On molecular chirality within naturally occurring secondary organic aerosol particles from the central Amazon Basin

In this perspectives article, we reflect upon the existence of chirality in atmospheric aerosol particles. We then show that organic particles collected at a field site in the central Amazon Basin under pristine background conditions during the wet and dry seasons consist of chiral secondary organic material. We show how the chiral response from the aerosol particles can be imaged directly without the need for sample dissolution, solvent extraction, or sample preconcentration. By comparing the chiral-response images with optical images, we show that chiral responses always originate from particles on the filter, but not all aerosol particles produce chiral signals. The intensity of the chiral signal produced by the size resolved particles strongly indicates the presence of chiral secondary organic material in the particle. Finally, we discuss the implications of our findings on chiral atmospheric aerosol particles in terms of climate-related properties and source apportionment.

Organic molecule assembled between carbon nanotubes: A highly efficient switch device

We report a highly efficient switch built from an organic molecule assembled between single-wall carbon nanotube electrodes. We theoretically show that changes in the distance between the electrodes alter the molecular conformation within the gap, affecting in a dramatic way the electronic and charge transport properties, with an on/off ratio larger than 300. This opens up the perspective of combining molecular electronics with carbon nanotubes, bringing great possibilities for the design of nanodevices.

Surface Plasmon-Induced Band Gap in the Photocurrent Response of Organic Solar Cells

A 260 nm layer of organic bulk heterojunction blend of the polymer poly(3-hexylthiophene) (P3HT) and the fullerene [6,6]-phenyl C(61)-butyric (PCBM) was spin-coated in between aluminum and gold electrodes, respectively, on top of a laser inscribed azo polymer surface-relief diffraction grating. Angle-dependent surface plasmons (SPs) with a large band gap were observed in the normalized photocurrent by the P3HT-PCBM layer as a function of wavelength. The SP-induced photocurrents were also investigated as a function of the grating depth and spacing.

Antimicrobial mechanisms behind photodynamic effect in the presence of hydrogen peroxide

This study describes the use of methylene blue (MB) plus light (photodynamic inactivation, PDI) in the presence of hydrogen peroxide (H(2)O(2)) to kill Staphylococcus aureus, Escherichia coli, and Candida albicans. When H(2)O(2) was added to MB plus light there was an increased antimicrobial effect, which could be due to a change in the type of ROS generated or increased microbial uptake of MB. To clarify the mechanism, the production of ROS was investigated in the presence and absence of H(2)O(2). It was observed that ROS production was almost inhibited by the presence of H(2)O(2) when cells were not present. In addition, experiments using different sequence combinations of MB and H(2)O(2) were performed and MB optical properties inside the cell were analyzed. Spectroscopy experiments suggested that the amount of MB was higher inside the cells when H(2)O(2) was used before or simultaneously with PDI, and ROS formation inside C. albicans cells confirmed that ROS production is higher in the presence of H(2)O(2). Moreover enzymatic reduction of MB by E. coli during photosensitizer uptake to the photochemically inactive leucoMB could be reversed by the oxidative effects of hydrogen peroxide, increasing ROS formation inside the microorganism. Therefore, the combination of a photosensitizer such as MB and H(2)O(2) is an interesting approach to improve PDI efficiency.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

On the template synthesis of nanostructured inorganic/organic hybrid films

Prussian Blue has been introduced as a mediator to achieve stable, sensitive, reproducible, and interference-free biosensors. However, Na(+), Li(+), H(+), and all group II cations are capable to block the activity of Prussian Blue and, because Na(+) can be found in most human fluids, Prussian Blue analogs have already been developed to overcome this problem. These analogs, such as copper hexacyanoferrate, have also been introduced in a conducting polypyrrole matrix to create hybrid materials (copper hexacyanoferrate/polypyrrole, CuHCNFe/Ppy) with improved mechanical and electrochemical characteristics. Nowadays, the challenges in amperometric enzymatic biosensors consist of improving the enzyme immobilization and in making the chemical signal transduction more efficient. The incorporation of nanostructured materials in biosensors can optimize both steps and a nanostructured hybrid CuHCNFe/Ppy mediator has been developed using a template of colloidal polystyrene particles. The nanostructured material has achieved sensitivities 7.6 times higher than the bulk film during H(2)O(2) detection and it has also presented better results in other analytical parameters such as time response and detection limit. Besides, the nanostructured mediator was successfully applied at glucose biosensing in electrolytes containing Prussian Blue blocking cations. (C) 2008 The Electrochemical Society.

