Aerosol and precipitation chemistry measurements in a remote site in Central Amazonia: the role of biogenic contribution

In this analysis a 3.5 years data set of aerosol and precipitation chemistry, obtained in a remote site in Central Amazonia (Balbina, (1A degrees 55' S, 59A degrees 29' W, 174 m a.s.l.), about 200 km north of Manaus) is discussed. Aerosols were sampled using stacked filter units (SFU), which separate fine (d < 2.5 mu m) and coarse mode (2.5 mu m < d < 10.0 mu m) aerosol particles. Filters were analyzed for particulate mass (PM), Equivalent Black Carbon (BCE) and elemental composition by Particle Induced X-Ray Emission (PIXE). Rainwater samples were collected using a wet-only sampler and samples were analyzed for pH and ionic composition, which was determined using ionic chromatography (IC). Natural sources dominated the aerosol mass during the wet season, when it was predominantly of natural biogenic origin mostly in the coarse mode, which comprised up to 81% of PM10. Biogenic aerosol from both primary emissions and secondary organic aerosol dominates the fine mode in the wet season, with very low concentrations (average 2.2 mu g m(-3)). Soil dust was responsible for a minor fraction of the aerosol mass (less than 17%). Sudden increases in the concentration of elements as Al, Ti and Fe were also observed, both in fine and coarse mode (mostly during the April-may months), which we attribute to episodes of Saharan dust transport. During the dry periods, a significant contribution to the fine aerosols loading was observed, due to the large-scale transport of smoke from biomass burning in other portions of the Amazon basin. This contribution is associated with the enhancement of the concentration of S, K, Zn and BCE. Chlorine, which is commonly associated to sea salt and also to biomass burning emissions, presented higher concentration not only during the dry season but also for the April-June months, due to the establishment of more favorable meteorological conditions to the transport of Atlantic air masses to Central Amazonia. The chemical composition of rainwater was similar to those ones observed in other remote sites in tropical forests. The volume-weighted mean (VWM) pH was 4.90. The most important contribution to acidity was from weak organic acids. The organic acidity was predominantly associated with the presence of acetic acid instead of formic acid, which is more often observed in pristine tropical areas. Wet deposition rates for major species did not differ significantly between dry and wet season, except for NH4+, citrate and acetate, which had smaller deposition rates during dry season. While biomass burning emissions were clearly identified in the aerosol component, it did not present a clear signature in rainwater. The biogenic component and the long-range transport of sea salt were observed both in aerosols and rainwater composition. The results shown here indicate that in Central Amazonia it is still possible to observe quite pristine atmospheric conditions, relatively free of anthropogenic influences.

Influence of the deposition parameters on the morphology and electrical conductivity of PANI/PSS self-assembled films

The influence of deposition parameters, namely polymer concentration and pH of the deposition solution, cleaning, and drying steps on the morphology and electrical characteristics of polyaniline and sulfonated polystyrene (PANI/PSS) nanostructured films deposited by the self-assembly technique is evaluated by UV-Vis spectroscopy, optical and atomic force microscopy, and electrical resistance measurements. It is found that stirring the cleaning solution during the cleaning step is crucial for obtaining homogenous films. Stirring of the cleaning solution also influences the amount of PANI adsorbed in the films. In this regard, the drying process seems to be less critical since PANI amount and film thickness are similar in films dried with N-2 flow or with an absorbent tissue. It is observed, however, that drying with N-2 flow results in rougher films. As an additional point, an assessment of the influence of the deposition method (manual versus mechanical) on the film characteristics was carried out. A significant difference on the amount of PANI and film thickness between films prepared by different human operators and by a homemade mechanical device was observed. The variability in film thickness and PANI adsorbed amount is smaller in films mechanically assembled. (c) 2007 Elsevier B.V. All rights reserved.

