Comparative respiratory toxicity of particles produced by traffic and sugar cane burning

The impact of particle emissions by biomass burning is increasing throughout the world. We explored the toxicity of particulate matter produced by sugar cane burning and compared these effects with equivalent mass of traffic-derived particles. For this purpose, BALB/c mice received a single intranasal instillation of either distilled water (C) or total suspended particles (15 mu g) from an urban area (SP group) or biomass burning-derived particles (Bio group). Lung mechanical parameters (total, resistive and viscoelastic pressures, static elastance, and elastic component of viscoelasticity) and histology were analyzed 24h after instillation. Trace elements and polycyclic aromatic hydrocarbons (PAHs) metabolites of the two sources of particles were determined. All mechanical parameters increased similarly in both pollution groups compared with control, except airway resistive pressure, which increased only in Bio. Both exposed groups showed significantly higher fraction area of alveolar collapse, and influx of polymorphonuclear cells in lung parenchyma than C. The composition analysis of total suspended particles showed higher concentrations of PAHs and lower concentration of metals in traffic than in biomass burning-derived particles. In conclusion, we demonstrated that a single low dose of ambient particles, produced by traffic and sugar cane burning, induced significant alterations in pulmonary mechanics and lung histology in mice. Parenchymal changes were similar after exposure to both particle sources, whereas airway mechanics was more affected by biomass-derived particles. Our results indicate that biomass particles were at least as toxic as those produced by traffic. (C) 2008 Elsevier Inc. All rights reserved.

Atmospheric pollutants monitoring by analysis of epiphytic lichens

The Canoparmelia texana epiphytic lichenized fungi was used to monitor atmospheric pollution in the Sao Paulo metropolitan region, SP, Brazil. The cluster analysis applied to the element concentration values confirmed the site groups of different levels of pollution due to industrial and vehicular emissions. In the distribution maps of element concentrations, higher concentrations of Ba and Mn were observed in the vicinity of industries and of a petrochemical complex. The highest concentration of Co found in lichens from the Sao Miguel Paulista site is due to the emissions from a metallurgical processing plant that produces this element. For Br and Zn, the highest concentrations could be associated both to vehicular and industrial emissions. Exploratory analyses revealed that the accumulation of toxic elements in C. texana may be of use in evaluating the human risk of cardiopulmonary mortality due to prolonged exposure to ambient levels of air pollution. (c) 2007 Elsevier Ltd. All rights reserved.

X-ray fluorescence with synchrotron radiation to elemental analysis of lead and calcium content of primary teeth

Primary teeth were analyzed by micro-SRXRF. The aim of this study was to determine the elemental distribution of lead and calcium in different regions of primary incisor of children living in a notoriously contaminated area (Santo Amaro da Purificacao, Bahia State, Brazil). The measurements were performed in standard geometry of 45 incidence, exciting with a white beam and using a conventional system collimation (orthogonal slits) in the XRF beamline at the Synchrotron Light National Laboratory (Campinas, Brazil). (C) 2009 Elsevier Ltd. All rights reserved.

Should we measure serum or plasma lead concentrations?

Project: Serum samples may not be appropriate to assess lead (Pb) concentrations because they may contain artificially higher Pb concentrations compared with those measured in plasma samples. Here, we compared Pb concentrations in serum versus heparin plasma separated from blood collected with or without vacuum. We have also examined the effects of sample standing time on Pb concentrations measured in serum, heparin plasma, and EDTA plasma. Procedure: We studied plasma and serum samples from twelve healthy subjects. Blood samples were collected via venous drainage phlebotomy with and without vacuum into trace metal free tubes containing no anticoagulants (serum), or lithium heparin, or EDTA (to obtain plasma). Variable sample standing times (0, 5, and 30 min) prior to centrifugation were allowed. Plasma and serum Pb and iron concentrations were determined by inductively coupled plasma mass spectrometry. Plasma and serum cell-free hemoglobin concentrations were measured. Results: Pb concentrations in serum and in heparin plasma from blood samples collected with or without vacuum were similar and not associated with significant changes in iron or hemoglobin concentrations. The sample standing time (up to 30 min) did not affect Pb concentrations in serum or in heparin plasma, which were approximately 50% lower than those found in EDTA plasma. Conclusions: Serum or heparin plasma separated from blood samples collected via venous phlebotomy with or without vacuum are appropriate medium to assess Pb concentrations, independently of the sample standing time. (C) 2010 Elsevier GmbH. All rights reserved.

