Geraldo Resende Boaventura

Rapid neodymium release to marine waters from lithogenic sediments in the Amazon estuary.

Rare earth element (REE) concentrations and neodymium isotopic composition (ɛNd) are tracers for ocean circulation and biogeochemistry. Although models suggest that REE release from lithogenic sediment in river discharge may dominate all other REE inputs to the oceans, the occurrence, mechanisms and magnitude of such a source are still debated. Here we present the first simultaneous observations of dissolved (<0.45 μm), colloidal and particulate REE and ɛNd in the Amazon estuary. A sharp drop in dissolved REE in the low-salinity zone is driven by coagulation of colloidal matter. At mid-salinities, total dissolved REE levels slightly increase, while ɛNd values are shifted from the dissolved Nd river endmember (−8.9) to values typical of river suspended matter (−10.6). Combining a Nd isotope mass balance with apparent radium isotope ages of estuarine waters suggests a rapid (3 weeks) and globally significant Nd release by dissolution of lithogenic suspended sediments.

Metal Distribution in Sediments from the Ribeira Bay, Rio de Janeiro - Brazil

Investigation of metal distribution in preserved areas is highly relevant due to the present-day lack of reliable databases against which to assess contamination. 23 samples of surface sediments from the Ribeira Bay, Rio de Janeiro State, Brazil, were analyzed by ICP/AES for Ti, Ca, Mg, Fe, Al, Sr, La, V, Y, Ni, Cu, Cr, Mn and Zn. Hg concentrations were determined by CVAAS. With respect to Al, metals were classified as strongly correlated, correlated, inversely correlated and non-correlated. Cluster analysis of the concentration data confirmed this, except for Hg. Cluster analysis of the sampling sites produced three groups, on the basis of grainsize, continental input, and marine input. Climatic and hydrodynamic factors, as well as soil characteristics, are important controls of the metal distribution in this region. The Ribeira Bay has a natural background metal content, when compared with average shales and with other impacted and non-impacted regions.

Rare earth element analysis in natural waters by multiple isotope dilution – sector field ICP-MS

The rare earth elements (REEs) are valuable tracers in the earth, ocean and environmental sciences. Ten out of fourteen stable REEs have two or more isotopes, making them suitable for quantification by isotope dilution. We present a plasma mass spectrometry based multiple isotope dilution method for high precision REE concentration analysis in aqueous media. Key aspects of the method are: (i) flexible spiking of ten REEs via two LREE and HREE mixed spike solutions. (ii) Offline pre-concentration and matrix removal, by ion chromatography for freshwater samples and by iron co-precipitation or ion chromatography with the Nobias™ resin for seawater samples. (iii) High sensitivity detection by sector field-inductively coupled plasma mass spectrometry (SF-ICP-MS). (vi) The use of a desolvation micro-nebulization introduction system to lower polyatomic Ba and LREE-oxide interferences on HREEs. The method is suitable for a range of freshwater to seawater type samples, and was validated against SLRS-4, SLRS-5, and CASS-5 reference materials and two GEOTRACES marine inter-comparison samples. Long-term external precision on all REEs was <2% RSD, except La and Ce. Minimum sample volumes are 1 ml for freshwater and 50 ml for seawater. The multispike SF-ICP-MS method should be of particular interest in exploring subtle variations in aqueous REE fractionation patterns and anomalies in large numbers of samples.

Seasonal dissolved rare earth element dynamics of the Amazon River main stem, its tributaries, and the Curuaí floodplain

We present a comprehensive dissolved rare earth element (REE) data set for the Amazon River and its main tributaries, Rio Negro, Solimoes, and Madeira, as well as the Curuai floodplain. The two-year time series show that REE vary seasonally with discharge in each of the tributaries, and indicate a hydrologically dominated control. Upper crust normalized REE patterns are relatively constant throughout the year, with Ce/Ce* anomalies being positively related to discharge. We propose revised annual dissolved REE fluxes to the surface Atlantic Ocean based on an integration of the seasonal data. For Nd (<0.22 μm) this results in an average flux of 607 ± 43 T/yr, which is at least 1.6 times larger than the previous estimate of 374 T/yr (<0.45 μm) based on low water stage data. Moreover, during the high water season the maximum Nd flux measures 1277 t.yr−1, constituting 30% of the required flux to the Atlantic Ocean (Tachikawa et al., 2003). Consequently, a smaller contribution of Nd from atmospheric and river particle desorption is required than was previously suggested. A mass balance of Amazon tributaries and observed fluxes at Obidos indicates that dissolved LREE behave quasi-conservatively. Conversely, the HREE mass balance presents a deficit during the high water stages, which could be related to the passage of water through the floodplain system accompanied by solid/dissolved phase transfer.