Lignin phenols used to infer organic matter sources to Sepetiba Bay - RJ, Brasil

Lignin phenols were measured in the sediments of Sepitiba Bay, Rio de Janeiro, Brazil and in bedload sediments and suspended sediments of the four major fluvial inputs to the bay: Sao Francisco and Guandu Channels and the Guarda and Cacao Rivers. Fluvial suspended lignin yields (Sigma 8 3.5-14.6 mgC 10 g dw(-1)) vary little between the wet and dry seasons and are poorly correlated with fluvial chlorophyll concentrations (0.8-50.2 mu gC L(-1)). Despite current land use practices that favor grassland agriculture or industrial uses, fluvial lignin compositions are dominated by a degraded leaf-sourced material. The exception is the Guarda River, which has a slight influence from grasses. The Lignin Phenol Vegetation Index, coupled with acid/aldehyde and 3.5 Db/V ratios, indicate that degraded leaf-derived phenols are also the primary preserved lignin component in the bay. The presence of fringe Typha sp. and Spartina sp. grass beds surrounding portions of the Bay are not reflected in the lignin signature. Instead, lignin entering the bay appears to reflect the erosion of soils containing a degraded signature from the former Atlantic rain forest that once dominated the watershed, instead of containing a significant signature derived from current agricultural uses. A three-component mixing model using the LPVI, atomic N:C ratios, and stable carbon isotopes (which range between -26.8 and -21.8 parts per thousand) supports the hypothesis that fluvial inputs to the bay are dominated by planktonic matter (78% of the input), with lignin dominated by leaf (14% of the input) over grass (6%). Sediments are composed of a roughly 50-50 mixture of autochthonous material and terrigenous material, with lignin being primarily sourced from leaf. (C) 2010 Elsevier Ltd. All rights reserved.

Stable isotopes of bulk organic matter to trace carbon and nitrogen dynamics in an estuarine ecosystem in Babitonga Bay (Santa Catarina, Brazil)

The biogeochemical processes affecting the transport and cycling of terrestrial organic carbon in coastal and transition areas are still not fully understood One means of distinguishing between the sources of organic materials contributing to particulate organic matter (POM) in Babitonga Bay waters and sediments is by the direct measurement of delta(13)C of dissolved inorganic carbon (DIC) and delta(13)C and delta(15)N in the organic constituents. An isotopic survey was taken from samples collected in the Bay in late spring of 2004. The results indicate that the delta(13)C and delta(15)N compositions of OM varied from -21.7 parts per thousand to -26 2 parts per thousand. and from + 9 2 parts per thousand. to -0 1 parts per thousand, respectively. delta(13)C from DIC ranges from +0.04 parts per thousand to -12.7 parts per thousand The difference in the isotope compositions enables the determination of three distinct end-members terrestrial, marine and urban Moreover, the evaluation of source contribution to the particulate organic matter (POM) in the Bay, enables assessment of the anthropogenic impact. Comparing the depleted values of delta(13)C(DIC) and delta(13)C(POC) it is possible to further understand the carbon dynamic within Babitonga Bay (C) 2010 Elsevier BV All rights reserved

Changes in soil organic carbon storage under different agricultural management systems in the Southwest Amazon Region of Brazil