The Impact of Vitamin A Supplementation on the Immune System of Vitamin A-deficient Children

Background & Aims: To investigate the effect of vitamin A supplementation on parameters of the immune system of vitamin A-deficient children. Methods: The study was carried out in four phases: 1) determination of serum retinol in 631 children from 36 to 83 months of age; 2) assessment of immunological markers [immunoglobulins and complement fractions, immunophenotyping of T and B lymphocytes, and natural killer (NK) cells], blood count, and serum ferritin of 52 vitamin A-deficient children (serum retinol <0.70 mu mol/L); 3) supplementation of the 52 deficient children with 200,000 IU of vitamin A; 4) determination of serum retinol and the immunological parameters 2 months after vitamin A supplementation. Results: Before vitamin A supplementation, 24.0% of the children were anemic and 4.3 %had reduced ferritin concentrations. There was no significant difference between mean values of retinol according to the presence/absence of anemia. The mean values of the humoral and cellular immunological parameters did not show a statistically significant difference before and after supplementation with vitamin A. Children with concomitant hypovitaminosis A and anemia presented a significant increase in absolute CD4 and CD8 T-cell counts after vitamin A supplementation (p < 0.05). Conclusion: Vitamin A had an effect on the recruitment of T and B lymphocytes to the circulation of children with hypovitaminosis A and anemia.

Vehicular particulate matter emissions in road tunnels in Sao Paulo, Brazil

In the metropolitan area of Sao Paulo, Brazil, ozone and particulate matter ( PM) are the air pollutants that pose the greatest threat to air quality, since the PM and the ozone precursors ( nitrogen oxides and volatile organic compounds) are the main source of air pollution from vehicular emissions. Vehicular emissions can be measured inside road tunnels, and those measurements can provide information about emission factors of in-use vehicles. Emission factors are used to estimate vehicular emissions and are described as the amount of species emitted per vehicle distance driven or per volume of fuel consumed. This study presents emission factor data for fine particles, coarse particles, inhalable particulate matter and black carbon, as well as size distribution data for inhalable particulate matter, as measured in March and May of 2004, respectively, in the Janio Quadros and Maria Maluf road tunnels, both located in Sao Paulo. The Janio Quadros tunnel carries mainly light-duty vehicles, whereas the Maria Maluf tunnel carries light-duty and heavy-duty vehicles. In the Janio Quadros tunnel, the estimated light-duty vehicle emission factors for the trace elements copper and bromine were 261 and 220 mu g km(-1), respectively, and 16, 197, 127 and 92 mg km(-1), respectively, for black carbon, inhalable particulate matter, coarse particles and fine particles. The mean contribution of heavy-duty vehicles to the emissions of black carbon, inhalable particulate matter, coarse particles and fine particles was, respectively 29, 4, 6 and 6 times higher than that of light-duty vehicles. The inhalable particulate matter emission factor for heavy-duty vehicles was 1.2 times higher than that found during dynamometer testing. In general, the particle emissions in Sao Paulo tunnels are higher than those found in other cities of the world.

