Copper and lead removal by peanut hulls: equilibrium and kinetic studies

This research work aims to study the use of peanut hulls, an agricultural and food industry waste, for copper and lead removal through equilibrium and kinetic parameters evaluation. Equilibrium batch studies were performed in a batch adsorber. The influence of initial pH was evaluated (3–5) and it was selected between 4.0 and 4.5. The maximum sorption capacities obtained for the Langmuir model were 0.21 ± 0.03 and 0.18 ± 0.02 mmol/g, respectively for copper and lead. In bi-component systems, competitive sorption of copper and lead was verified, the total amount adsorbed being around 0.21 mmol of metal per gram of material in both mono and bi-component systems. In the kinetic studies equilibrium was reached after 200 min contact time using a 400 rpm stirring rate, achieving 78% and 58% removal, in mono-component system, for copper and lead respectively. Their removal follows a pseudo-second-order kinetics. These studies show that most of the metals removal occurred in the first 20 min of contact, which shows a good uptake rate in all systems.

Evaluation of the role of glutathione in the lead-induced toxicity in saccharomyces cerevisiae

The effect of intracellular reduced glutathione (GSH) in the lead stress response of Saccharomyces cerevisiae was investigated. Yeast cells exposed to Pb, for 3 h, lost the cell proliferation capacity (viability) and decreased intracellular GSH level. The Pb-induced loss of cell viability was compared among yeast cells deficient in GSH1 (∆gsh1) or GSH2 (∆gsh2) genes and wild-type (WT) cells. When exposed to Pb, ∆gsh1 and ∆gsh2 cells did not display an increased loss of viability, compared with WT cells. However, the depletion of cellular thiols, including GSH, by treatment of WT cells with iodoacetamide (an alkylating agent, which binds covalently to thiol group), increased the loss of viability in Pb-treated cells. In contrast, GSH enrichment, due to the incubation of WT cells with amino acids mixture constituting GSH (l-glutamic acid, l-cysteine and glycine), reduced the Pb-induced loss of proliferation capacity. The obtained results suggest that intracellular GSH is involved in the defence against the Pb-induced toxicity; however, at physiological concentration, GSH seems not to be sufficient to prevent the Pb-induced loss of cell viability.

Evolução hidrogeoquímica das águas sulfúreas de Entre-os-Rios: avaliação preliminar

O principal objectivo desta dissertação foi avaliar a evolução hidrogeoquímica das águas minerais de Entre‐os‐Rios, para uma melhor compreensão do modelo hidrogeológico conceptual deste sistema hidromineral. Desta forma, foram coligidos diversos dados hidroquímicos, quer das nascentes clássicas (Torre, Curveira, Ardias, Arcos Esquerda e Arcos Direita), quer do furo Barbeitos. Foram compiladas e analisadas oitenta análises hidroquímicas no período 1938‐2012, incluindo características organolépticas (cheiro, cor e turbidez), diversas propriedades físico-químicas (temperatura, pH, condutividade eléctrica, sulfuração, etc), os principais catiões e aniões (bicarbonato, fluoreto, sódio, lítio, etc) e os elementos vestigiários (chumbo, tungsténio, boro, etc). Além disso, foram integrados os dados históricos disponíveis de finais do século XIX e inícios do século XX. Foram igualmente reunidos e discutidos alguns dados isotópicos (oxigénio‐18, deutério e trítio). O recurso hidromineral de Entre‐os‐Rios está condicionado pela litologia e pelas condições tectónicas. As análises químicas revelaram que as águas minerais de Entre‐os‐Rios apresentam uma estabilidade química nos últimos 100 anos. Estas águas são orto‐ a hipertermais, fracamente mineralizadas, de reacção alcalina, sulfídricas, bicarbonatadas sódicas, carbonatadas e muito fluoretadas. Estas características são claramente distintas das águas normais da região. As águas de Entre‐os‐Rios são muito semelhantes às águas minerais de S. Vicente e, em diversos parâmetros, bastante diferentes das águas minerais das Caldas da Saúde. Os dados isotópicos permitiram concluir que as águas de Entre‐os‐Rios têm uma origem meteórica, com um tempo de residência longo no sistema aquífero, e que são, muito provavelmente, submodernas, com uma recarga anterior a 1952. Na região de Entre‐os‐Rios coexistem três sistemas aquíferos, um sistema granítico superficial, livre e um sistema livre a semi‐confinado, ambos com circulação de águas normais, e um sistema aquífero granítico, profundo, confinado, com circulação de água mineral.

