Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < PH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbOx (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at PH 2.2 and potential of +2.4 V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 K PH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1 h of electrolysis the results indicated total color removal and 37% of mineralization. (c) 2004 Elsevier Ltd. All rights reserved.

Degradation of the herbicide tebuthiuron using solar photo-Fenton process and ferric citrate complex at circumneutral pH

The influence of pH on the degradation of the herbicide tebuthiuron (TBH) was investigated using in situ generated Fe(III)-citrate complexes (Fe:cit) submitted to the photo-Fenton process under solar irradiation. Using Fe:cit in a wide pH range (2.5-7.5), 100-78% TBH oxidation was achieved respectively from a UV dose of 2.0 J cm(-2) (15 min). Moreover, the oxidation of TBH obtained in the presence of Fe:cit at pH 6.0 was higher than that obtained using Fe(NO3)3 at pH 2.5. A similar behavior is observed for the removal of total organic carbon (TOC) in TBH solutions. In the presence of Fe:cit, 20% and 85% of TOC was removed at pH 7.5 and 2.5, respectively, after 7.5 J cm-2 irradiation, while no mineralization was observed employing Fe(NO3)(3) for the same UV dose. Using Fe(NO3)(3), mineralization was observed only after 11 J cm-2 (8%). A higher mineralization rate was obtained with Fe(NO3)(3) only when a concentration three times higher was employed at pH 2.5. Besides the high efficiency of TBH degradation observed using the ferric citrate complex in the solar photo-Fenton process, it also offers the advantage of application at a pH of up to 7.5. (c) 2007 Elsevier B.V. All rights reserved.

Evaluation of the influences of solution path length and additives concentrations on the solar photo-Fenton degradation of 4-chlorophenol using multivariate analysis

This study reports the photodegradation of 4-chlorophenol (4-CP) in aqueous solution by the photo-Fenton process using solar irradiation. The influence of solution path length, and Fe(NO3)(3) and H2O2 concentrations on the degradation of 4-CP is evaluated by response surface methodology. The degradation process was monitored by the removal of total organic carbon (TOC) and the release of chloride ion. The results showed a very important role of iron concentration either for TOC removal or dechlorination. on the other hand, a negative effect of increasing solution path length on mineralization was observed, which can be compensated by increasing the iron concentration. This permits an adjustment of the iron concentration according to the irradiation exposure area and path length (depth of a tank reactor). Under optimum conditions of 1.5 mM Fe(NO3)(3), 20.0 mM H2O2 and 4.5 cm solution path length, 17 min irradiation under solar light were sufficient to reduce a 72 mg C L-1 solution of 4-CP by 91 (c) 2006 Elsevier B.V. All rights reserved.

Treatment of 1,10-phenanthroline laboratory wastewater using the solar photo-Fenton process

The red Fe2+-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30 min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4500 mg L-1 total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150 min, in the presence of either FeOx or ferric nitrate. A ratio of 1: 10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120 min, while use of ferric nitrate resulted in only 6% mineralization over the same period. (c) 2007 Elsevier B.V. All rights reserved.

Leaching of nitrate and ammonium from cover crop straws as affected by rainfall

Nitrogen (N) mineralization dynamics in no-till systems is affected, among other factors, by N amount and quality in the mulch and by climatic conditions. Leaching of NO3-N and NH4-N from six plant species used as soil cover crops in tropical environments were evaluated when the straw was submitted to rainfall after chemical desiccation. Millet (Pennisetum glaucum), guinea sorghum (Sorghum vulgare), black oat (Avena strigosa), triticale (Triticum secale), Indian hemp (Crotalaria juncea), and brachiaria (Brachiaria decumbens) were grown in a greenhouse, in Botucatu-SP, Brazil. Forty-five days after emergence, the plants were cut at the root collar, oven-dried, and submitted to simulated rainfalls of 4.4, 8.7, 17.04, 34.9, and 69.8 mm, considering an amount of straw equivalent to 8 t ha(-1) of dry matter. The amounts of N-NO3- extracted from the straw by rainwater were very small. However, accumulated rainfall around 70 mm caused ammonium leaching ranging from 2.5 to 9.5kg ha(-1), depending on the species. Plant residues of triticale and black oat (grasses) and Indian hemp (legume) showed high N leaching intensity with the first rains after chemical desiccation. The amount of N leached from straw was highly correlated with N tissue content.