(40)Ar/(39)Ar ages and Sr-Nd-Pb-Os geochemistry of CAMP tholeiites from Western Maranhao basin (NE Brazil)

The Central Atlantic Magmatic Province (CAMP), emplaced at the Triassic-Jurassic (T-J) boundary (-200 Ma), is among the largest igneous provinces on Earth. The Maranhao basin in NE Brazil is located around 700 km inland and 2000 km from the site of the earliest Pangea disruption. The CAMP tholeiites occur only in the western part of the basin and have been described as low and high-Ti. Here we document the occurrence of two sub-groups among the high-Ti tholeiites in the Western Maranhao basin. The major and trace elements and the Sr-Nd-Pb isotopic ratios define three chemical groups corresponding to the low-Ti (TiO(2)< 1.3 wt.%), high-Ti (TiO(2)-2.0 wt.%) and evolved high-Ti (TiO(2 >)3 wt.%) western Maranhao basin tholeiites (WMBT). The new (40)Ar/(39)Ar plateau ages obtained on plagioclase separates for high-Ti (199.7 +/- 2.4 Ma) and evolved high-Ti WMBT (197.2 +/- 0.5 Ma and 198.2 +/- 0.6 Ma) are indistinguishable and identical to those of previously analyzed low-Ti WMBT (198.5 +/- 0.8 Ma) and to the mean (40)Ar/(39)Ar age of the CAMP (199 +/- 2.4 Ma). We also present the first Re-Os isotopic data for CAMP basalts. The low and high-Ti samples display mantle-like initial ((187)Os/(188)Os)(i) ranging from 0.1267 to 0.1299, while the evolved high-Ti samples are more radiogenic (((187)Os/ (188)Os)(i) up to 0.184) We propose that the high-Ti WMBT were derived from the sub-lithospheric asthenosphere, and contaminated during ascent by interaction with the subcontinental lithospheric mantle (SCLM). The evolved high-Ti WMBT were derived from the same asthenospheric source but experienced crustal contamination. The chemical characteristics of the low-Ti group can be explained by partial melting of the most fertile portions of the SCLM metasomatized during paleo-subduction. Alternatively, the low-Ti WMBT could be derived from the sub-lithospheric asthenosphere but the resulting melts may have undergone contamination by the SCLM. The occurrences of high-Ti basalts are apparently not restricted to the area of initial continental disruption which may bring into question previous interpretations such as those relating high-Ti CAMP magmatism to the initiation of Atlantic ridge spreading or as the expression of a deep mantle plume. We propose that the CAMP magmatism in the Maranhao basin may be attributed to local hotter mantle conditions due to the combined effects of edge-driven convection and large-scale mantle warming under the Pangea supercontinent. The involvement of a mantle-plume with asthenosphere-like isotopic characteristics cannot be ruled out either as one of the main source components of the WMBT or as a heat supplier. (C) 2010 Elsevier BM. All rights reserved.

Combustion iron distribution and deposition

[1] Iron is hypothesized to be an important micronutrient for ocean biota, thus modulating carbon dioxide uptake by the ocean biological pump. Studies have assumed that atmospheric deposition of iron to the open ocean is predominantly from mineral aerosols. For the first time we model the source, transport, and deposition of iron from combustion sources. Iron is produced in small quantities during fossil fuel burning, incinerator use, and biomass burning. The sources of combustion iron are concentrated in the industrialized regions and biomass burning regions, largely in the tropics. Model results suggest that combustion iron can represent up to 50% of the total iron deposited, but over open ocean regions it is usually less than 5% of the total iron, with the highest values (< 30%) close to the East Asian continent in the North Pacific. For ocean biogeochemistry the bioavailability of the iron is important, and this is often estimated by the fraction which is soluble ( Fe(II)). Previous studies have argued that atmospheric processing of the relatively insoluble Fe(III) occurs to make it more soluble ( Fe( II)). Modeled estimates of soluble iron amounts based solely on atmospheric processing as simulated here cannot match the variability in daily averaged in situ concentration measurements in Korea, which is located close to both combustion and dust sources. The best match to the observations is that there are substantial direct emissions of soluble iron from combustion processes. If we assume observed soluble Fe/black carbon ratios in Korea are representative of the whole globe, we obtain the result that deposition of soluble iron from combustion contributes 20-100% of the soluble iron deposition over many ocean regions. This implies that more work should be done refining the emissions and deposition of combustion sources of soluble iron globally.