Inoculation with Metal-Mobilizing Plant-GrowthPromoting Rhizobacterium Bacillus sp. SC2b and Its Role in Rhizoremediation

A plant growth-promoting bacterial (PGPB) strain SC2b was isolated from the rhizosphere of Sedum plumbizincicola grown in lead (Pb)/zinc (Zn) mine soils and characterized as Bacillus sp. based on (1) morphological and biochemical characteristics and (2) partial 16S ribosomal DNA sequencing analysis. Strain SC2b exhibited high levels of resistance to cadmium (Cd) (300 mg/L), Zn (730 mg/L), and Pb (1400 mg/L). This strain also showed various plant growth-promoting (PGP) features such as utilization of 1-aminocyclopropane-1-carboxylate, solubilization of phosphate, and production of indole-3-acetic acid and siderophore. The strain mobilized high concentration of heavy metals from soils and exhibited different biosorption capacity toward the tested metal ions. Strain SC2b was further assessed for PGP activity by phytagar assay with a model plant Brassica napus. Inoculation of SC2b increased the biomass and vigor index of B. napus. Considering such potential, a pot experiment was conducted to assess the effects of inoculating the metal-resistant PGPB SC2b on growth and uptake of Cd, Zn and Pb by S. plumbizincicola in metal-contaminated agricultural soils. Inoculation with SC2b elevated the shoot and root biomass and leaf chlorophyll content of S. plumbizincicola. Similarly, plants inoculated with SC2b demonstrated markedly higher Cd and Zn accumulation in the root and shoot system, indicating that SC2b enhanced Cd and Zn uptake by S. plumbizincicola through metal mobilization or plant-microbial mediated changes in chemical or biological soil properties. Data demonstrated that the PGPB Bacillus sp. SC2b might serve as a future biofertilizer and an effective metal mobilizing bioinoculant for rhizoremediation of metal polluted soils.

ABCC Subfamily Vacuolar Transporters are Involved in Pb (Lead) Detoxification in Saccharomyces cerevisiae

The present work has as objective to contribute for the elucidation of the mechanism associated with Pb detoxification, using the yeast Saccharomyces cerevisiae as a model organism. The deletion of GTT1 or GTT2 genes, coding for functional glutathione transferases (GST) enzymes in S. cerevisiae, caused an increased susceptibility to high Pb concentrations (500-1000 μmol L(-1)). These results suggest that the formation of glutathione-Pb conjugate (GS-Pb), dependent of GSTs, is important in Pb detoxification. The involvement of ATP-binding cassette (ABC) vacuolar transporters, belonging to class C subfamily (ABCC) in vacuolar compartmentalization of Pb, was evaluated. For this purpose, mutant strains disrupted in YCF1, VMR1, YBT1 or BPT 1 genes were used. All mutants tested, without vacuolar ABCC transporters, presented an increased sensitivity to 500-1000 μmol L(-1) Pb comparative to wild-type strain. Taken together, the obtained results suggest that Pb detoxification, by vacuolar compartmentalization, can occur as a result of the concerted action of GSTs and vacuolar ABCC transporters. Pb is conjugated with glutathione, catalysed by glutathione transferases and followed to the transport of GS-Pb conjugate to the vacuole by ABCC transporters.

Trace Elements in Ambient Air at Porto Metropolitan Area—Checking for Compliance with New European Union (Eu) Air Quality Standards

Because of the scientific evidence showing that arsenic (As), cadmium (Cd), and nickel (Ni) are human genotoxic carcinogens, the European Union (EU) recently set target values for metal concentration in ambient air (As: 6 ng/m3, Cd: 5 ng/m3, Ni: 20 ng/m3). The aim of our study was to determine the concentration levels of these trace elements in Porto Metropolitan Area (PMA) in order to assess whether compliance was occurring with these new EU air quality standards. Fine (PM2.5) and inhalable (PM10) air particles were collected from October 2011 to July 2012 at two different (urban and suburban) locations in PMA. Samples were analyzed for trace elements content by inductively coupled plasma–mass spectrometry (ICP-MS). The study focused on determination of differences in trace elements concentration between the two sites, and between PM2.5 and PM10, in order to gather information regarding emission sources. Except for chromium (Cr), the concentration of all trace elements was higher at the urban site. However, results for As, Cd, Ni, and lead (Pb) were well below the EU limit/target values (As: 1.49 ± 0.71 ng/m3; Cd: 1.67 ± 0.92 ng/m3; Ni: 3.43 ± 3.23 ng/m3; Pb: 17.1 ± 10.1 ng/m3) in the worst-case scenario. Arsenic, Cd, Ni, Pb, antimony (Sb), selenium (Se), vanadium (V), and zinc (Zn) were predominantly associated to PM2.5, indicating that anthropogenic sources such as industry and road traffic are the main source of these elements. High enrichment factors (EF > 100) were obtained for As, Cd, Pb, Sb, Se, and Zn, further confirming their anthropogenic origin.