Temporal variation in egg-capsule deposition by Nassarius vibex (Gastropoda: Nassariidae)

The morphology and the deposition periods of egg capsules by the bruised nassa Nassarius vibex were investigated on two beaches located on the southeast coast of Brazil. The nassariids were associated with the charru mussel Mytella charruana, which forms beds on soft mud-bottoms. A total of 1558 capsules were collected, only from the fronds of the green alga Ulva lactuca, 859 for Camaroeiro Beach and 699 for Cidade Beach. The mean sizes of the egg capsules and numbers of eggs or larvae per capsule were similar on the two beaches, as were the periods of capsule deposition. At Camaroeiro Beach, capsules first appeared in May 2006, reached a peak in August 2006, and disappeared in December 2006. At Cidade Beach, the first capsules were recorded in July 2006, with a peak in August 2006. A second peak was also observed at this beach between January 2007 and April 2007. The two periods of deposition recorded at the latter beach may indicate two periods of recruitment in the same year for N. vibex. Regarding the influence of intertidal level on capsule deposition, there was a significant difference in the number of capsules between the levels at Camaroeiro Beach (F= 7.445, p<0.05), and for the second capsule-deposition peak at Cidade Beach (F= 6.382, p<0.05). This study revealed a selective pattern of capsule deposition, with individuals of N. vibex using only fronds of U. lactuca. This process was influenced by the morphodynamics of the two beaches, with the nassariids maximizing the survival of embryos by depositing more capsules and more eggs per capsule in better-protected parts of the mytilid beds.

Faeces deposition on Amazonian Anthrosols as assessed from 5 beta-stanols

In the Amazon Basin, within a landscape of infertile soils, fertile Anthrosols of pre-Columbian origin occur (Amazonian Dark Earths or terra preta de Indio). These soils are characterized by high amounts of charred organic matter (black carbon, biochar) and high nutrient stocks. Frequently, they were considered as sign for intensive landscape domestication by way of sedentary agriculture and as sign for large settlements in pre-Columbian Amazonia. Beyond the archaeological interest in Amazonian Dark Earths, they increasingly receive attention because it is assumed that they could serve as a model for sustainable agriculture in the humid tropics (terra preta nova). Both questions lack information about the pre-Columbian practices which were responsible for the genesis of Amazonian Dark Earths. It has often been hypothesized that deposition of faeces could have contributed to the high nutrient stocks in these soils, but no study has focussed on this question yet. We analyzed the biomarkers for faeces 5 beta-stanols as well as their precursors and their 5 alpha-isomers in Amazonian Dark Earths and reference soils to investigate the input of faeces into Amazonian Dark Earths. Using Amazonian Dark Earths as example, we discuss the application of threshold values for specific stanols to evaluate faeces deposition in archaeological soils and demonstrate an alternative approach which is based on a comparison of the concentration patterns of 5 beta-stanols with the concentration patterns of their precursors and their 5 alpha-isomers as well as with local backgrounds. The concentration patterns of sterols show that faeces were deposited on Amazonian Dark Earths. (C) 2011 Elsevier Ltd. All rights reserved.

Archaeofacies Analysis: Using Depositional Attributes to Identify Anthropic Processes of Deposition in a Monumental Shell Mound of Santa Catarina State, Southern Brazil

In the coast of Santa Catarina State (southern Brazil), a large population of monumental shell mounds characterizes a highly dynamic coastal setting. In this paper, sedimentary facies analysis was adapted for description, sampling, and interpretation of shell mound complex and repetitive archaeostratigraphic successions. Archaeofacies identification in the field, according to depositional attributes, is tested by contrasting field description with multi-element chemical analyses, total carbon and nitrogen determinations, and micromorphological descriptions. Two vertical sequences at the black deposit of Jabuticabeira II shell mound were studied and preliminary results showed that: (1) depositional attributes are a reliable base for archaeofacies identification in the field, (2) the formation process of this site involved a sequence of anthropic depositional processes, where burned refuse was redeposited over the shell mound following a ritual construction pattern, and (3) the black deposit includes a double palimpsest that refers to provenance and meaning of mound construction material. (C) 2009 Wiley Periodicals, Inc.

Shape Changes of Pt Nanoparticles Induced by Deposition on Mesoporous Silica

Polyvinylpyrollidone (PVP)-capped platinum nanoparticles (NPs) are found to change shape from spherical to flat when deposited on mesoporous silica substrates (SBA-15). Transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and extended X-ray absorption fine structure (EXAFS) analyses are used in these studies. The SAXS results indicate that, after deposition, the 2 nm NPs have an average gyration radius 22% larger than in solution, while the EXAFS measurements indicate a decrease in first neighbor co-ordination number from 9.3 to 7.4. The deformation of these small capped NPs is attributed to interactions with the surface of the SBA-15 support, as evidenced by X-ray absorption near-edge structure (XANES).