Water quality assessment of Toledo River and determination of metal concentrations by using SR-TXRF technique

The region of Toledo River, Parana, Brazil is characterized by intense anthropogenic activities. Hence, metal concentrations and physical-chemical parameters of Toledo River water were determined in order to complete an environmental evaluation catalog. Samples were collected monthly during one year period at seven different sites from the source down the river mouth, physical-chemical variables were analyzed, and major metallic ions were measured. Metal analysis was performed by using the synchrotron radiation total reflection X-ray fluorescence technique. A statistical analysis was applied to evaluate the reliability of experimental data. The analysis of obtained results have shown that a strong correlation between physical-chemical parameters existed among sites 1 and 7, suggesting that organic pollutants were mainly responsible for decreasing the Toledo River water quality.

The Determination of Total Hydrogen, Carbon, Nitrogen and Sulfur in Silicates, Silicate Rocks, Soils and Sediments

Determinations of the volatile elements carbon, hydrogen, sulfur and nitrogen in many geological RM, performed with the LECO CHN and SC analysers, are presented. The method allowed the determination of S in concentrations from a few % m/m to 0.001% m/m or less, of C from % m/m to 0.01% m/m and of H from % m/m to 0.004% m/m. Accuracy was usually better than the XRF method (for S). All obtained values passed the Sutarno-Steger test, which establishes that vertical bar(mean(analysed) - mean(certified))vertical bar/ S(certified) < 2, for the cases with an appropriate number of determinations (n > 10 for each element). It was possible to perform routine determination of C, H and S with the instrumentation, coupled with the determination of major and minor elements in geological materials. Determination of nitrogen could also be performed on an exploratory basis, with improvements in the method dependent on the future availability of more reference materials with reliable composition of this element.

HYDROTHERMAL REE FLUOROCARBONATE MINERALIZATION AT BARRA DO ITAPIRAPUA, A MULTIPLE STOCKWORK CARBONATITE, SOUTHERN BRAZIL

The Barra do Itapirapua ( BIT) carbonatites in southern Brazil belong to the final stages of the Early Cretaceous alkaline rock - carbonatite magmatism of the Ponta Grossa Arch Province. The BIT complex is a dyke and vein stockwork in which four main carbonatitic phases are recognized, mainly magnesiocarbonatites and ferrocarbonatites. These carbonatites are generally overprinted by pervasive hydrothermal events. The C-O stable isotopic data indicate re-equilibration under hydrothermal conditions at temperatures between 375 and 80 degrees C. Significant amounts of REE fluorocarbonate minerals, relatively Sr- and Th-rich, were deposited. Syntaxy between synchysite-(Ce) and parisite-(Ce) is very common owing to the similarity in structures, with alternating (001) layers of (CeF), (CO3) and (Ca). However, bastnasite-(Ce) occurs as individual crystals, overgrown by the synchysite and parisite polycrystals. Textural and chemical reactions between the REE fluorocarbonates provide insights into the mobility of rare-earth elements during fluid-rock interaction. The BIT complex is considered to be of potential economic interest for production of the rare-earth concentrates.

Age and geochemistry of mantle peridotites and diorite dykes from the Baldissero body: Insights into the Paleozoic-Mesozoic evolution of the Southern Alps