Influence of the iron source on the solar photo-Fenton degradation of different classes of organic compounds

In this work the influence of two different iron sources, Fe(NO3)(3) and complexed ferrioxalate (FeOx), on the degradation efficiency of 4-chlorophenol (4CP), malachite green, formaldehyde, dichloroacetic acid (DCA) and the commercial products of the herbicides diuron and tebuthiuron was studied. The oxidation of 4CP, DCA, diuron and tebuthiuron shows a strong dependence on the iron source. While the 4CP degradation is favored by the use of Fe(NO3)(3), the degradation of DCA and the herbicides diuron and tebuthiuron is most efficient when ferrioxalate is used. on the other hand, the degradation of malachite green and formaldehyde is not very influenced by the iron source showing only a slight improvement when ferrioxalate is used. In the case of formaldehyde, DCA, diuron and tebuthiuron, despite of the additional carbon introduced by the use of ferrioxalate, higher mineralization percentages were observed, confirming the beneficial effect of ferrioxalate on the degradation of these compounds. The degradation of tebuthiuron was studied in detail using a shallow pond type solar flow reactor of 4.5 L capacity and 4.5 cm solution depth. Solar irradiation of tebuthiuron at a flow rate of 9 L h(-1), in the presence of 10.0 mmol L-1 H2O2 and 1.0 mmol L-1 ferrioxalate resulted in complete conversion of this herbicide and 70% total organic carbon removal. (c) 2005 Elsevier Ltd. All rights reserved.

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondonia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondonia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Barbara deposit (Rondonia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sri (+/-W, +/-Ta, +/-Nb), and base-metal suite (Zn-Cu-Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0-19 wt.% NaCl eq.) CO2-bearing aqueous fluids homogenizing at 245-450 degreesC, and (2) aqueous solutions with low CO2, low to moderate salinity (0-14 wt.% NaCl eq.), which homogenize between 100 and 340 T. In the Santa Barbara deposit, the early inclusions are represented by (1) low-salinity (5-12 wt.% NaCl eq.) aqueous fluids with variable CO2 contents, homogenizing at 340 to 390 T, and (2) low-salinity (0-3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320380 degreesC. Cassiterite, wolframite, columbite-tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0-6 wt.% NaCl eq.) CO2-free aqueous solution, which homogenizes at (100-260 degreesC) and characterizes the sulfide fluorite-sericite association in the Correas deposit. The late fluid in the Santa Barbara deposit has lower salinity (0-3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240-450 degreesC, and 1,0-2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (delta(18)O quartz from 9.9parts per thousand to 10.9parts per thousand, deltaDH(2)O from 4.13parts per thousand to 6.95parts per thousand) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 degreesC. In the Santa Barbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 degreesC, respectively), and that for the cassiterite-quartz-veins is 415 degreesC. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (delta(18)O(qtz-H2O)=5.5-6.1parts per thousand) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (delta(18)O(mica-H2O)=33-9.8parts per thousand) suggest mixing with meteoric water. Late muscovite veins (delta(18)O(qtz-H2O)=-6.4parts per thousand) and late quartz (delta(18)O(mica-H2O)=-3.8parts per thousand) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor coluChange in the redox conditions related to mixing-of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit. (C) 2004 Elsevier B.V. All rights reserved.