Cadmium hyperaccumulation and genetic differentiation of Thlaspi caerulescens populations

Although the knowledge on heavy metal hyperaccumulation mechanisms is increasing, the genetic basis of cadmium (Cd) hyperaccurnulation remains to be elucidated. Thlaspi caerulescens is an attractive model since Cd accumulation polymorphism observed in this species suggests genetic differences between populations with low versus high Cd hyperaccumulation capacities. In our study, a methodology is proposed to analyse at a regional scale the genetic differentiation of T. caerulescens natural populations in relation to Cd hyperaccumulation capacity while controlling for different environmental, soil, plant parameters and geographic origins of populations. Twenty-two populations were characterised with AFLP markers and cpDNA polymorphism. Over all loci, a partial Mantel test showed no significant genetic structure with regard to the Cd hyperaccumulation capacity. Nevertheless, when comparing the marker variation to a neutral model, seven AFLP fragments (9% of markers) were identified as presenting particularly high genetic differentiation between populations with low and high Cd hyperaccurnulation capacity. Using simulations, the number of outlier loci was showed to be significantly higher than expected at random. These loci presented a genetic structure linked to Cd hyperaccumulation capacity independently of the geography, environment, soil parameters and Zn, Pb, Fe and Cu concentrations in plants. Using a canonical correspondence analysis, we identified three of them as particularly related to the Cd hyperaccumutation capacity. This study demonstrates that populations with low and high hyperaccurnulation capacities can be significantly distinguished based on molecular data. Further investigations with candidate genes and mapped markers may allow identification and characterization of genomic regions linked to factors involved in Cd hyperaccumulation.

Mutations of the Serine Protease CAP1/Prss8 Lead to Reduced Embryonic Viability, Skin Defects, and Decreased ENaC Activity.

CAP1/Prss8 is a membrane-bound serine protease involved in the regulation of several different effectors, such as the epithelial sodium channel ENaC, the protease-activated receptor PAR2, the tight junction proteins, and the profilaggrin polypeptide. Recently, the V170D and the G54-P57 deletion mutations within the CAP1/Prss8 gene, identified in mouse frizzy (fr) and rat hairless (fr(CR)) animals, respectively, have been proposed to be responsible for their skin phenotypes. In the present study, we analyzed those mutations, revealing a change in the protein structure, a modification of the glycosylation state, and an overall reduction in the activation of ENaC of the two mutant proteins. In vivo analyses demonstrated that both fr and fr(CR) mutant animals present analogous reduction of embryonic viability, similar histologic aberrations at the level of the skin, and a significant decrease in the activity of ENaC in the distal colon compared with their control littermates. Hairless rats additionally had dehydration defects in skin and intestine and significant reduction in the body weight. In conclusion, we provided molecular and functional evidence that CAP1/Prss8 mutations are accountable for the defects in fr and fr(CR) animals, and we furthermore demonstrate a decreased function of the CAP1/Prss8 mutant proteins. Therefore, fr and fr(CR) animals are suitable models to investigate the consequences of CAP1/Prss8 action on its target proteins in the whole organism.