Trace element and isotopic data obtained for mantle spinel Iherzolites and diorite dykes from the Baldissero massif (Ivrea-Verbano Zone, Western Italy) provide new, valuable constraints on the petrologic and geodynamic evolution of the Southern Alps in Paleozoic to Mesozoic times. Whole rock and mineral chemistry indicates that Baldissero Iherzolites can be regarded as refractory mantle residues following limited melt extraction. In particular, the Light Rare Earth Elements (LREE)-depleted and fractionated compositions of whole rock and clinopyroxene closely match modelling results for refractory residues after low degrees (similar to 4-5%) of near-fractional melting of depleted mantle, possibly under garnet-facies conditions. Following this, the peridotite sequence experienced subsolidus re-equilibration at lithospheric spinel-facies conditions and intrusion of several generations of dykes. However, Iherzolites far from dykes show very modest metasomatic changes, as evidenced by the crystallisation of accessory titanian pargasite and the occurrence of very slight enrichments in highly incompatible trace elements (e.g. Nb). The Re-Os data for Iherzolites far from the dykes yield a 376 Ma (Upper Devonian) model age that is considered to record a partial melting event related to the Variscan orogenic cycle s.l. Dioritic dykes cutting the mantle sequence have whole rock, clinopyroxene and plagioclase characterised by high radiogenic Nd and low radiogenic Sr, which point to a depleted to slightly enriched mantle source. Whole rock and mafic phases of diorites have high Mg# values that positively correlate with the incompatible trace element concentrations. The peridotite at the dyke contact is enriched in orthopyroxene, iron and incompatible trace elements with respect to the Iherzolites far from dykes. Numerical simulations indicate that the geochemical characteristics of the diorites can be explained by flow of a hydrous, silica-saturated melt accompanied by reaction with the ambient peridotite and fractional crystallisation. The composition of the more primitive melts calculated in equilibrium with the diorite minerals show tholeiitic to transitional affinity. Internal Sm-Nd, three-point isochrons obtained for two dykes suggest an Upper Triassic-Lower Jurassic emplacement age (from 204 31 to 198 29 Ma). Mesozoic igneous events are unknown in the southern Ivrea-Verbano Zone (IVZ), but the intrusion of hydrous melts, mostly silica-saturated, have been well documented in the Finero region, i.e. the northernmost part of IVZ and Triassic magmatism with calc-alkaline to shoshonitic affinity is abundant throughout the Central-Eastern Alps. The geochemical and chronological features of the Baldissero diorites shed new light on the geodynamic evolution of the Southern Alps before the opening of the Jurassic Tethys. (C) 2010 Elsevier B.V. All rights reserved.

ASSOCIATED A-TYPE SUBALKALINE AND HIGH-K CALC-ALKALINE GRANITES IN THE ITU GRANITE PROVINCE, SOUTHEASTERN BRAZIL: PETROLOGICAL AND TECTONIC SIGNIFICANCE

The 590-580 Ma Itu Granite Province (IGP) is a roughly linear belt of post-orogenic granite plutons similar to 60 km wide extending for some 350 km along the southern edge of the Apia-Guaxupe Terrane in southeastern Brazil. Typical components are subalkaline A-type granites (some with rapakivi texture) that crystallized at varied, but mostly strongly oxidizing conditions, and contrast with a coeval association of also oxidized high-K calc-alkaline granites in terms of major (e. g., lower Ca/Fe) and trace elements (higher Nb, Y, Zr). Mantle-derived magmas (such as those forming the LILE-rich Piracaia Monzodiorite, with epsilon(Nd(t)) = -7 to -10, (87)Sr/(86)Sr((t)) = 0.7045-0.7055) are inferred to derive from enriched subcontinental lithosphere modified during previous subduction, and may have played a role in the generation of the A-type granites, adding melts or fluids or both to the lower crust from which the latter were generated. The IGP is interpreted as a reflection of crust uplift and increased heat flux during ascent of hot, less dense asthenosphere after continental collision, probably reflecting breakoff of an oceanic slab coeval to the right-lateral accretion of a terrane related to the Mantiqueira Orogenic System.

