination levels and the localization of contaminants. In general, TPHs were found in all the pumping stations analyzed in this study. Regarding maximal TPHs concentrations at the stations, their order of contamination was as follows: SIBO>CE>PER>MAY>JIM>GOPA. PAHs were found only in a few points at concentrations above the detection limit. At the Jimenez, Gomez Palacio, Peronal, and Ceballos stations, only one point, with PAHs values over the detection limit was found, whereas two points were found at Mayran, and finally at the Simon Bolivar station there were four points with measurable amounts of PAHs. Given the areas and volumes that need to be treated (32835 m3), as well as the physical position of contaminants, it is considered that excavation of the contaminated soil is feasible and the cleaning process could be soil washing assisted with surfactants, though bioremediation should not been discharged as a possible remediation technique.     

Influence of the chemical structure on mobility of PCB congeners in female and male sardine (Sardina pilchardus) from Portuguese coast

Concentrations of 30 polychlorinated biphenyl congeners (CBs) were determined in muscle, liver and gonad tissues of female and male sardines (Sardina pilchardus) collected in February-May 2000 and September-January 2001 from purse seine vessels operating around Peniche, Portugal. The determined CBs were aggregated in four groups (I, II, III and IV), according to similarities of their chemical structures. Muscle and liver of males contained significantly higher concentrations of groups I and II than females during the final period of spawning (February-April). A less contrast was observed for the groups III and IV. This seasonal fluctuation associated with the spawning indicates that female sardines regulate the excess of CBs sequestrated during fatten period. On the contrary, levels of groups I and II were higher in males than in females indicating slower mobility of these compounds as lipids were consumed during the final period of spawning. The deficient regulation of those CBs in muscle of male sardines can not be attributed to selective transfer to gonads and subsequent excretion. Although the full explanation was not found for the different mobility of PCBs with the gender, the results provide evidence of slower elimination of group I and II congeners in male sardines.     

Mercury and selenium in blue shark (Prionace glauca, L. 1758) and swordfish (Xiphias gladius, L. 1758) from two areas of the Atlantic Ocean

Muscle, liver and stomach contents of 64 blue sharks and 52 swordfishes, caught between September 2004 and February 2005 near the Azores (area A) and the Equator (area E), were analysed for mercury and selenium. Levels of mercury were relatively high (blue shark: 0.032-2.5microgg(-1); swordfish: 0.031-9.8microgg(-1)) and comparable to values reported in the literature. However, mercury and organic mercury concentrations in muscle and liver of specimens from E were significantly higher than those from A. A similar trend was registered in stomach contents, suggesting higher uptake of Hg in specimens from E. This difference was also observed in the relationship between concentration in muscle and size, indicating a higher accumulation rate in specimens from E. The accumulation of Se in the liver of both species showed a positive correlation with inorganic mercury concentrations, pointing to a detoxifying mechanism of organic mercury in these species through Se-Hg liasons.     

Bioaccumulation of metals and effects of a landfill in small mammals. Part II. The wood mouse, Apodemus sylvaticus

We assess the bioaccumulation of metals (Pb, Hg, Cd, Fe, Mg, Zn, Cu, Mn, Mo, Cr) and effects of landfill leachates on morphological (RI, relative weights), plasma (GPT, GOT, creatinine), and genotoxic (MNT) parameters in wood mice, Apodemus sylvaticus, inhabiting close the Garraf landfill site (NE Spain). Due to the high age- and sex-dependent variation in wild populations, we also studied the effect of these biotic factors on the parameters studied. Wood mice from the landfill site, sited in a partially protected area, showed more Cd, Fe, Zn, Cu, Mn, Mo, and Cr than specimens from the reference site. Moreover, mice near the landfill registered low RI and high relative renal weight, GPT, and MN frequency, which indicate that the landfill affects the health of wild mice. In contrast to sympatric shrews from a previous study, wood mice showed lower bioaccumulation of metals and lower variation caused by biotic factors. Moreover, the morphological and physiological alterations demonstrated that they were also more sensitive at environmental pollution. Given the contribution of small mammals to ecosystem function and the scarce ecotoxicological data on the effects of landfill pollution on wild terrestrial mammals, we consider that our study can be used to improve the management of this protected area.     

Cephalopods and cetaceans as indicators of offshore bioavailability of cadmium off Central South Brazil Bight

Regarding Brazilian coast, industrial and urban developments are concentrated along Central South Brazil Bight. Samples from inshore and offshore species from the concerned area were analyzed, comprising 24 cetaceans (9 species) and 32 squids (2 species). Cadmium was determined by GFAAS and our results were in agreement with certified values (DOLT-2, NRCC). Mean cadmium concentration (in microg/g, wet weight) observed in the digestive gland of sexually mature Argentine short-finned squids (Illex argentinus) was 1002.9. To our knowledge this is the highest cadmium level ever reported for a cephalopod. Concerning cetaceans, our results include one of the highest renal cadmium concentrations described for striped dolphins (71.29 microg/g, wet weight). Anthropogenic action, upwelling and cannibalism of Argentine short-finned squid on the studied area are possible reasons for such remarkable cadmium concentrations.