Application of dendrogeomorphology on the study of soil sediment deposition in the stems of Guarea guidonea trees in a disturbed riparian forest in Goias state, Brazil

The sediments resulting of natural or anthropic erosion are deposited on the soil surface and around the trunks of trees occurring in riparian forests. For assessment of the erosion, tree-rings of roots and stems were analyzed. Guarea guidonea trees from a riparian forest affected by the sedimentation of soil erosion from pastures and soybean fields in state of Goias were selected. Wood samples were extracted through a non-destructive method at three heights from trunks of trees located in three positions (top, middle and bottom) of a riparian slope. The evaluation revealed a deposition of a thick sediment layer up to 34 cm around the base of tree trunks during the past 24 years. The inter-correlations between the tree-rings widths present in wood samples at the base and at 50 and 100 cm from Guarea guidonea tree trunks presented low, medium and high values. These values resulted from the low tree-rings distinctiveness in the wood; the absence of some rings as well as the eccentricity of the pith. The analyses of dendrogeomorphology allowed the determination of the date of seed germination and tree growth and inference on the periods of sediment deposition in the trunk of the trees.

Nitric oxide modulates metalloproteinase-2, collagen deposition and adhesion rate after polypropylene mesh implantation in the intra-abdominal wall

Prosthetic meshes are commonly used to correct abdominal wall defects. However, the inflammatory reaction induced by these devices in the peritoneum is not completely understood. We hypothesized that nitric oxide (NO), produced by nitric oxide synthase 2 (NOS2) may modulate the response induced by mesh implants in the abdominal wall and, consequently, affect the outcome of the surgical procedure. Polypropylene meshes were implanted in the peritoneal side of the abdominal wall in wild-type and NOS2-deficient (NOS2(-/-)) mice. After 15 days tissues around the mesh implant were collected, and inflammatory markers (the cytokine interleukin 1 beta (IL-1 beta) and NO) and tissue remodeling (collagen and metalloproteinases (MMP) 2 and 9) were analyzed. The lack of NOS2-derived NO induced a higher incidence of visceral adhesions at the mesh implantation site compared with wild-type mice that underwent the same procedure (P < 0.05). Additionally, higher levels of IL-1 beta were present in the mesh-implanted NOS2(-/-) animals compared with control and wild-type mice. Mesh implantation induced collagen I and III deposition, but in smaller amounts in NOS2(-/-) mice. MMP-9 activity after the surgical procedure was similarly increased in both groups. Conversely, MMP-2 activity was unchanged in mesh-implanted wild-type mice, but was significantly increased in NOS2(-/-) mice (P < 0.01), due to decreased S-nitrosylation of the enzyme in these animals. We conclude that NOS2-derived NO is crucial for an adequate response to and integration of polypropylene mesh implants in the peritoneum. NO deficiency results in a prolonged inflammatory reaction to the mesh implant, and reduced collagen deposition may contribute to an increased incidence of visceral adhesions. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Size distributions and temporal variations of biological aerosol particles in the Amazon rainforest characterized by microscopy and real-time UV-APS fluorescence techniques during AMAZE-08

As a part of the AMAZE-08 campaign during the wet season in the rainforest of central Amazonia, an ultraviolet aerodynamic particle sizer (UV-APS) was operated for continuous measurements of fluorescent biological aerosol particles (FBAP). In the coarse particle size range (> 1 mu m) the campaign median and quartiles of FBAP number and mass concentration were 7.3x10(4) m(-3) (4.0-13.2x10(4) m(-3)) and 0.72 mu g m(-3) (0.42-1.19 mu g m(-3)), respectively, accounting for 24% (11-41%) of total particle number and 47% (25-65%) of total particle mass. During the five-week campaign in February-March 2008 the concentration of coarse-mode Saharan dust particles was highly variable. In contrast, FBAP concentrations remained fairly constant over the course of weeks and had a consistent daily pattern, peaking several hours before sunrise, suggesting observed FBAP was dominated by nocturnal spore emission. This conclusion was supported by the consistent FBAP number size distribution peaking at 2.3 mu m, also attributed to fungal spores and mixed biological particles by scanning electron microscopy (SEM), light microscopy and biochemical staining. A second primary biological aerosol particle (PBAP) mode between 0.5 and 1.0 mu m was also observed by SEM, but exhibited little fluorescence and no true fungal staining. This mode may have consisted of single bacterial cells, brochosomes, various fragments of biological material, and small Chromalveolata (Chromista) spores. Particles liquid-coated with mixed organic-inorganic material constituted a large fraction of observations, and these coatings contained salts likely from primary biological origin. We provide key support for the suggestion that real-time laser-induce fluorescence (LIF) techniques using 355 nm excitation provide size-resolved concentrations of FBAP as a lower limit for the atmospheric abundance of biological particles in a pristine environment. We also show some limitations of using the instrument for ambient monitoring of weakly fluorescent particles < 2 mu m. Our measurements confirm that primary biological particles, fungal spores in particular, are an important fraction of supermicron aerosol in the Amazon and that may contribute significantly to hydrological cycling, especially when coated by mixed inorganic material.