Quantitative analysis of mineral content in enamel using synchrotron microtomography and microhardness analysis. - art. no. 631824

Synchrotron microtomography is a tool to quantify the mineralization of dental tissues as well as microhardness analysis, since they provide adequate precision and contrast sensitivity. This study evaluates synchrotron microtomography and microhardness analysis for quantifying the mineral content of bovine enamel. Fifty enamel blocks were submitted individually for 5 days to a pH-cycling model at 37 degrees C and remained in the remineralizing solution for 2 days. The blocks were treated twice daily for 1 min with NaF dentifrices (Placebo, 275, 550, 1,100 mu g F/g and Crest (R)) diluted in deionized water. Surface microhardness changes (%SMH) and mineral loss (Delta Z) were then calculated. Synchrotron microtomography was also used to measure total mineral lost (SMM). Pearson's correlation (p < 0.05) was used to determine the relationship between different methods of analysis and dose-response between treatments. Dentifrice fluoride concentration and %SMH and Delta Z were correlated (p < 0.05). There was a positive relationship (p < 0.05) when comparing SMM vs. Delta Z; a negative relationship (p < 0.05) was found for %SMH vs. SMM and %SMH vs. Delta Z. Based on the results of this study, it was possible to conclude that synchrotron microtomography provides the best spatial resolution and contrast sensitivity for quantifying mineral gradients.

Isotope geochemistry of the mafic dikes from the Vazante nonsulfide zinc deposit, Brazil

The Vazante Group, located in the northwestern part of Minas Gerais, hosts the most important zinc mine in Brazil, the Vazante Mine, which represents a major known example of a hypogene nonsulfide zinc deposit. The main zinc ore is represented by willemite and differs substantially from other deposits of the Vazante-Paracatu region, which are sulfide-dominated zinc-lead ore. The age of the Vazante Group and the hosted mineralization is disputable. Metamorphosed mafic dikes (metabasites) that cut the metasedimentary sequence and are affected by hydrothermal processes recently were found and may shed light on the geochronology of this important geological unit. Zircon crystals recovered from the metabasites are xenocrystic grains that yield U-Pb conventional ages ranging from 2.1 to 2.4 Ga, so the basement of the Vazante Group is Paleoproterozoic or has metasedinientary rocks whose source area was Paleoproterozoic. Pb isotopes determined for titanite separated from the metabasites have common, nonradiogenic Ph compositions, which prevents determination of their crystallization age. However, the Pb signatures observed for the titanite crystals are in agreement with those determined for galena from the carbonate-hosted Zn-Pb deposits hosted by the Vazante Group, including galena from minor sulfide ore bodies of the Vazante deposit. These similarities suggest that the metalliferous fluids that affected the metabasites may have been those responsible for galena formation, which could imply a similar lead source for both nonsulfide and sulfide zinc deposits in the Vazante-Paracatu district. This common source could be related to deep-seated, basin-derived, metalliferous fluids associated with a long-lived hydrothermal system related to diagenesis and deformation of the Vazante Group during the Neoproterozoic. (c) 2005 Elsevier Ltd. All rights reserved.

Degradation of metallophtalocyanine dye by combined processes of electrochemistry and photoelectrochemistry

Photoelectrocatalytic degradation of metallophtalocyanine reactive dye (turquoise blue 15) was performed using a Ti/TiO2 thin film photoanode prepared by sol-get method. Hundred percent of color removal and almost complete mineralization (95% at pH 2 and 85% at pH 8) where achieved after 6 h of photolectrocatalytic oxidation of 2.5 x 10(-5) mol L-1 AT15 dye in Na2SO4 mol L-1 under E = +1.2 V versus SCE. The method limitation occurs at dye concentration higher than 4 x 10-5 mol L-1, where the degradation rate becomes markedly slower. An important improvement in color removal and TOC reduction for 1 x 10(-3) mol L-1 metallophtalocyanine dye was achieved using a combined process. After 4 h of potential controlled electrolysis at -1.2 V on a cathode of platinum followed by 6 h of photoelectrocatalytic oxidation leads to 100% of color removal and 83% of TOC decay and eletrodeposition of 69% of the released copper originally presented as copperphtalocyanine complex, by electrodeposition on the cathode without any other treatment. (C) 2005 Elsevier Ltd. All rights reserved.