Calidad ambiental de las bahías Samanco y Tortuga, Áncash, Perú: 2010-2011

Se efectuaron estudios en junio y octubre-noviembre 2010 y en julio y noviembre-diciembre 2011. Se hicieron muestreos por mar para determinar parámetros físicos, químicos y microbiológicos, empleando protocolos y metodologías nacionales e internacionales (USEPA, APHA). En Samanco el oxígeno disuelto varió entre 7,00 y 8,20 mg/L; en Tortuga de 6,46 a 7,42 mg/L. Los sólidos suspendidos totales en Samanco fueron 37,00 mg/L y en Tortuga 33,28 mg/L; aceites y grasa fueron >1,00 mg/L superando los Estándares Nacionales de Calidad Ambiental (ECA) categoría 4. Los valores de demanda bioquímica de oxígeno (DBO5) fueron <10,00 mg/L. Las concentraciones de cadmio (4,21 μg/g) y plomo (30,24 μg/g) en sedimento no sobrepasaron los valores de Protección Costera y Restauración (USA). Se detectó que la bahía Samanco presenta mayor grado de impacto ambiental que la bahía Tortuga.

Strategic supply lead time management. Case Nokia Networks, Hardware Services

Teollisuuden palveluiden on huomattu olevan potentiaalinen lisätulojen lähde. Teollisuuden palveluiden dynaamisessa maailmassa räätälöinti ja kyky toimia nopeasti ovat kriittisiä asiakastyytyväisyyden ja kilpailuedun luomisprosessin osia. Toimitusketjussa käytetyn ajan lyhentämisellä voidaan saavuttaa sekä paremmat vasteajat, että alhaisemmat kokonaiskustannukset. Tutkielman tavoitteena on kuvata teollisuuden palveluiden dynaamista ympäristöä: asiakastarvetta, sekä mahdollisuuksia kaventaa pyydetyn ja saavutetun toimitusajan välistä eroa. Tämä toteutetaan pääosin strategisen toimitusajan hallinnan keinoin. Langattomien tietoliikenneverkkojen operaattorit haluavat vähentää ydinosaamiseensa kuulumatomiin toimintoihin, kuten ylläpitoon sitoutuneita pääomia. Tutkielman case osiossa varaosapalvelujen toimitusketjun kysyntä-, materiaali- ja informaatiovirtoja analysoidaan niin kvalitatiivisten haastatteluiden, sisäisten dokumenttien, kuin kvantitatiivisten tilastollisten menetelmienkin avulla. Löydöksiä peilataan vallitsevaa toimitusketjun ja ajanhallinnan paradigmaa vasten. Tulokset osoittavat, että vahvan palvelukulttuurin omaksuminen ja kokonaisvaltainen toimitusketjun tehokkuuden mittaaminen ovat ajanhallinnan lähtökohtia teollisuuden palveluissa.

Flow injection analysis (FIA) determination of lead by hydride generation in banded coral skeletons /

A flow injection hydride generation direct current plasma atomic emission spectrometric (FI-HG-DCP-AES) method was developed for the determination of lead at ng.ml-l level. Potassium ferricyanide (K3Fe(CN)6) was used along with sodium tetrahydroborate(III) (NaBH4) to produce plumbane (PbH4) in an acid medium. The design of a gas-liquid separator (hydride generator) was tested and the parameters of the flow injection system were optimized to achieve a good detection limit and sample throughput. The technique developed gave a detection limit of 0.7 ng.ml-l(3ob). The precision at 20 ng.ml"* level was 1.6 % RSD with 1 1 measurements (n=l 1). Volume of sample loop was 500 |J.l. A sample throughput of 120 h"^ was achieved. The transition elements, Fe(II), FeOH), Cd(n), Co(II), Mn(n), Ni(II) and Zn(n) do not interfere in this method but 1 mg,l'l Cu(II) will suppress 50 % of the signal from a sample containing 20 ng.ml'l Pb. This method was successfully applied to determine lead in a calcium carbonate (CaC03) matrix of banded coral skeletons from Si-Chang Island in Thailand.

Arsenic and germanium determination by hydride generation in the D.C. plasma optical emission spectrometer