Gold nanoparticle formation in diamond-like carbon using two different methods: Gold ion implantation and co-deposition of gold and carbon

We describe work in which gold nanoparticles were formed in diamond-like carbon (DLC), thereby generating a Au-DLC nanocomposite. A high-quality, hydrogen-free DLC thin film was formed by filtered vacuum arc plasma deposition, into which gold nanoparticles were introduced using two different methods. The first method was gold ion implantation into the DLC film at a number of decreasing ion energies, distributing the gold over a controllable depth range within the DLC. The second method was co-deposition of gold and carbon, using two separate vacuum arc plasma guns with suitably interleaved repetitive pulsing. Transmission electron microscope images show that the size of the gold nanoparticles obtained by ion implantation is 3-5 nm. For the Au-DLC composite obtained by co-deposition, there were two different nanoparticle sizes, most about 2 nm with some 6-7 nm. Raman spectroscopy indicates that the implanted sample contains a smaller fraction of sp(3) bonding for the DLC, demonstrating that some sp(3) bonds are destroyed by the gold implantation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4757029]

Biogenic Potassium Salt Particles as Seeds for Secondary Organic Aerosol in the Amazon

The fine particles serving as cloud condensation nuclei in pristine Amazonian rainforest air consist mostly of secondary organic aerosol. Their origin is enigmatic, however, because new particle formation in the atmosphere is not observed. Here, we show that the growth of organic aerosol particles can be initiated by potassium-salt-rich particles emitted by biota in the rainforest. These particles act as seeds for the condensation of low- or semi-volatile organic compounds from the atmospheric gas phase or multiphase oxidation of isoprene and terpenes. Our findings suggest that the primary emission of biogenic salt particles directly influences the number concentration of cloud condensation nuclei and affects the microphysics of cloud formation and precipitation over the rainforest.

Measurement of the concentration and size of aerosol particles and identification of the sources in orthopedic surgeries

In this study, the measurement of the concentration and size of particles and the identification of their sources were carried out at five orthopedic surgeries. The aerosol concentration and particle size distribution, ranging from 0.3 mu m 10 mu m, were measured and related to the type of indoor activity. The handling of surgical linen and gowns, handling of the patient, use of electrosurgical apparatus, use of a bone saw, handling of equipment, and cleaning of the room were identified as the most important sources of particles, with each of these activities posing different risks to the health of the patients and workers. The results showed that most of the particles were above 0.5 mu m and that there was a strong correlation among all particles of sizes above 1 mu m. Particles with diameters in the range of 0.3 mu m-0.5 mu m had a good correlation only with particles in the ranges of 0.5 mu m-1.0 mu m and 1.0 mu m-3.0 mu m in three of the surgeries analyzed. Findings led to the conclusion that most of the events responsible for generating aerosol particles in an orthopedic surgery room are brief, intermittent, and highly variable, thus requiring the use of specific instrumentation for their continuous identification and characterization.

Use of levoglucosan, potassium, and water-soluble organic carbon to characterize the origins of biomass-burning aerosols

