Maria Luiza D.P. Godoy

Metal concentrations, fluxes, inventories and chronologies in sediments from Sepetiba and Ribeira Bays: a comparative study.

Three sediment cores were sampled at Sepetiba Bay and four cores at Ribeira Bay, Rio de Janeiro State, Brazil. Sediment accumulation rates and chronologies were obtained from (210)Pb activity-depth profiles. Sediment accumulation rates in Ribera Bay ranged from 1.2 mm y(-1) in the inner bay to 2.6 mm y(-1) close to its entrance. In Sepetiba Bay two sediment accumulation rates were observed: a lower rate of 0.35 cm y(-1) before the 1960s and 0.76 cm y(-1) since then. The cause of this change is due to the construction of the Santa Cecília impoundment (1955) that brings water from the Paraíba do Sul Basin into the Guandu River, which increased its flow from the original 20 m(3)s(-1) to 160 m(3)s(-1). Concentration of 44 elements was obtained by ICP-MS after total dissolution of samples from two selected cores. The relative differences between the concentrations of crustal elements, such as Al, Fe and Ti are only about 20% (p<0.05). Cd and Zn are 15 and four times larger in Sepetiba Bay than in Ribeira Bay, respectively. Other major and minor elements show lower statistically significant differences. The enrichment factors and metal inventories show that Sepetiba Bay can be considered polluted with Bi, Cd, Cr, Cu, Sb and Zn. Particularly, Cd and Zn present concentrations three and four times higher than the Brazilian existing limits.

Use of multitracers for the study of water mixing in the Paraíba do Sul River estuary

Multitracers were used to study water mixing in the Paraíba do Sul River estuary region in August 2007 (dry season) and March 2008 (rainy season) and to evaluate the reach of the river plume in the direction of the open ocean. Two sampling campaigns were carried out, each in a different season. Based on these results, it was possible to conclude that the multitracers used in this study (salinity, Si, Ba and U, as well as the radium isotopes 223Ra, 224Ra, 226Ra and 228Ra) presented satisfactory results toward defining the plume reach and determining the residence time and water-mixing processes in the estuary. A strong correlation was observed between tracers and the distance to the coast. During the low river water discharge period, the riverine water took about 10 days to reach open ocean waters (salinity approximately 35). During the rainy period this value decreased to 6 days. Based on the radium results, it was possible to calculate diffusion coefficients (K(h)) of 23 km(2) d(-1) and 38 km(2) d(-1) for 224Ra and 223Ra, respectively, during the dry season (winter). Values of 65 km(2) d(-1) and 68 km(2) d(-1) for 223Ra and 224Ra, respectively, were found for the rainy period (summer).

Natural radionuclides in Brazilian mineral water and consequent doses to the population.

Based on production data published by the Brazilian Mineral Water Producers Association, bottled mineral waters were bought at the market, covering, at least, 50% of the annual production of each Brazilian geographical region. 228Ra, 226Ra and 210Pb were analyzed and the weighted mean values obtained for Brazilian mineral waters were 0.097, 0.027 and 0.066 Bq l-1 respectively. Individual effective dose rate estimates due to ingestion of mineral water in Brazil were of the order of 10-100 microSv yr-1, depending on the geographical region. Based on the available data, it was also possible to evaluate the per caput effective dose rate and the highest value obtained was 4.3 microSv yr-1 for the northern region.

Determination of total content and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes by ICP-QMS

The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8fg for (239)Pu and 1ng (238)U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian-Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, (240)Pu/(239)Pu, (241)Pu/(239)Pu, (234)U/(238)U and (235)U/(238)U atomic ratio results.

Application of inductively coupled plasma quadrupole mass spectrometry for the determination of monazite ages by lead isotope ratios

In order to evaluate the applicability of inductively coupled plasma quadrupole mass spectrometry to the determination of Pb/Pb, U/Pb and Th/Pb ages of monazite, studies were carried out initially applying lead atom ratio reference standards (NIST SRM 981 and 982). Further, the optimized methodology was applied to monazite sands from three different sites, Sugar Loaf Hill (Rio de Janeiro city), Buena (Rio de Janeiro state) and Black Sands Beach (Guarapari, Espirito Santo state); the obtained mean ages, (581 ± 21)Myears, (552 ± 32)Myears and (535 ± 3)Myears, respectively, are in agreement with the literature values for zircon and monazite samples from the same sites. Single grain Th/Pb ages were also determined for the monazite sample from Black Sands beach, nine grains were analyzed and the mean value, (530 ± 26)Myears, is in agreement with the value obtained with bulk samples. Finally, the method was applied to a thorianite sample from Amapa state and the observed Th-Pb, U-Pb and Pb-Pb ages obtained were (2.15 ± 0.05)Gyears, (2.03 ± 0.01)Gyears anda (2.044 ± 0.006)Gyears respectively, with a mean value of (2.08 ± 0.07)Gyears. This value is coherent with the (2.08 ± 0.02)Gyears age of the Bacuri complex, Amapa, reported in the literature.