Modifications to the commercial hydride generator, manufactured by Spectrametrics, resulted in improved operating procedure and enhancement of the arsenic and germanium signals. Experiments with arsenic(III) and arsenic(V) showed that identical reiults could be produced from both oxidation states. However, since arsenic(V) is reduced more slowly than arsenic(III), peak areas and not peak heights must be measured when the arsine is immediately stripped from the system (approximately 5 seconds reaction). When the reduction is allowed to proceed for 20 seconds before the arsine is stripped, peak heights may be used. For a 200 ng/mL solution, the relative standard deviation is 2.8% for As(III) and 3.8% for As(V). The detection limit for arsenic using the modified system is 0.50 ng/mL. Studies performed on As(V) standards show that the interferences from 1000 mg/L of nickel(II), cobalt(II), iron(III), copper(II), cadmium(II), and zinc(II) can be eliminated with the aid of 5 M Hel and 3% L-cystine. Conditions for the reduction of germanium to the corresponding hydride were investigated. The effect of different concentrations of HCl on the reduction of germanium to the covalent hydride in aqueous media by means of NaBH 4 solutions was assessed. Results show that the best response is accomplished at a pH of 1.7. The use of buffer solutions was similarly characterized. In both cases, results showed that the element is best reduced when the final pH of the solution after reaction is almost neutral. In addition, a more sensitive method, which includes the use of (NH4)2S208' has been developed. A 20% increase in the germanium signal is registered when compared to the signal achieved with Hel alone. Moreover, under these conditions, reduction of germanium could be accomplished, even when the solution's pH is neutral. For a 100 ng/mL germanium standard the rsd is 3%. The detection limit for germanium in 0.05 M Hel medium (pH 1.7) is 0.10 ng/mL and 0.09 ng/mL when ammonium persulphate is used in conjunction with Hel. Interferences from 1000 mg/L of iron(III), copper(II), cobalt(II), nickel(II), cadmium(II), lead(II), mercury(II), aluminum(III), tin(IV), arsenic(III), arsenic(V) and zinc(II) were studied and characterized. In this regard, the use of (NH4)ZS20S and Hel at a pH of 1.7 proved to be a successful mixture in the sbppression of the interferences caused by iron, copper, aluminum, tin, lead, and arsenic. The method was applied to the determination of germanium in cherts and iron ores. In addition, experiments with tin(IV) showed that a 15% increase in the tin signal can be accomplished in the presence of 1 mL of (NH4)2S20S 10% (m/V).

NMR studies of strong hydrogen bond to fluoride ion

Systems such as MF/diol (M = alkali metal) and }1F/carboxylic acid were subjected to IH, I9F and 13C nmr study to investigate the nature of the very strong H-bonding of fluoride ions with these systems. Evidence indicates a strong H-bond in diol-fluoride systems (~H ~ -(56) kJ mol-I) which is stronger than most 'typical' H-bonds (~H = -(12-40) kJ mol-I), but weaker than that reported for carboxylic acid-fluoride systems (~H ~ -(120) kJ mol-I). Approximate fluoride H-bonded shifts (o(OH)OHF) were evaluated for MF/diol systems from IH chemical shift measurements. No direct correlation was observed between I9F chemical shift and H-bond strength. Thermodynamic parameters were calculated from temperature dependent IH and 19F shifts. Preliminary studies of BUn 4NF-acetylacetone by I9F nmr were conducted at low temperatures and a possible Jmax (ca. 400 Hz) is reported for the fluoride ion H-bonded to acetylacetone. Highfield shift for non-protonated carbons and downfield shift for protonated carbons were observed in carboxylic acid/KF systems. Significant decreas$in I3C TI due to strong H-bonding to fluoride ions were also detected in both diol and carboxylic acid systems. Anomalous results were obtained, such as increasing NOE with increasing temperature in neat 1,2-ethanediol (values above the theoretical maximum of 1.988) and in 1,2-ethanediol/KF. The large 13C NOE's for carboxy carbons in neat carboxylic acids which are. further enhanced by the addition of KF are also unusual.

Synthesis of nanoporous materials for preconcentration and determination of trace elements by ICP-AES ; Investigation and elimination of the memory effects of mercury, gold, silver and boron in ICP-AES

Nanoporous materials with large surface area and well-ordered pore structure have been synthesized. Thiol groups were grafted on the materials' surface to make heavy metal ion pre-concentration media. The adsorption properties ofthe materials were explored. Mercury, gold and silver can be strongly adsorbed by these materials, even in the presence of alkaline earth metal ion. Though the materials can adsorb other heavy metal ions such as lead and copper, they show differential adsorption ability when several ions are present in solution. The adsorption sequence is: mercury> == silver> copper » lead and cadmium. In the second part of this work, the memory effects of mercury, gold, silver and boron were investigated. The addition of 2% L-cysteine and 1% thiourea eliminates the problems of the three metal ions completely. The wash-out time for mercury dropped from more than 20 minutes to 18 seconds, and the wash-out time for gold decreased from more than 30 minutes to 49 seconds. The memory effect of boron can be reduced by the use of mannitol.