Green Chemistry-Sensitive Analytical Procedure for Photometric Determination of Orthophosphate in River and Tap Water by Use of a Simple LED-Based Photometer

In the current work a Green Analytical Chemistry (GAC) procedure for photometric determination of orthophosphate in river water at mu g L-1 concentration level is described. The flow system module and the LED-based photometer were assembled together to constitute a compact unit in order to allow that a flow cell with optical path-length of 100mm was coupled to them. The photometric procedure based on the molybdenum blue method was implemented employing the multicommuted flow injection analysis approach, which provided facilities to allow reduction of reagent consumption and as well as waste generation. Aiming to prove the usefulness of the system, orthophosphate in river and tap waters was determined. Accuracy was ascertained by spiking samples with orthophosphate solution yielding recoveries ranging from 96% up to 107%. Other profitable features such as a wide linear response range between 10 to 800 mu g L-1 [image omitted]; a detection limit (3 sigma criterion) of 2.4 mu g L-1 [image omitted]; a relative standard deviation (n=7) of 2% using a typical water sample with concentration of 120 mu g L-1 [image omitted]; reagent consumption of 3.0mg ammonium molybdate, 0.3mg hydrazine sulfate, and 0.03mg stannous chloride per determination; a waste generation of 2.4mL per determination; and a sampling throughput of 20 determination per hours were also achieved.

Single reaction interface flow system for chemiluminescent monitoring of mannitol based on its hydroxyl radical scavenger activity

A single reaction interface flow analysis (SIFA) system for the monitoring of mannitol in pharmaceutical formulations and human urine is presented. The developed approach takes advantage of the mannitol scavenger aptitude to inhibit the chemiluminescent reaction between luminol and myoglobin in the absence of H(2)O(2). The SIFA system facilitated the fully automation of the developed methodology, allowing the in-line reproducible handling of chemical species with a very short lifetime as is the case of the hydroxyl radical generated in the abovementioned luminol/myoglobin reaction. The proposed methodology allowed the determination of mannitol concentrations between 25 mmol L(-1) and 1 mol L(-1), with good precision (R.S.D. < 4.7%, n = 3) and a sampling frequency of about 60 h(-1). The procedure was applied to the determination of mannitol in pharmaceuticals and in human urine samples Without any pretreatment process. The results obtained for pharmaceutical formulations were statistically comparable to those provided by the reference method (R.D. < 4.6%); recoveries values obtained in the analysis of spiked urine samples (between 94.9 and 105.3% of the added amount) were also satisfactory. (C) 2008 Elsevier B.V. All rights reserved.

A new monitor for routine thermal and epithermal neutron fluence rate monitoring in k(0) INAA

The Zr-Au set for monitoring the thermal and epithermal neutron fluence rate and the epithermal spectrum parameter a is not always practicable for routine application of INAA in well-thermalized facilities. An alternative set consisting of Cr, Au and Mo provides values for the thermal neutron fluence rate, f and alpha that are not significantly different from those found via the Zr-Au method and the Cd-covered Zr-method. The IRMM standard SMELS-II was analyzed using the (Au-Cr-Mo) monitor and a good agreement was obtained. (C) 2008 Elsevier Ltd. All rights reserved.

Monitoring stress tolerance and occurrences of upper respiratory illness in basketball players by means of psychometric tools and salivary biomarkers

The aim of the study was to evaluate the possible relationships between stress tolerance, training load, banal infections and salivary parameters during 4 weeks of regular training in fifteen basketball players. The Daily Analysis of Life Demands for Athletes` questionnaire (sources and symptoms of stress) and the Wisconsin Upper Respiratory Symptom Survey were used on a weekly basis. Salivary cortisol and salivary immunoglobulin A (SIgA) were collected at the beginning (before) and after the study, and measured by enzyme-linked immunosorbent assay (ELISA). Ratings of perceived exertion (training load) were also obtained. The results from ANOVA with repeated measures showed greater training loads, number of upper respiratory tract infection episodes and negative sensation to both symptoms and sources of stress, at week 2 (p < 0.05). Significant increases in cortisol levels and decreases in SIgA secretion rate were noted (before to after). Negative sensations to symptoms of stress at week 4 were inversely and significantly correlated with SIgA secretion rate. A positive and significant relationship between sources and symptoms of stress at week 4 and cortisol levels were verified. In summary, an approach incorporating in conjunction psychometric tools and salivary biomarkers could be an efficient means of monitoring reaction to stress in sport. Copyright (C) 2010 John Wiley & Sons, Ltd.