Groundwater geochemical evolution in the northern portion of the Guarani Aquifer System (Brazil) and its relationship to diagenetic features

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Atividade microbiana em solos, influenciada por resíduos de algodão e torta de mamona

Microbial activity constitutes a good indicator of soil quality, and is influenced by the addition of carbon in the system serving as a substrate for microorganisms that increase their activity and release of CO2, comprising the edaphic respiration of the soil. The objective of this study was to evaluate the microbial activity in different soil types with the addition of cake press of castor bean and cotton textile residue. The study was conducted in a greenhouse at the headquarters of Empresa Brasileira de Pesquisa Agropecuária (EMBRAPA) Cotton in randomized block design in 4 x 3 factorial arrangement with four replications. At predetermined intervals of 4 days, the containers were opened and the solution of NaOH titrated with HCl 2N in the presence of acid/base indicator phenolphthalein. After reading, the same amount of NaOH was added and the containers were closed again. The difference between the amounts of acid needed to neutralize the sodium hydroxide in a control container and the treatments was equivalent to the amount of carbon dioxide produced by soil microorganisms. It was found that the residues influenced the microbial activity in different soil types, especially in the initial determinations, presenting themselves as good sources for mineralization and nutrient supply, the castor bean proportionating higher cumulative release of CO2 by microorganisms.

Efeito da aplicação de água residuária de suinocultura no solo e na qualidade dos seus lixiviados

This study evaluates the behavior of swine effluent for their effects on soil and the quality of the leachate. In the incubation of soil with effluent were used 48 units in total with experimental application rates of 0, 50, 100 and 150 m(3). ha(-1). The soil pH and leached after the application of different rates remained acid and the values of ammonia in the argisols (Pax; Ultisol) showed minor values than in the witness soil while at the nitosols the values increased due to the application rates. The cation exchange capacity increased with greater intensity in argisols. The carbon/nitrogen relation was low showing a rapid mineralization of organic waste. The values of nitrate in leachate and the first of the phosphorus nitosol were higher than in the argisols, depending on the rate of application.

Gold-bearing iron duricrust in Central Brazil

In the Cuiabá region-State of Mato Grosso, Central Brazil-primary gold mineralization is hosted by two generations of quartz veins in Precambrian metamorphic terrains of the Cuiabá Group. Gold is mined from the veins and mainly from the eluvial horizons that cover the deeply altered basement. In the lodes gold occurs as small particles (less than 1 mm) associated with pyrite and contains up to 5% Ag. Larger particles and nuggets of almost pure gold are found in the iron duricrust which caps the upper levels of the weathering profile. It is difficult to determine the average grade of this kind of deposit but some prospects in the Cuiabá region produce up to 2 g gold per ton of ore. Lateritization is responsible for both the formation of the iron crust and the concentration of gold within the regolith. Under a tropical climate, the supergene alteration of phyllites of the Cuiabá Group has led to the formation of a weathering profile consisting typically of saprolite, mottled clay zone and duricrust, from bottom to top. The duricrust is directly derived form the in situ weathering of phyllites. Geochemical balance calculations indicate that in the transition from the saprolite to the duricrust lateritization has promoted a progressive loss of Si, Al and K, and more than 500% of absolute Fe enrichment. Gold underwent a supergene evolution related to the development of the weathering profile. In the saprolite and mottled clay zone, associated with quartz and oxidized sulfides, gold dissolves as demonstrated by corrosion features at the surface of the particles. The formation of secondary gold in the duricrust is indicated by the larger size of the nuggets, their higher fineness and the close relationship between gold and the neoformed iron oxy-hydroxides. © 1991.