The Cerrado and Amazon regions of Brazil are probably the largest agricultural frontier of the world, and Could be a sink or source for C depending on the net effect of land use change and subsequent management on soil organic C pools. We evaluated the effects of agricultural management systems on soil organic C (SOC) stocks in the Brazilian states of Rondonia and Mato Grosso, and derived regional specific factors for soil C stock change associated with different management systems. We used 50 observations (data points) in this study, including 42 dealing with annual cropping practices and 8 dealing with perennial cropping, and analyzed the data in linear mixed-effect models. No tillage (NT) systems in Cerrado areas increased SOC Storage by 1.08 +/- 0.06 relative to SOC stocks under native conditions, while SOC storage increased by a modest factor of 1.01 +/- 0.17 in Cerradao and Amazon Forest conditions. Full tillage (FT) had negative effect on SOC storage relative to NT, decreasing SOC stocks by a factor of 0.94 +/- 0.04. but did not significantly reduce SOC stocks relative to native levels when adopted in the Cerrado region. Perennial cropping had a minimal impact on SOC stocks, estimated at a factor Value of 0.98 +/- 0.14, suggesting these systems maintain about 98% of the SOC stock found under native vegetation. The results Suggest that NT adoption may be increasing SOC with land use change from native vegetation to cropland management in the Cerrado region of Brazil. (C) 2009 Elsevier B.V. All rights reserved.

Soil organic carbon and fertility interactions affected by a tillage chronosequence in a Brazilian Oxisol

No-till (NT) adoption is an essential tool for development of sustainable agricultural systems, and how NT affects the soil organic C (SOC) dynamics is a key component of these systems. The effect of a plow tillage (PT) and NT age chronosequence on SOC concentration and interactions with soil fertility were assessed in a variable charge Oxisol, located in the South Center quadrant of Parana State, Brazil (50 degrees 23`W and 24 degrees 36`S). The chronosequence consisted of the following six sites: (i) native field (NF); (ii) PT of the native field (PNF-1) involving conversion of natural vegetation to cropland; (iii) NT for 10 years (NT-10); (iv) NT for 20 years (NT-20); (v) NT for 22 years (NT-22); and (vi) conventional tillage for 22 years (CT-22) involving PT with one disking after summer harvest and one after winter harvest to 20 cm depth plus two harrow disking. Soil samples were collected from five depths (0-2.5; 2.5-5; 5-10; 10-20; and 20-40 cm) and SOC, pH (in H(2)O and KCl), Delta pH, potential acidity, exchangeable bases, and cation exchangeable capacity (CEC) were measured. An increase in SOC concentration positively affected the pH, the negative charge and the CEC and negatively impacted potential acidity. Regression analyses indicated a close relationship between the SOC concentration and other parameters measured in this study. The regression fitted between SOC concentration and CEC showed a close relationship. There was an increase in negative charge and CEC with increase in SOC concentration: CEC increased by 0.37 cmol(c) kg(-1) for every g of C kg(-1) soil. The ratio of ECEC:SOC was 0.23 cmol(c) kg(-1) for NF and increased to 0.49 cmol(c) kg(-1) for NT-22. The rates of P and K for 0-10 cm depth increased by 9.66 kg ha(-1) yr(-1) and 17.93 kg ha(-1) yr(-1), respectively, with NF as a base line. The data presented support the conclusion that long-term NT is a useful strategy for improving fertility of soils with variable charge. (C) 2008 Elsevier B.V. All rights reserved.

Sedimentary Organic Matter in Cores of the Cananeia-Iguape Lagoonal-Estuarine System, Sao Paulo State, Brazil

