Trace-metal biogeochemistry in the Mediterranean Thau Lagoon, a shellfish farming area

The present study contributes to the knowledge of the biogeochemistry of Pb, Cd, Cu, and Ni in the Mediterranean Than Lagoon, southern France, which is an important shellfish farming system. The concentrations of the metals were determined in sediment cores and the overlying waters using inductively coupled plasma mass spectrometry. Particular attention was given to the determination of dissolved Cu species because of their dual role as essential nutrient and toxicant to planktonic organisms. Dissolved Cu speciation was determined using the diffusive gradient in thin-film technique (DGT) and competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV). Our data indicated a significant historical contamination of the sediments, which commenced in the second half of the 19th century, with trace metal inputs persisting until the end of the 20th century. In recent years a decrease in metal contamination has become apparent. The maxima observed for Pb, Cd, and Cu profiles probably indicate the occurence of anoxia crises. A strong complexation of the dissolved Cu species was observed in the waters of the Than Lagoon, which reduced the bioavailability of Cu. The dissolved Cu(2+) concentrations were probably too low to cause direct toxic effects on shellfish, but the highest concentration (5.29 pM) observed in this study can potentially influence phytoplankton communities. A comparison between the Cu speciation data indicates that up to 50% of the complexed Cu determined using CLE-ACSV was DGT labile.

Automated two-dimensional separation flow system with electrochemical preconcentration, stripping, capillary electrophoresis and contactless conductivity detection for trace metal ion analysis

This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C(4)D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C(4)D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C(4)D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.

Trace element impurity determination in aspirin tablets by INAA

Instrumental neutron activation analysis (INAA) was applied to assess trace element concentrations in six samples of aspirin tablets acquired in SA o pound Paulo city, Brazil. Concentrations of the elements Br, Ca, Co, Cr, Fe, K, La, Na, Sc and Zn were determined. Comparisons were made between the results obtained with published data for aspirins from foreign countries. Certified reference materials, INCT-MPH-2 Mixed Polish Herbs were analyzed for quality control of the analytical results.

Uma Proposta de uso da Arquitetura Trace como um sistema de detecção de intrusão

Este trabalho propõe a utilização da arquitetura Trace como um sistema de detecção de intrusão. A arquitetura Trace oferece suporte ao gerenciamento de protocolos de alto nível, serviços e aplicações através de uma abordagem baseada na observação passiva de interações de protocolos (traços) no tráfego de rede. Para descrever os cenários a serem monitorados, é utilizada uma linguagem baseada em máquinas de estado. Esta linguagem permite caracterizar aspectos observáveis do tráfego capturado com vistas a sua associação com formas de ataque. O trabalho mostra, através de exemplos, que esta linguagem é adequada para a modelagem de assinaturas de ataques e propõe extensões para permitir a especificação de um número maior de cenários ligados ao gerenciamento de segurançaa. Em seguida, é descrita a implementação do agente de monitoração, componente-chave da arquitetura Trace, e sua utilização para detectar intrusões. Esse agente (a) captura o tráfego da rede, (b) observa a ocorrência dos traços programados e (c) armazena estatísticas sobre a sua ocorrência em uma base de informações de gerenciamento (MIB { Management Information Base). O uso de SNMP permite a recuperação destas informações relativas µa ocorrências dos ataques. A solução apresentada mostrou ser apropriada para resolver duas classes de problemas dos sistemas de detecção de intrusão: o excesso de falsos positivos e a dificuldade em se modelar certos ataques.

Central limit theorem for asymmetric kernel functionals

Asymmetric kernels are quite useful for the estimation of density functions with bounded support. Gamma kernels are designed to handle density functions whose supports are bounded from one end only, whereas beta kernels are particularly convenient for the estimation of density functions with compact support. These asymmetric kernels are nonnegative and free of boundary bias. Moreover, their shape varies according to the location of the data point, thus also changing the amount of smoothing. This paper applies the central limit theorem for degenerate U-statistics to compute the limiting distribution of a class of asymmetric kernel functionals.

Bounds on functionals of the distribution treatment effects

Bounds on the distribution function of the sum of two random variables with known marginal distributions obtained by Makarov (1981) can be used to bound the cumulative distribution function (c.d.f.) of individual treatment effects. Identification of the distribution of individual treatment effects is important for policy purposes if we are interested in functionals of that distribution, such as the proportion of individuals who gain from the treatment and the expected gain from the treatment for these individuals. Makarov bounds on the c.d.f. of the individual treatment effect distribution are pointwise sharp, i.e. they cannot be improved in any single point of the distribution. We show that the Makarov bounds are not uniformly sharp. Specifically, we show that the Makarov bounds on the region that contains the c.d.f. of the treatment effect distribution in two (or more) points can be improved, and we derive the smallest set for the c.d.f. of the treatment effect distribution in two (or more) points. An implication is that the Makarov bounds on a functional of the c.d.f. of the individual treatment effect distribution are not best possible.