Three chemical species related to biomass burning, levoglucosan, potassium and water-soluble organic carbon (WSOC), were measured in aerosol samples collected in a rural area on the outskirts of the municipality of Ourinhos (Sao Paulo State, Brazil). This region is representative of the rural interior of the State, where the economy is based on agro-industrial production, and the most important crop is sugar cane. The manual harvesting process requires that the cane be first burned to remove excess foliage, leading to large emissions of particulate materials to the atmosphere. Most of the levoglucosan (68-89%) was present in small particles (<1.5 mu m), and its concentration in total aerosol ranged from 25 to 1186 ng m(-3). The highest values were found at night, when most of the biomass burning occurs. In contrast, WSOC showed no diurnal pattern, with an average concentration of 5.38 +/- 2.97 mu g m(-3) (n = 27). A significant linear correlation between levoglucosan and WSOC (r = 0.54; n = 26; p < 0.0001) confirmed that biomass burning was in fact an important source of WSOC in the study region. A moderate (but significant) linear correlation between levoglucosan and potassium concentrations (r = 0.62; n = 40; p < 0.0001) was indicative of the influence of other sources of potassium in the study region, such as soil resuspension and fertilizers. When only the fine particles (<1.5 pm; typical of biomass burning) were considered, the linear coefficient increased to 0.91 (n = 9). In this case, the average levoglucosan/K+ ratio was 0.24, which may be typical of biomass burning in the study region. This ratio is about 5 times lower than that previously found for Amazon aerosol collected during the day, when flaming combustion prevails. This suggests that the levoglucosan/K+ ratio may be especially helpful for characterization of the type of vegetation burned (such as crops or forest), when biomass-burning is the dominant source of potassium. The relatively high concentrations of WSOC (and inorganic ions) suggest an important influence on the formation of cloud condensation nuclei, which is likely to affect cloud formation and precipitation patterns. (C) 2012 Elsevier Ltd. All rights reserved.

Aerosol profiling with lidar in the Amazon Basin during the wet and dry season

For the first time, multiwavelength polarization Raman lidar observations of optical and microphysical particle properties over the Amazon Basin are presented. The fully automated advanced Raman lidar was deployed 60 km north of Manaus, Brazil (2.5 degrees S, 60 degrees W) in the Amazon rain forest from January to November 2008. The measurements thus cover both the wet season (Dec-June) and the dry or burning season (July-Nov). Two cases studies of young and aged smoke plumes are discussed in terms of spectrally resolved optical properties (355, 532, and 1064 nm) and further lidar products such as particle effective radius and single-scattering albedo. These measurement examples confirm that biomass burning aerosols show a broad spectrum of optical, microphysical, and chemical properties. The statistical analysis of the entire measurement period revealed strong differences between the pristine wet and the polluted dry season. African smoke and dust advection frequently interrupt the pristine phases during the wet season. Compared to pristine wet season conditions, the particle scattering coefficients in the lowermost 2 km of the atmosphere were found to be enhanced, on average, by a factor of 4 during periods of African aerosol intrusion and by a factor of 6 during the dry (burning) season. Under pristine conditions, the particle extinction coefficients and optical depth for 532 nm wavelength were frequently as low as 10-30 Mm(-1) and <0.05, respectively. During the dry season, biomass burning smoke plumes reached to 3-5 km height and caused a mean optical depth at 532 nm of 0.26. On average during that season, particle extinction coefficients (532 nm) were of the order of 100 Mm(-1) in the main pollution layer (up to 2 km height). Angstrom exponents were mainly between 1.0 and 1.5, and the majority of the observed lidar ratios were between 50-80 sr.

Synthesis of a functionalized europium complex and deposition of luminescent Langmuir-Blodgett (LB) films

The synthesis, characterization and formation of Langmuir-Blodgett (LB)films for the luminescent [(C12H25)(2)(CH3)(2)N][Eu(tta)(4)] complex, where [(C12H25)(2)(CH3)(2)](N+) is didodecyldimethylammonium and the tta ligand is thenoyltrifluoroacetone, are reported. The coordination of tta ligands to the Eu3+ ion was confirmed by FTIR spectroscopy and the emission spectrum comprised bands corresponding to D-5(0) -> F-7(0-4) transitions. The lifetime (tau) from the emission state (D-5(0))was 0.41 ms, measured by monitoring the hypersensitive D-5(0) -> F-7(2) transition, with the curve being fitted with a first-order exponential function. The surface pressure-area isotherm indicated that the anionic complex may form condensed structures at the air-water interface due to the amphiphilic properties of the counter ion and the beta-diketone ligand. Y-type LB films of [(C12H25)(2)(CH3)(2)N][Eu(tta)(4)] were deposited on quartz substrates, with preserved luminescence and a band assigned to the D-5(0) -> F-7(2) transition. The molecular arrangement at the air/water interface and the preserved luminescence in LB films are consistent with theoretical predictions using a semi-empirical Sparkle/AM1 calculation method for the molecule in vacuum. These tools were used for the first time to predict the behavior of organized films.