Alkaline magmatism in the Amambay area, NE Paraguay: The Cerro Sarambi complex

The Early Cretaceous alkaline magmatism in the northeastern region of Paraguay (Amambay Province) is represented by stocks, plugs, dikes, and dike swarms emplaced into Carboniferous to Triassic-Jurassic sediments and Precambrian rocks. This magmatism is tectonically related to the Ponta Pora Arch, a NE-trending structural feature, and has the Cerro Sarambi and Cerro Chiriguelo carbonatite complexes as its most significant expressions. Other alkaline occurrences found in the area are the Cerro Guazu and the small bodies of Cerro Apua, Arroyo Gasory, Cerro Jhu, Cerro Tayay, and Cerro Teyu. The alkaline rocks comprise ultramafic-mafic, syenitic, and carbonatitic petrographic associations in addition to lithologies of variable composition and texture occurring as dikes; fenites are described in both carbonatite complexes. Alkali feldspar and clinopyroxene, ranging from diopside to aegirine, are the most abundant minerals, with feldspathoids (nepheline, analcime), biotite, and subordinate Ti-rich garnet; minor constituents are Fe-Ti oxides and cancrinite as the main alteration product from nepheline. Chemically, the Amambay silicate rocks are potassic to highly potassic and have miaskitic affinity, with the non-cumulate intrusive types concentrated mainly in the saturated to undersaturated areas in silica syenitic fields. Fine-grained rocks are also of syenitic affiliation or represent more mafic varieties. The carbonatitic rocks consist dominantly of calciocarbonatites. Variation diagrams plotting major and trace elements vs. SiO(2) concentration for the Cerro Sarambi rocks show positive correlations for Al(2)O(3), K(2)O, and Rb, and negative ones for TiO(2), MgO, Fe(2)O(3), CaO, P(2)O(5), and Sr, indicating that fractional crystallization played an important role in the formation of the complex. Incompatible elements normalized to primitive mantle display positive spikes for Rb, La, Pb, Sr, and Sm, and negative for Nb-Ta, P, and Ti, as these negative anomalies are considerably more pronounced in the carbonatites. Chondrite-normalized REE patterns point to the high concentration of these elements and to the strong LRE/HRE fractionation. The Amambay rocks are highly enriched in radiogenic Sr and have T(DM) model ages that vary from 1.6 to 1.1 Ga. suggesting a mantle source enriched in incompatible elements by metasomatic events in Paleo-Mesoproterozoic times. Data are consistent with the derivation of the Cerro Sarambi rocks from a parental magma of lamprophyric (minette) composition and suggest an origin by liquid immiscibility processes for the carbonatites. (C) 2011 Elsevier Ltd. All rights reserved.

Dating coeval mafic magmatism and ultrahigh temperature metamorphism in the Anapolis-Itaucu Complex, Central Brazil

Dating granulites has always been of great interest because they represent one of the most extreme settings of an orogen. Owing to the resilience of zircon, even in such severe environments, the link between P-T conditions and geological time is possible. However, a challenge to geochronologists is to define whether the growth of new zircon is related to pre- or post-P-T peak conditions and which processes might affect the (re) crystallization. In this context, the Anapolis-Itaucu Complex, a high-grade complex in central Brazil with ultrahigh temperature (UHT) granulites, may provide valuable information within this topic. The Anapolis-Itaucu Complex (AIC) includes ortho- and paragranulites, locally presenting UHT mineral assemblages, with igneous zircon ages varying between 760 and 650 Ma and metamorphic overgrowths dated at around 650-640 Ma. Also common in the Anapolis-Itaucu Complex are layered mafic-ultramafic complexes metamorphosed under high-grade conditions. This article presents the first geological and geochronological constraints of three of these layered complexes within the AIC, the Damolandia, Taquaral and Goianira-Trindade complexes. U-Pb (LA-MC-ICPMS, SHRIMP and ID-TIMS) zircon analyses reveal a spread of concordant ages spanning within an age interval of similar to 80 Ma with an ""upper"" intercept age of similar to 670 Ma. Under cathodoluminescence imaging, these crystals show partially preserved primary sector zoning, as well as internal textures typical of alteration during high-grade metamorphism, such as inward-moving boundaries. Zircon grains reveal homogeneous initial (176)Hf/(177)Hf values in distinct crystal-scale domains in all samples. Moreover. Hf isotopic ratios show correlation neither with U-Pb ages nor with Th/U ratios, suggesting that zircon grains crystallized during a single growth event. It is suggested, therefore, that the observed spread of concordant U-Pb ages may be related to a memory effect due to coupled dissolution-reprecipitation process during high grade metamorphism. Therefore, understanding the emplacement and metamorphism of this voluminous mafic magmatism is crucial as it may represent an additional heat source for the development of the ultrahigh temperature paragenesis recorded in the paragranulites. (C) 2010 Elsevier B.V. All rights reserved.