Sensorless synchronization method for thin-film direct optical broadband monitoring system

Optical monitoring systems are necessary to manufacture multilayer thin-film optical filters with low tolerance on spectrum specification. Furthermore, to have better accuracy on the measurement of film thickness, direct monitoring is a must. Direct monitoring implies acquiring spectrum data from the optical component undergoing the film deposition itself, in real time. In making film depositions on surfaces of optical components, the high vacuum evaporator chamber is the most popular equipment. Inside the evaporator, at the top of the chamber, there is a metallic support with several holes where the optical components are assembled. This metallic support has rotary motion to promote film homogenization. To acquire a measurement of the spectrum of the film in deposition, it is necessary to pass a light beam through a glass witness undergoing the film deposition process, and collect a sample of the light beam using a spectrometer. As both the light beam and the light collector are stationary, a synchronization system is required to identify the moment at which the optical component passes through the light beam.

Connection Admission Control for a WDM Optical Network Based on Traffic Monitoring and Bandwidth Release

We proposed a connection admission control (CAC) to monitor the traffic in a multi-rate WDM optical network. The CAC searches for the shortest path connecting source and destination nodes, assigns wavelengths with enough bandwidth to serve the requests, supervises the traffic in the most required nodes, and if needed activates a reserved wavelength to release bandwidth according to traffic demand. We used a scale-free network topology, which includes highly connected nodes ( hubs), to enhance the monitoring procedure. Numerical results obtained from computational simulations show improved network performance evaluated in terms of blocking probability.

Laboratory measurements of biomarkers and individual performances in Chironomus xanthus to evaluate pesticide contamination of sediments in a river of southeastern Brazil

This study aimed at evaluating biomarkers, individual and population responses in the native Chironomus xanthus to assess the toxicity of pesticide-contaminated sediments from the Monjolinho River (Southeast Brazil). We measured cholinesterase (ChE) and glutathione S-transferase activities (GST), as biomarkers and survival, individual growth and adult emergence, as individual performances. There was no response of the ChE activity and a tendency to decreased GST activity in contaminated sites, but this was generally not statistically significant. Therefore, there was no association of the biomarker responses with exposure to sediment containing pesticides. In contrast, ash free dry mass was significantly increased and male emergence was decreased in C. xanthus exposed to the same sediments. In conclusion, the selected biomarkers were not sensitive and specific enough to detect and anticipate effects of pesticide contamination at the levels measured in the study area. Nevertheless, individual performances alterations pointed to potential pollution problems and possible ecological consequences. (C) 2010 Elsevier Inc. All rights reserved.

Rural and Urban Streams: Anthropogenic Influences and Impacts on Water and Sediment Quality

The Pirapo river watershed (Parana State, Brazil) compounds a relatively industrialized and urbanized region, undergoing great pressure from the discharge of industrial, agricultural and domestic wastes. We evaluated the environmental quality of ten streams belonging to this watershed in April and June 2008 by performing acute and chronic toxicity tests with Daphnia similis and Ceriodaphnia silvestrii from water and sediment samples. We tested the hypothesis that the streams located in urban areas are more exposed to the influence of pollutants, than those outside the city limits. In addition, we obtained the measures of physical and chemical parameters, and identified the main polluted sources. Contrary to what was expected, the rural streams were more toxic than those located in urban area. These results demonstrate that the water bodies located in rural areas are being affected by the pollution of aquatic ecosystems as far as those found in urban areas, requiring the same attention of environmental managers in relation to its monitoring.

The recent occurrence, establishment and potential impact of Geophagus proximus (Cichlidae : Perciformes) in the Tiete River reservoirs: an Amazonian fish species introduced in the Parana Basin (Brazil)

The introduction of allochthonous fish species happens constantly in large bodies of freshwater, like as the reservoirs of Parana Basin, located in Brazilian southeast, representing a threat for local biodiversity. The fish species Plagioscion squamosissimus and Cichla ocellaris were introduced from the 1970s in several water bodies of this basin and had successfully established themselves in all six reservoirs located in the middle and lower Tiete River (SP, Brazil), particularly. After six decades from the first recorded species introduction, this hydrographic system remains open to the invasion of further fish species, owing to widespread fish-farming activity and by the channels opened between this system and other reservoirs and river basin. This study was an effort to confirm the Geophagus proximus occurrence in the six Tiete River reservoirs, verifying the actual introduction status and analyzing its potential environmental impacts on local species by the analysis of the population structure (abundance, body dimensions and feeding habits). By the results, this species was confirmed in the Ibitinga, Nova Avanhandava and Tres Irmaos reservoirs. The abundance and feeding analysis shows, respectively, it is successfully established in the Tres Irmaos reservoir with the same feeding habitats of local species, such as Geophagus brasiliensis. It was further shown to be very likely that G. proximus would spread throughout the reservoir system of the middle and lower Tiete River, in the manner of P. squamosissimus and C. ocellaris, and the competition pressure for food resources between G. proximus and the local species which represents a potential environmental impact system. These scientific evidences fortifies the knowledge basin for the implantation of a fish management system, to control and reduce the abundance of the invader and to prevent its becoming established in all the Tiete River Basin, avoiding the disastrous consequences for the native species of Parana River Basin.

Oxidative stress biomarkers of exposure in the blood of cichlid species from a metal-contaminated river

The oxidative stress biomarkers of exposure, such as reduced glutathione (GSH), activity of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) and the levels of lipid peroxidation (LPO), were measured in the blood of three cichlid fish (Oreochromis niloticus, Tilapia rendalli, and Geophagus brasiliensis) taken during two seasons from two sites, unpolluted and polluted by industrial effluents, to evaluate the effectiveness of these biomarkers in assessing the impact of water contamination. The LPO levels in the blood were higher in fish from the metal-contaminated site and the chronic exposure led to significant changes in GPx, CAT, and SOD activities in all three cichlid species. The considerable variation of responses in these cichlids to water contamination evidenced differences in sensitivity to the metal contamination and/or in the potential to respond to it highlighting the importance of using a set of related biomarkers to assess the impact of water contamination. (C) 2007 Elsevier Inc. All rights reserved.

Monitoring Services for Industrial Applications

Sao Paulo Research Foundation (FAPESP) in Brazil

Rotifer abundance, biomass, and secondary production after the recovery of hydrologic connectivity between a river and two marginal lakes (Sao Paulo, Brazil)

Rotifera density, biomass, and secondary production on two marginal lakes of Paranapanema River were compared after the recovery of hydrologic connectivity with the river (Sao Paulo State, Brazil). Daily samplings were performed in limnetic zone of both lakes during the rainy season immediately after lateral inflow of water and, in the dry period, six months after hydrologic connectivity recovery. In order to identify the factors that affect rotifer population dynamics, lake water level, volume, depth, temperature, transparency, dissolved oxygen, pH, alkalinity, conductivity, suspended solids, nutrients, and chlorophyll-a were determined. Variations of water physical and chemical factors that affect rotifer population were related to the lake-river degree of connection and to water level rising after drought. The water lateral inflow from the river resulted in an increase in lake water volume, depth, and transparency and a decrease in water pH, alkalinity, and suspended solids. The lake with the wider river connection, more frequent biota exchange, and larger amount of particulate and dissolved materials was richer and more diverse, while rotifer density, biomass, and productivity were lower in both periods studied. Density, biomass, and secondary production were higher in the lake with the smaller river connection and the higher physical and chemical stability. Our results show that the connectivity affects the limnological stability, associated to seasonality. Stable conditions, caused by low connectivity in dry periods, were related with high density, biomass and secondary production. Conversely, instability conditions in rainy periods were associated to elevated richness and diversity values, caused by exchange biota due to higher connectivity. (C) 2008 Elsevier GmbH. All rights reserved.

Changes in optical properties caused by UV-irradiation of aquatic humic substances from the amazon river basin: Seasonal variability evaluation

Aquatic humic substances (AHS) isolated from two characteristic seasons of the Negro river, winter and summer corresponding to floody and dry periods, were structurally characterized by (13)C nuclear magnetic ressonance. Subsequently, AHS aqueous solutions were irradiated with a polychromatic lamp (290-475 nm) and monitored by its total organic carbon (TOC) content, ultraviolet-visible (UV-vis) absorbance, fluorescence and Fourier transformed infrared spectroscopy (FTIR). As a result, a photobleaching upto 80% after irradiation of 48 h was observed. Conformational rearrangements and formation of low molecular complexity structures were formed during the irradiation, as deduced from the pH decrement and the fluorescence shifting to lower wavelengths. Additionally a significant mineralization with the formation Of CO(2), CO, and inorganic carbon compounds was registered, as assumed by TOC losses of up to 70%. The differences in photodegradation between samples expressed by photobleaching efficiency were enhanced in the summer sample and related to its elevated aromatic content. Aromatic structures are assumed to have high autosensitization capacity effects mediated by the free radical generation from quinone and phenolic moieties.

In-Line Monitoring of Particle Size during Emulsion Polymerization under Different Operational Conditions using NIR Spectroscopy

In the present work, the sensitivity of NIR spectroscopy toward the evolution of particle size was studied during emulsion homopolymerization of styrene (Sty) and emulsion copolymerization of vinyl acetate-butyl acrylate conducted in a semibatch stirred tank and a tubular pulsed sieve plate reactor, respectively. All NIR spectra were collected online with a transflectance probe immersed into the reaction medium. The spectral range used for the NIR monitoring was from 9 500 to 13 000 cm(-1), where the absorbance of the chemical components present is minimal and the changes in the NIR spectrum can be ascribed to the effects of light scattering by the polymer particles. Off-line measurements of the average diameter of the polymer particles by DLS were used as reference values for the development of the multi-variate NIR calibration models based on partial least squares. Results indicated that, in the spectral range studied, it is possible to monitor the evolution of the average size of the polymer particles during emulsion polymerization reactions. The inclusion of an additional spectral range, from 5 701 to 6 447 cm(-1), containing information on absorbances (""chemical information"") in the calibration models was also evaluated.

Biogeochemical cycles of nutrients in tropical Eucalyptus plantations Main features shown by intensive monitoring in Congo and Brazil

The sustainability of fast-growing tropical Eucalyptus plantations is of concern in a context of rising fertilizer costs, since large amounts of nutrients are removed with biomass every 6-7 years from highly weathered soils. A better understanding of the dynamics of tree requirements is required to match fertilization regimes to the availability of each nutrient in the soil. The nutrition of Eucalyptus plantations has been intensively investigated and many studies have focused on specific fluxes in the biogeochemical cycles of nutrients. However, studies dealing with complete cycles are scarce for the Tropics. The objective of this paper was to compare these cycles for Eucalyptus plantations in Congo and Brazil, with contrasting climates, soil properties, and management practices. The main features were similar in the two situations. Most nutrient fluxes were driven by crown establishment the two first years after planting and total biomass production thereafter. These forests were characterized by huge nutrient requirements: 155, 10, 52, 55 and 23 kg ha(-1) of N, P, K, Ca and Mg the first year after planting at the Brazilian study site, respectively. High growth rates the first months after planting were essential to take advantage of the large amounts of nutrients released into the soil solutions by organic matter mineralization after harvesting. This study highlighted the predominant role of biological and biochemical cycles over the geochemical cycle of nutrients in tropical Eucalyptus plantations and indicated the prime importance of carefully managing organic matter in these soils. Limited nutrient losses through deep drainage after clear-cutting in the sandy soils of the two study sites showed the remarkable efficiency of Eucalyptus trees in keeping limited nutrient pools within the ecosystem, even after major disturbances. Nutrient input-output budgets suggested that Eucalyptus plantations take advantage of soil fertility inherited from previous land uses and that long-term sustainability will require an increase in the inputs of certain nutrients. (C) 2009 Elsevier B.V. All rights reserved.