Carbon fiber microelectrodes for adsorptive stripping analysis of trace nucleic acids

Carbon fiber ultramicroelectrodes are shown to be suitable for adsorptive stripping potentiometric measurements of trace DNA and RNA. The origin of the carbon fiber has a profound effect upon its suitability for trace analysis of nucleic acids, with the 'Aesar' materials performing most favorably. The resulting ultramicroelectrodes offer effective adsorptive accumulation of DNA and RNA from unstirred microliter-volume solutions, and are shown to be useful in adsorptive stripping transfer experiments. The influence of the surface pretreatment and accumulation conditions is described, along with the analytical-performance characteristics. The detection limits are 6, 15 and 40 mu g/l tRNA, ssDNA and dsDNA, respectively (5 min accumulation). (C) 1998 Elsevier B.V. S.A.

Effects of dietary trace mineral sources and levels fed to layers in their second laying cycle on the quality of eggs stored at different temperatures and for different periods

This study aimed at evaluating the effects of trace mineral levels and sources supplemented to diets fed to semi-heavy layers in their second laying cycle on the quality of eggs stored for 14 days at different temperatures. The experimental diets consisted of the inclusion of inorganic trace minerals (T1 - control: 100% ITM) and five supplementation levels of organic trace minerals (carboaminophopho chelates) (110, 100, 90, 80, and 70% OTM). Trace mineral inclusion levels (mg/kg feed) were: T1: control - 100% ITM: Zn (54), Fe (54), Mn (72), Cu (10), I (0.61) Se (0.3); T2 - 110% OTM: Zn (59.4), Fe (59.4), Mn (79.2), Cu (11.88), I (1.21) Se (0.59); T3 - 100%: OTM: Zn (54), Fe (54), Mn (72), Cu (10.8), I (1.10) Se (0.54); T4 - 90% OTM: Zn (48.6), Fe (48.6), Mn (64.8), Cu (9.72), I (0.99) Se (0.49); T5 - 80% OTM: Zn (43.2), Fe (43.2), Mn (57.6), Cu (8.64), I (0.88), Se (0.43); T6 - 70% OTM: Zn (37.8), Fe (37.8), Mn (50.4), Cu (7.56), I (0.77) Se (0.38). A completely randomized experimental design in a split-plot arrangement with 60 treatments of four replicates each was applied. The combination of six diets versus storage temperature (room or under refrigeration) was randomized in plots, whereas the sub-plots consisted of storage times (0, 3, 7, 10, and 14 days). Data were submitted to analysis of variance of a model in slip-plots in time using the software package SAS (2000) at 5% probability level. It was concluded that 70% OTM supplementation can be used with no damage to egg quality, independently from storage temperature or time. The quality of refrigerated eggs stored up to 14 days is better than those stored at room temperature.

Sources of organic trace minerals in diets for weaned piglets

One hundred and twenty six piglets from a commercial genetic strain weaned at 21 days of age (6.11±0.42 kg) were used to evaluate the effects of supplementation levels of organic sources of trace minerals in the diets of weaned piglets on performance, occurrence of diarrhea, excretion of copper and zinc in the feces, and hematological parameters. A completely randomized block design was adopted, composed of six treatments (diets containing 100% of inorganic trace minerals premix at 3.00 kg/T; diets containing 0, 25, 50, 75 or 100% of organic trace minerals premix, equivalent to 0; 0.75; 1.50; 2.25 or 3.00 kg/T, respectively), seven replicates and three animals per plot. During the experimental period (from 21 to 63 days of age), the increasing levels of organic trace minerals premix in the diets determined a quadratic effect on daily weight gain (DWG), feed conversion (FC), percentage of hematocrit (Ht), hemoglobin (Hb), mean corpuscular hemoglobin (MCH), mean corpuscular volume (MCV), platelets (Pt), and a linear increase of Cu and Zn concentrations in feces. The comparison of means between the treatment with inorganic trace minerals premix and the other treatments showed that piglets fed diets without trace minerals premix had lower values of DWG, Ht, Hb, MCH, MCV, Pt and the worst FC value of piglets fed diets containing 25% of organic trace minerals premix presented lower values of Ht and Hb, in comparison with those fed diets with 100% of inorganic trace minerals premix. Inorganic trace minerals premix can be substituted by organic trace minerals premix at a lower level of inclusion in diets for weaned piglets.