Multivessel system for cold-vapor mercury generation determination of mercury in hair and fish

A multivessel system for the determination of mercury (Hg) by cold-vapor atomic absorption spectrometry (CV-AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) was developed. The performance of the proposed device was tested by determining total Hg in quality-control samples of hair and fishes following acid digestion. Application of the apparatus to the determination of Hg by CV-AAS following alkaline digestion was studied as well. The detection limit obtained for CV-AAS was 0.11 ng/mL and for ICP-AES 1.39 ng/mL. The results show that the system is appropriate to be used in techniques involving cold-vapor generation of Hg.

Multielement Determination in Small Samples of Human Milk by Inductively Coupled Plasma Atomic Emission Spectrometry

Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was used for routine analysis of small samples of human milk. The concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), phosphorus (P), and zinc (Zn) were determined in 203 milk samples from postpartum women at different stages of lactation after stepwise digestion in HNO3, HCIO4, and H2O2 under heat. Validation of the procedure was achieved using certified reference material of bovine liver (NBS 1577) with mean recoveries of 103.5%. The concentrations of the above elements in milk matrix were comparable with previously reported values. The analytical results from breast milk will provide reference information for mineral studies of Brazilian mothers and breast-fed infants.

Determination of molybdenum in silicates by flame atomic absorption spectrometry exploiting activated carbon as collector

An analytical procedure has been developed for molybdenum determination in geological silicate materials using flame atomic absorption spectrometry (injection method), after sorption of the molybdenum-ammonium pyrrolidinedithiocarbamate complex (MoAPDC) on activated carbon.

Geological and anthropogenic influences on sediment metal composition in the upper Paracatu River Basin, Brazil

This work reports a geochemical study of sediments from the upper Paracatu River Basin. The objective is to define the influences of Au, Zn, and Pb mineral deposits and mining activities on the sediment metal sources, distribution, and accretion. The samples were analyzed using ICP/OES, AAS, and XRD techniques and were treated with principal components analysis and the geo-accumulation index. The main geochemical processes that control the sediment composition are pyrite oxidation, muscovite weathering, carbonate dissolution, and the erosion of oxisols enriched with Zn and Pb. The upper Rico Stream has high Al, Fe, Cu, Cr, Co, and Mn concentrations due erosion of oxisols and pyrite oxidation and muscovite alteration present in the parental rock. The artisanal alluvial gold mining increased the primary rock-minerals’ weathering and Hg sediment concentration. The lower Escuro River and Santa Catarina Stream are enriched with Zn and Pb due the erosion of metal-rich soils formed over galena, sphalerite, calamine, and willemite mineral deposits located upstream. Elements such as Ca, Mg, and Ba have low concentrations throughout the sampled area due the high solubility of these metals-bearing minerals. The dispersion of metals is limited by the basin geomorphology and their affinity to silt-clayey minerals and Fe and Mn oxides and hydroxides in circumneutral pH waters.

Geoquímica das águas da bacia hidrográfica do Rio Descoberto, Brasília/DF - Brasil

The objective of this paper is to investigate the physical and chemical quality of the water of the Descoberto River during the dry and rainy seasons by measuring pH, temperature, electric conductivity, total dissolved solids, turbidity, color, alkalinity and NO3-, SO42-, PO43-, NH4+, Cl- and HCO3-, and the elements Sr, Mo, Cd, Y, Ti, Ca, V, Mg, Fe, Si, Ni, Zr, Cu, Al, Cr, Mn, Ba, Co, Zn, P, Na and K. The results showed high concentrations in both seasons, with dilution along the course of the river, minimizing for a while problems that compromise the quality of the water of this source. However, a progressive deterioration can occur due to an increase in the discharge of pollutants, resulting from population growth, agricultural activities and other factors.

Ion Exchange Chromatography and Mass Bias Correction for Accurate and Precise Zn Isotope Ratio Measurements in Environmental Reference Materials by MC-ICP-MS

Precise and accurate d66/64Zn data for environmental reference materials (RMs) including rocks, sediments, soils and plants are presented in order to improve the metrological traceability and analytical control of Zn isotope ratio determinations in future environmental studies. Previously developed ion exchange chromatography protocols were adjusted to enable faster sample throughput and instrumental mass bias processes were investigated. The improved chromatographic protocol yielded precise and quantitative recoveries (99 ± 7%, σ, n = 16), while the mass bias correction using Cu as external dopant provided precisions better than 0.02‰, 2σ, n = 7. Investigations into spectral and non-spectral interferences identified significant formation of Cr and Ti oxides and hydroxide ionic species. Analysis of six RMs (BHVO-2 basalt (USGS), BCR-2 basalt (USGS), AGV-2 andesite (USGS), 2709 San Joaquin soil (NIST), 1646a estuarine sediment (NIST) and 1573a tomato leaves (NIST)) showed good reproducibility (< 0.01‰, 2s, 5 ≤ n ≥ 1).