Humic acids in bottom sediments of the Western Pacific

Elemental composition, functional groups, and molecular mass distribution were determined in humic acids from the Western Pacific abyssal and coastal bottom sediments. Humic acid structure was studied by oxidative degradation with alkaline nitrobenzene and potassium permanganate, p-coumaric, guaiacilic, and syringilic structural units typical for lignin of terrestrial plants were identified in humic acids by chromatographic analysis of oxidation products. Polysubstituted and polycondensed aromatic systems with minor proportion of aliphatic structures were basic structural units of humic acids in abyssal sediments.

Control of nutrient solutions for studies at high pH

Little is known about factors effecting plant growth at high pH, with research often limited by the inability to separate nutritional deficiencies and HCO3- toxicity from the direct limitations imposed under high pH conditions. Various methods of controlling dilute nutrient solutions for studies at high pH were investigated. For short-term studies, it was found that a solution without Cu, Fe, Mn and Zn and aerated with CO2 depleted air, greatly reduced nutrient precipitation at high pH, thus eliminating nutritional differences between treatments. Manual pH adjustment and the use of ion exchange resins as pH buffers were unsuitable methods of pH control. However, pH control by automated titration had little effect on solution composition while maintaining constant pH. The system described is suitable for studies in which the pH of the bulk nutrient solution must be maintained. The system was used to examine OH- toxicity in mungbeans (Vigna radiata (L.) Wilczek cv. Emerald), with root length reduced at a bulk solution pH of 8.5 and greater.

Rhizotoxicity of aluminate and polycationic aluminium at high pH

Although monomeric Al species are often toxic in acidic soils, the effects of the aluminate ion (Al(OH)4-) on roots grown in alkaline media are still unclear. Dilute, alkaline (pH 9.5) nutrient solutions were used to investigate the effects of Al(OH)4- on root growth of mungbean (Vigna radiata L.). Root growth was reduced by 13 % after 3 d growth in solutions with an Al(OH)4- activity of 16 μM and no detectable polycationic Al (Al13). This decrease in root growth was associated with the formation of lesions on the root tips (due to the rupturing of the epidermal and outer cortical cells) and a slight limitation to root hair growth (particularly on the lateral roots). When roots displaying these symptoms were transferred to fresh Al(OH)4- solutions for a further 12 h, no root tip lesions were observed and root hair growth on the lateral roots improved. The symptoms were similar to those induced by Al13 at concentrations as low as 0.50 μM Al which are below the detection limit of the ferron method. Thus, Al(OH)4- is considered to be non-toxic, with the observed reduction in root growth in solutions containing Al(OH)4- due to the gradual formation of toxic Al13 in the bulk nutrient solution resulting from the acidification of the alkaline nutrient solution by the plant roots.

Efeito da adição de uréia e sulfato de amônio sobre o pH e nitrificação em um solo ácido

A variação do pH e a produção de nitrato foram estudados em um Latossolo Vermelho Escuro, