Soils of Sao Domingos mine: REE chemical characterization

This work addresses the chemical features of topsoils from São Domingos mine, Portugal, an abandoned mining area since middle of twentieth century. The fractions below 1 mm of the surface-soil samples (0–15 cm) were measured by k₀-standardized, instrumental neutron activation analysis in order to determine the levels of rare earth element concentrations in comparison to control soils. A fractionation between the heavy and light rare-earth elements (REEs) occurred, with the latter enriched relatively to the first ones. The REEs pattern is similar in all sites with higher concentrations in the mine area as compared to the control site. The ratios between REEs are conventional for three subsamples but slightly diverge for the other sites. The REEs pattern is similar to one of the volcanic islands still with activity as Sao Miguel in Azores, Portugal, and similar to the one of an industrial area containing coal power plant and refinery.     

Determination of phytoextraction potential of plant species for toxic elements in soils of abandoned sulphide-mining areas

This study has determined contamination levels in soils and plants from the São Domingos mining area, Portugal, by k ₀-INAA. Total concentrations of As, Sb, Cr, Hg, Cu, Zn and Fe in soils were very high, exceeding the maximum limits in Portuguese legislation. Concentrations of toxic elements like As, Sb and Zn were highest in roots of Erica andevalensis, Juncus acutus, Agrostis castellana and Nicotiana glauca. Additionally, As, Br, Cr, Fe, Sb and Zn in all organs of most plants were above toxicity levels. Those species that accumulated relatively high concentrations of toxic elements in roots (and tops) may be cultivated for phytostabilisation of similar areas.     

Biomonitoring of coastal regions of São Paulo State,Brazil, using mussels <Emphasis Type="Italic">Perna perna</Emphasis>

The marine environment is constantly affected by anthropic actions, with causes consequent degradation of the waters and marine biota by various discharges of xenobiotics. In the present study, the focus was the study of a region of the marine coast of the State of São Paulo (city of Santos), which is one of the most industrialized parts of Brazil and suffers also from a strong impact of domestic effluents. The mussel Perna perna, very abundant in the coast of the State of São Paulo, Brazil, was selected as the biomonitoring organism for the determination of inorganic elements and a passive biomonitoring was performed. The organisms were collected at two sites in São Paulo State coast: Cocanha beach in Caraguatatuba (mussel farm) and Santos Bay (Itaipu and Palmas). Seasonally, the Perna perna were collected between September/08 and July/09 in each study sites. After removal and sample preparation, the elements As, Co, Cr, Fe, Se and Zn were determined by instrumental neutron activation analysis (INAA) and Cd, Pb and Hg were determined by atomic absorption spectroscopy (AAS) in this organism.     

Air-quality assessment of Pico-mountain environment (Azores) by using chemometric and trajectory analyses

This article illustrates the use of chemometrics in the interpretation of aerosol data collected by a seven-wavelength aethalometer at the PICO-NARE observatory, in Pico island, Azores, Portugal. Samples were assessed through k ₀-standardized, instrumental neutron activation analysis (k ₀-INAA), and concentrations of up to 20 airborne elements were determined. The chemometric analysis by self-organizing maps (SOM) tried to identify groups of similarity for sampling events and chemical tracers, discriminating in this way each group of similarity thus obtained. Additionally, synoptic back trajectories for each of the sampling days distributed into four clusters were calculated, in order to associate the classified groups with possible pollution sources.     

Catalytic effects of cationic nanoparticle (CTABr/NaX/H<Subscript>2</Subscript>O,X = Cl,Br) for the piperidinolysis of phenyl salicylate ions

The expression of pseudo-second-order rate constants (k _X) for cationic nanoparticle (CN) [CTABr/NaX/H₂O, X = Br, Cl, CTABr = cetyltrimethylammonium bromide] catalyzed piperidinolysis-ionized phenyl salicylate (PSa^–), at constant [CTABr]_T, 0.1 M piperidine (Pip), and 35°C, were calculated from the relationship: k _obs = (k ₀ + k _X[NaX])/(1 + K ^X/S[NaX]), in which k ₀, k _X, and K ^X/S are constant kinetic parameters and k _obs represents the pseudo-first-order rate constant for Pip reaction with phenyl salicylate ion in the presence of CN. The source of the large catalytic effect of CN catalyst was shown to be due to the transfer of PSa^– from pseudo-phase of the CNs to the bulk aqueous phase through X^–/PSa^– ion exchange at the surface of the CNs.     

Dissolution kinetics of silver metal nanoparticles in their reaction with nitric acid in an reverse micelle solution of AOT

The dissolution of silver nanoparticles in their reaction with aqueous HNO₃ solubilized to an reverse micelle solution of sodium bis(2-ethylhexyl)sulfosuccinate in decane is studied spectrophotometrically. A physicochemical model is advanced for quantifying the process kinetics on th basis of the following autocatalytic scheme: Ag⁰ + H⁺ + NO ₃ ^? → Ag⁺ + products (k ₁), and Ag⁰ + Ag⁺ + NO ₃ ^? → 2Ag⁺ + products (k ₂). The effective rate constant k ₂ decreases with decreasing solubilization capacity V _S/V _O (where V _S is the volume of the solubilized dispersed aqueous phase and V _O is the volume of the micelle solution); the solubilization capacity determines the size of the micelle cavities in which the reaction between Ag⁰ and HNO₃ occurs: k ₂ = 74 (V _S/V _O) · 100% ≈ 3.8%), 41 (2.9), and 35 (2.0) L/(mol s). The effective constant k ₁ is determined with a high uncertainty; the effect of V _S/V _O on k ₁ has the opposite tendency.     

Random packing of monoatomic structures

The dependence of the first coordination number k _n on the packing factor k _y is obtained for four cubic structures: fcc, bcc, simple cubic, and diamond. The k _n (k _y ) dependence is described by a third-degree polynomial k _n = ?71.76782 + 467.78914 k _y ? 925.48451 k _y ² + 603.01146 k _y ³ with the confidence factor R _d = 1. The k _n (k _y ) function has an N loop with a maximum at k _n = 6.32; k _y = 0.454 and a minimum at k _n = 5.84; k _y = 0.573. The tangents intersect the k _n (k _y ) curve at extrema at k _y = 0.4 and k _y = 0.625. Around the N loop, i.e., at 5.84 ≤ k _n ≤ 6.32 and 0.4 ≤ k _y ≤ 0.625, two or three packing factors correspond to a certain value of the coordination number. Therefore, this range of the k _n and k _y values can be defined as a “random packing” region. Estimations presented here agree well with the results of calculations, both geometric and numerical. For monoatomic solids with the random packing parameters, the difference between the specific volumes of the solid and liquid phases is insignificant. The dilatancy effect is possible in the region where ?k _n / ?k _y ≤ 0.     

Arsenic and cadmium content in edible mushrooms from São Paulo,Brazil determined by INAA and GF AAS

Arsenic and cadmium contents in eight edible mushroom species (Agaricus bisporus, Agaricus sp, Pleurotus ostreatus, Pleorotus florida, Pleorotus eryngui, Pleurotus osteatus, Pleurotus salmoneostramineus, Lentinula edodes) consumed by Brazilian population were determined by instrumental neutron activation analysis (INAA) and graphite furnace atomic absorption spectrometry (GF AAS), respectively. Arsenic concentrations varied from 0.009 mg/kg in P. eryngui to 0.210 mg/kg dry weight in L. edodoes and Cd from 0.011 g/kg in P. eryngui to 0.229 mg/kg dw in P. salmoneostramineus. The consumption of mushrooms in São Paulo-Brazil may be considered safe from a toxicological point of view as As and Cd presented levels of ingestion are below the maximum levels recommended by the World Health Organization.     

Bestimmung der Dissoziationskonstanten der Formen H5 Y +, H4 Y und H3 Y − der ÄDTE

A critical examination of the methods used in evaluating the constantsk ₆, k₅, k₁ andk ₂ of EDTA shows that potentiometric titration is suitable for the determination of the constantsk ₁ andk ₂ only, but not fork ₆ andk ₅. On the other hand the dependence of the solubility of EDTA upon pH can be used to evaluatek ₁,k ₂ andk ₅, but notk ₆ for the applied experimental conditions (25°C; ionic strength 0,1 m).     

Vanadium biomonitoring by using <Emphasis Type="Italic">Perna perna</Emphasis> (Linnaeus, 1758) mussels transplanted in the coast of the State of São Paulo,Brazil

The increased pollution in the aquatic ecosystem has led to the investigation of toxic elements in sea water by using marine organisms to assess marine pollution from human activities. Among these organisms, the mollusks bivalves have been used as biomonitors since they can accumulate trace elements and other substances, without the occurrence of their death. In this study, Perna perna mussels were transplanted from a mussel farm (reference region) to four sites located in coastal regions of São Paulo State, Brazil, close to anthropic discharge areas. Vanadium was determined in mussel tissues by instrumental neutron activation analysis (INAA). Quality control of V analysis was checked by analyzing biological reference materials and the results obtained were precise and in good agreement with the certified values. Comparisons between the V concentrations obtained in transplanted mussels indicated that those from São Sebastião region, close to an oil terminal presented the highest concentration of this element, during spring.     

Biomonitoring of the atmospheric pollution using lichens in the metropolitan area of São Paulo city,Brazil

The atmospheric pollution of São Paulo city is a serious problem due to the expansion of industrial area, increasing number of vehicles and population density. This work presents results obtained in the analysis of lichens collected in different sites of São Paulo city and in non-polluted areas of Atlantic Forest. Concentrations of twenty elements were determined in Canoparmelia texana species and comparisons were made between the results obtained in lichens from different sites. High concentrations of the elements As, Ba, Cd, Co, Cr, Fe, La, Mn, Sb and Zn were found for samples collected in sites located near industries and petrochemical plant. Br and Sb concentrations were also high in lichens from sites affected by vehicular emissions.     

Von den Größen der chemischen Kinetik

An Hand der denkbar einfachsten chemischen Reaktion\(A\underset{2}{\overset{1}{\longleftrightarrow}}B\) wird gezeigt, daß die Geschwindigkeitskoeffizienten (Gk)k ₁ undk ₂ sowie ihr Quotient, also die Gleichgewichtskonstante (Glk)K=k ₁/k ₂,keine Eigene xistenz beistzen. Sie werden erst dann physikalischwinklich und sinnvoll, wenn sie mit ihrenStoffgrößen gepaart sind, ink ₁ A undk ₂ B und Geschwindigkeiten, inKA=B zum Gleichgewichte.     

Non-isothermal kinetic for lyophilized leachate from sanitary landfill and composting usine

Leachate samples from a sanitary landfill of Araraquara city and composting usine of Vila Leopoldina, São Paulo, Brazil were lyophilized to remove the water content. TG/DTG curves at different heating rates were recorded. The second step of the thermal decomposition of leachate from the Araraquara landfill (CB₁), from the composting usine from Vila Leopoldina (CB₂) from the organic phase extracted (FO) and aqueous phase (FA) were all kinetically evaluated using the non-isothermal method.By Flynn-Wall isoconversional method the following values were obtained: E=234±3.65 kJ mol^?1 and logA=29.7±0.58 min^?1 for CB₁; E=129±1.66 kJ mol^?1 and logA=11.8±0.10 min^?1 for CB₂; E=51.6±1.35 kJ mol^?1 and logA=6.09±0.09 min^?1 for FO and E=76.91±6.33 kJ mol^?1 and logA=8.88±0.7 min^?1 for FA with 95% confidence level. Applying the procedures of Málek and Koga, SB kinetic model (?esták-Berggren) is the most appropriate to describe the decomposition of CB₁, CB₂, FO and FA.     

Effect of solvent nature on the photoreduction kinetics of substituted benzoquinones

Effect of the solvent nature on the kinetics of photoreduction of substituted benzoquinones in the presence of hydrogen donors has been studied. It has been found that the effective photoreduction rate constant (k_H) for quinones decreases with an increase in solvent polarity. For the 3,6-di-tert-butylbenzoquinone–1,2-N,N-dimethylaniline pair, the dependence of ln k_H on the difference of the reciprocals of optical and static solvent permitivities (1/ε _∞–1/ε₀) is stepwise with a break point corresponding to CH₂Cl₂. A similar relationship lnk_H = f(1/ε _∞–1/ε₀) is observed for the p-chloranil–mesitylene pair. In the study of the photoreduction kinetics for a series of seven o-benzoquinones in the presence of p-derivatives of N,N-dimethylaniline in CH₂Cl₂, it has been found that the dependence of k_H on the free energy of electron transfer (ΔG_e) has a maximum for the 3,6-di-tert-butylquinone-1,2–N,N-dimethylaniline pair at ΔG_e = 0.11 eV.     

Substituent effects on the kinetics of acid-catalyzed hydrolysis of methyl cellulose

The kinetics of the hydrolysis of methyl cellulose (MC, DS 1.27 and 1.95) was studied by a two-step procedure, comprising partial hydrolysis in 1 M TFA in water and water/acetone at 120 °C for various time periods, labeling of generated reducing ends by reductive amination, complete depolymerization by methanolysis followed by trimethylsilylation, and gas chromatographic analysis of the two sets of partially O-methylated glucose derivatives. Rate constants of MCs were all in the order of 10^?4 s^?1. In aqueous TFA, overall rate of hydrolysis of the MC with lower DS was faster than of the MC with higher DS. When substituting half of the water by acetone, reaction was slowed down while selectivity regarding different O-methyl glucosyl residues increased. Compared to the parent glucosyl unit methylation at O-2 and at O-6 decreased rate of hydrolysis, while 3-O-methyl favored it especially in the early stage of the conversion of the macromolecules. Beside slight differences between the two MCs and reaction conditions, rate constants k _i (i = position of methyl) followed the order k ₃₆ ≈ k ₃ > k ₀ ≈ k ₂₃ > k ₆ > k ₂ ≥ k ₂₃₆ > k ₂₆. For the higher substituted MC2 an initial slow phase with more pronounced differences of k _i, followed by a faster less selective period was observed. Regioselectivity of hydrolysis with respect to methyl positions was expressed as standard deviation of k _i and was between 16 and 46% depending on MC and conditions. Findings are discussed with respect to electronic effects, solvent-effect, H-bonding pattern and solution state.     

Measurement of the neutron flux parameters <Emphasis Type="Italic">f</Emphasis> and <Emphasis Type="Italic">α</Emphasis> at the Pavia TRIGA Mark II reactor

In this paper, evaluation of neutron flux parameters of TRIGA Mark II reactor in Pavia was carried out. For any of the three irradiation positions investigated, this work represented the first experimental evaluation of α. Moreover, in addition to α, values of other parameters such as f, Φ _th and Φ _e were also calculated and compared with the existent literature data from other TRIGA Mark II reactors and the Pavia’s facility. Results obtained in the present study represent a mandatory step ahead for future application of k ₀-Neutron Activation Analysis method (k ₀-NAA) at Pavia’s facility.     

Metals and semi-metals in street soils of São Paulo city,Brazil

São Paulo is the largest city in Brazil and South America with about 20 million inhabitants in the metropolitan area, more than nine million motor vehicles and intense industrial activity, which are responsible for increasing pollution in the region. Nevertheless, little is known concerning metal and semi-metal content in the soils of this metropolitan region. This type of information could be extremely useful as a fingerprint of environmental pollution. The present study determined the elements As, Ba, Co, Cr, Sb, and Zn concentrations in soils adjacent to avenues of highly dense traffic in São Paulo city to assess their levels and possible sources. The analytical technique employed was Instrumental neutron activation analysis. The results showed, except for Co, concentration levels higher than the reference values for soils of São Paulo, according to the Environmental Protection Agency of the State of São Paulo guidelines. When compared to similar studies in other cities around the world, São Paulo soils presented higher levels, probably due to its high density traffic and industrial activity. The concentrations obtained for As and Cr indicate anthropogenic origin. The high levels of the traffic-related elements Ba, Sb, and Zn in soils nearby high density traffic avenues indicate they may originate from vehicular exhausts.     

New linear driving force correlation spanning long and short cycle time pressure swing adsorption processes

A simple, semi-empirical, generalized expression was developed for the LDF mass transfer coefficient k as a function of the half cycle time θ _c that encompasses and transitions between the well-known regions governed by the long cycle time constant Glueckauf k and the short cycle time dependent k. This new expression can be used to estimate k = f(θ _c ) for any system, irrespective of the loading and irrespective of θ _c , no matter if k is in the cycle time dependent region or not. A three times wider transition region between the Glueckauf k and the cycle time dependent k was also established, with the Glueckauf LDF limit now valid for θ _c  > 0.3 and the short cycle time limit now valid for θ _c  < 0.01. When evaluating this region for several adsorbate-adsorbent systems, the minimum Glueckauf θ _c spanned three orders of magnitude from thousands of seconds to just a few seconds, indicating a cycle time dependent k is not necessarily limited to what is normally considered a short cycle time. For virtually any θ _c less than this minimum Glueckauf θ _c , this new first-of-its-kind expression can be used to readily provide an accurate value of k = f(θ _c ). Since the widely accepted half cycle time concept does not apply to the actual simulation of a multi-step, unequal step time, pressure swing adsorption process, the value of k = f(θ _c ) from this new expression can be based on either the shortest cycle step in the cycle or a different value of k = f(θ _c ) for each cycle step time in the cycle, with validity confirmed either by experiment or by process simulation using the exact solution to the pore diffusion equation.     

Analysis of saliva from <Emphasis Type="Italic">Amblyomma cajennense</Emphasis> (Acari: Ixodidae) species from Brazil by NAA

The Amblyomma cajennense tick species is considered one of the most important and widespread species in Brazil. It salivary secretion has been a target of several studies in biocenology, as the vector of diseases and in investigations related to antihemostatic properties and antitumor. To complement this investigation, neutron activation analysis (NAA) was applied to determine concentrations of elements in saliva samples of this tick species. The saliva samples (50–554 μL) were collected at Butantan Institute (São Paulo city, Brazil) and they were investigated using the IEA-R1 nuclear reactor at IPEN/CNEN-SP-Brazil. These data were compared with the values established for Amblyomma americanum and Amblyomma variegatum species emphasizing agreement only for Cl, K and Na with the A. americanum species, suggesting similarities in the mechanisms that regulate the osmotic pressure in this hematophagous animal. The knowledge of these limits contributes for tick saliva characterization as well as for the understanding of the many physiological processes, especially those related to salivary secretion.