Sedimentary organic matter is a good tool for environmental evaluation where the sediments are deposited. We determined the elemental and C- and N-isotopic compositions of 211 sub-surface sediment samples from 13 cores (ranging from 18 to 46cm), collected in the Cananeia-Iguape estuarine-lagoonal system. The aim of this research is to evaluate the environmental variations of this tropical coastal micro-tidal system over the last decades, through SOM distribution. The studied parameters show differences between the cores located in the northern (sandy-silt sediments) and southern (sand and silty-sand) portions. The whole area presents a mixed organic matter origin signature (local mangrove plants: < -25.6 parts per thousand PDB/ phytoplancton delta(13)C values: -19.4 parts per thousand PDB). The northern cores, which submitted higher sedimentation deposition (1.46cm year(-1)), are more homogenous, presenting lower delta(13)C (< -25.2 parts per thousand PDB) and higher C/N values (in general >14), directly related to the terrestrial input from Ribeira de Iguape River (24,000 km(2) basin). The southern portion presents lower sedimentation rates (0.38cm year(-1)) and is associated to a small river basin (1,340 km(2)), presenting values Of delta(13)C: -25.0 to 23.0 parts per thousand PDB and of C/N ratio: 11 to 15. In general, the elemental contents in the 15 cores may be considered from low to medium (< 2.0% C - < 0.1% N), compared to similar environments. Although a greater marine influence is observed in the southern system portion, the majority of the cores present an elevated increase of continental deposition, most likely related to the strong silting process that the area has been subjected to since the 1850s, when an artificial channel was built linking, directly, the Ribeira River to the estuarine-lagoonal system.

Fertilizers applied to certified organic tomato culture

The tomato culture demands large quantities of mineral nutrients, which are supplied by synthetic fertilizers in the conventional cultivation system. In the organic cultivation system only alternative fertilizers are allowed by the certifiers and accepted as safe for humans and environment. The chemical composition of rice bran, oyster flour, cattle manure and ground charcoal, as well as soils and tomato fruits were evaluated by instrumental neutron activation analysis (INAA). The potential contribution of organic fertilizers to the enrichment of chemical elements in soil and their transfer to fruits was investigated using concentration ratios for fertilizer and soil samples, and also for soil and tomato. Results evidenced that these alternative fertilizers could be taken as important sources of Br, Ca, Ce, K, Na and Zn for the organic tomato culture.

Chemical characterization of agricultural supplies applied to organic tomato cultivation

The agricultural supplies used in the organic system to control pests and diseases as well as to fertilize soil are claimed to be beneficial to plants and innocuous to human health and to the environment. The chemical composition of six agricultural supplies commonly used in the organic tomato culture, was evaluated by instrumental neutron activation analysis (INAA). Results were compared to the maximum limits established by the Environment Control Agency of the Sao Paulo State (CETESB) and the Guidelines for Organic Quality Standard of Instituto Biodinamico (IBD). Concentrations above reference values were found for Co, Cr and Zn in compost, Cr and Zn in cattle manure and Zn in rice bran.

Chemical composition of tomato seeds affected by conventional and organic production systems

Tomato is amongst the most consumed vegetables in the world, not only for its culinary versatility but also for its high nutritional value. In the last years, consumers have shown an increased concern regarding food origin and safety. The organic tomato production has been a promising alternative for the consumer offering a safer food in relation to environmental, social and nutritional aspects. This study assessed the chemical composition of tomato seeds produced in both conventional and organic systems by INAA. The results showed significant differences (P <= 0.05) in the mass fractions of Br, Cs, Eu, Fe, K, Mo, Na, Rb and Sm between both systems, indicating influence of the crop management adopted in the different tomato production systems.

Hydrogen peroxide bleaching of cellulose pulps obtained from brewer`s spent grain

Brewer`s spent grain (BSG) was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were produced by soda pulping: one from the original raw material and the other from material pretreated by dilute acid. Both of them were bleached by a totally chlorine-free sequence performed in three stages, using 5% hydrogen peroxide in the two initial, and a 0.25 N NaOH solution in the last one. Chemical composition, kappa number, viscosity, brightness and yield of bleached and unbleached pulps were evaluated. The high hemicellulose (28.4% w/w) and extractives (5.8% w/w) contents in original BSG affected the pulping and bleaching processes. However, soda pulping of acid pretreated BSG gave a cellulose-rich pulp (90.4% w/w) with low hemicellulose and extractives contents (7.9% w/w and < 3.4% w/w, respectively), which was easily bleached achieving a kappa number of 11.21, viscosity of 3.12 cp, brightness of 71.3%, cellulose content of 95.7% w/w, and residual lignin of 3.4% w/w. Alkaline and oxidative delignification of acid pretreated BSG was found as an attractive approach for producing high-purity, chlorine-free cellulose pulp.