Application of multivariate statistical analysis to superficial soils around a coal burning power plant

The Thermoelectric Complex Jorge Lacerda (TCJL), located in the Santa Catarina State, Brazil, is the largest coal burning thermoelectric complex of Latin America and consists of seven power plants with a total capacity of 832 MWe. In order to estimate the contribution of the atmospheric releases from the TCJL to the elemental composition of surface soils around it, forty-five samples were collected at up to a distance of 8 km. Forty-two elements were determined by ICP-MS and ICP-AES after total acid dissolution. The technique of principal component analysis was employed to identify the major sources that contribute to surface soil composition. Additionally, a source apportioning using multiple regression on absolute principal component scores was performed in order to obtain quantitative information about the contribution of the different identified sources on the soil composition. Based on the results obtained, four sources were identified as the main contributors to the surface soil elemental composition. One of them was related to TCJL because it retains volatile elements enriched on fly ash and released from powerhouse stacks.

Pluriannual watershed discharges of hg into a tropical semi-arid estuary of the Jaguaribe river, NE Brazil

Mercury fluxes were measured during the dry and rainy seasons (2005 to 2009) at the Jaguaribe River estuary, which discharges into the Equatorial Atlantic Ocean in NE Brazil. During rainy periods, the water masses exhibited a short residence time within the estuary (0.8 days). During dry periods, seawater choked the fluvial discharge, resulting in longer residence times (3.1 days). Dissolved (< 0.7 µm) and particulate Hg concentrations and fluxes were greater from the river to the estuary than from the estuary to the sea, producing accumulated particulate Hg in the estuary. Particulate Hg export (1.8 to 12.6 mg s-1) to the ocean occurred during extremely rainy periods, while dissolved Hg export was practically nonexistent during rainy periods and increased up to 0.45 mg s-1 during dry periods. Because continental runoff in semi-arid regions is affected by land use and global climate changes, the increasing accumulation of particulate Hg in the estuaries and increasing export of dissolved Hg to the ocean are expected.

Multi-site PM2.5 and PM2.5-10 aerosol source apportionment in Rio de Janeiro, Brazil

Aerosol sampling was performed at ten sites distributed in different location of Rio de Janeiro city, from September/2003 to Sepetember/2004, on a weekly basis with 24 h sampling time interval. PM2.5 and PM2.5-10 aerosol particles were sampled using Stacked Filter Units (SFU). Aerosol mass, black carbon, water soluble ions concentration as well as total aluminum, calcium, iron, magnesium, potassium, sodium and titanium concentration were determined. Mean annual PM10 mass concentration ranged from 18 to 38 µg m-3, without violation of the Brazilian air quality standards. For fine and coarse modes, between 70 and 90% of the measured mass was apportioned to relatively few sources, soil dust accounts for 37-63% of the coarse mode mass. On the other hand, black carbon and secondary aerosol, related to anthropogenic sources as fuel burning, represents very high proportions (45-58%) of the PM2.5 mass.

228Ra and 226Ra in coastal seawater samples from the Ubatuba region: Brazilian southeastern coastal region

The present work reports 228Ra and 226Ra results obtained during the 4th Submarine Groundwater Discharge (SGD) intercomparison experiment realized in Ubatuba, November 2003, aiming to test the methodologies on a fractured crystalline rocks system. Although with distinct objectives, it was decided to participate in this experiment in order to verify if radium isotopes could be used to determine water mixing rates in this region and to test the laboratory capability to perform, later on, a marine dispersion model validation at Angra dos Reis reactor site, located nearby. The results show that the SGD model constrains seems to be valid, at least for a distance of 20 km offshore, that corresponds to the distance between the reactor site and Ilha Grande, a 193-km2 island existing at this site and probably an additional SGD source. Salinity, barium and silica results are also reported and their relation to 228Ra concentrations is discussed.

Evaluating sedimentation rates in the estuary and shelf region of the Paraíba do Sul River, Southeastern Brazil

This study aims to evaluate sedimentation rates in the Paraiba do Sul estuary and its shelf regions. These sedimentation rates were correlated with strong erosion occurring in Atafona, Rio de Janeiro. The results were based on four transects, from which 14 sediment cores with approximately 540 sediment samples were collected in January 2010 and February 2011. At sampling points south of the Paraiba do Sul River (PSR) mouth, 210Pb inventories were higher than those at the northern and central sampling locations, suggesting that sediment is transported southward by the alongshore current. The 210Pb dating results were validated based on the elemental concentration variation throughout two of the sediment cores. Heavy metal concentrations, such as Cd and Zn, increased significantly in 1982 and reached maximum values (0.5 mg kg-1 and 139 mg kg-1, respectively) in 1984. These maxima correspond to the Cia Paraibuna de Metais industry accident, which occurred in 1982.