Generalized squeezing operators, bipartite Wigner functions and entanglement via Wehrl's entropy functionals

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hydrothermal rare earth elements mineralization in the Barra do Itapirapua carbonatite, southern Brazil: behaviour of selected trace elements and stable isotopes (C, O)

The Bura do Itapira pua carbonatite is located in southern Brazil and belongs to the Cretaceous Ponta Grossa alkaline-carbonatitic province related to the opening of the South Atlantic. The carbonatite complex is emplaced in Proterozoic granites and is mainly composed of plutonic magnesio- to ferrocarbonatite, with smaller amounts of subvolcanic magnesiocarbonatite. Hydrothermal alteration of the carbonatite has led to the formation of quartz, apatite, fluorite, rue earth fluorocarbonates, barite and sulfides in variable proportions. Trace element data, delta(13)C and delta(18)O are presented here, with the aim of better understanding the geochemical nature of hydrothermal alteration related to rare earth elements (REE) mineralization. The non-overprinted plutonic carbonatite shows the lowest REE contents, and its primitive carbon and oxygen stable isotopic composition places it in the field of primary igneous carbonatites. Two types of hydrothermally overprinted plutonic carbonatites can be distinguished based on secondary minerals and geochemical composition. Type I contains mainly quartz, rare earth fluorocarbonates and apatite as hydrothermal secondary minerals, and has steep chondrite normalized REE patterns, with Sigma(REE+Y) of up to 3 wt.% (i.e., two orders of magnitude higher than in fresh plutonic samples). In contrast, the Type II overprint contains apatite, fluorite and barite as dominant hydrothermal minerals, and is characterized by heavy REE enrichment relative to the fresh samples, with flat chondrite normalized REE patterns. Carbon and oxygen stable isotope ratios of Types I and II are elevated (delta(18)O + 8 to + 12 parts per thousand; delta(13)C - 6 to - 2 parts per thousand) relative to the fresh samples. Hydrothermally overprinted carbonatites exposed to weathering show even higher delta(18)O values (delta(18)O 13 to 25 parts per thousand) but no additional REE enrichment. The subvolcanic carbonatite has anomalously high delta(13)C of up to + 1 parts per thousand, which suggests crustal contamination through interaction with carbonate-bearing metasediments. (C) 1999 Elsevier B.V. B.V. All rights reserved.

The use of Langmuir-Blodgett films of a perylene derivative and polypyrrole in the detection of trace levels of Cu2+ ions

Langmuir films of a tetracarboxylic perylene derivative and polypyrrole display condensed surface pressure isotherms that are shifted when Cu2+ ions are added to the ultrapure water subphase. These films were transferred onto interdigitated gold electrodes leading to Y-type Langmuir-Blodgett (LB) films. The electrodes modified with 5-layer LB films were immersed into a flask with ultrapure water and water containing Cu2+ ions at concentrations ranging from mM to muM. Impedance measurements indicated a distinct electrical response for the two types of films. Although the materials chosen have no specificity for ionic metals, they can be combined for detecting trace levels of Cu2+, which may be exploited in water quality monitoring. (C) 2004 Elsevier B.V. All rights reserved.

Evaluation of a highly sensitive amperometric biosensor with low cholinesterase charge immobilized on a chemically modified carbon paste electrode for trace determination of carbamates in fruit, vegetable and water samples

A highly sensitive amperometric biosensor for determination of carbamate pesticides directly in water, fruit and vegetable samples has been evaluated, electrochemically characterized and optimized. The biosensor strip was fabricated in screen printed technique on a ceramic support using silver-based paste for reference electrode, and platinum-based paste for working and auxiliary electrodes. The working electrode was modified by a layer of carbon paste mixed with cobalt(II) phthalocyanine and acetylcellulose. Cholinesterase (ChE) enzymes with low enzymatic charge were immobilized on this layer. The operational simplicity of the biosensor consists in that a small drop (similar to 50 mu l) of substrate or sample is deposited on a horizontally positioned biosensor strip representing the microelectrochemical cell. The working potential of the biosensor was 370 mV versus Ag/AgI on a ship reference electrode preventing the interference of electroactive species which are oxidable at more positive potentials. The biosensor was applied to investigate the degradation of two reference ChE inhibitors in freeze dried water under different storage conditions and for direct determination of some N-methylcarbamates (NMCs) in fruit and vegetable samples at ppb concentration levels without any sample pretreatment. A comparison of the obtained results for the total carbamate concentration was done against those obtained using HPLC measurements. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Adsorptive potentiometric stripping analysis of trace tamoxifen at a glassy carbon electrode

A highly sensitive adsorptive stripping procedure for trace measurement of the anticancer drug tamoxifen is described. The method is based on controlled adsorptive accumulation of the drug at an electrochemically treated glassy carbon electrode, followed by chronopotentiometric measurement of the surface species. The chronopotentiometric operation effectively addresses the large background contribution inherent to the glassy carbon electrode to yield a detection limit of 4 x 10(-10) M after 4 min preconcentration. The adsorptive stripping response is evaluated with respect to electrode type and conditioning, accumulation potential and lime, stripping current, pH, drug concentration, potential interferences, and other variables. Applicability to urine samples is illustrated. (C) 1997 Elsevier B.V. B.V.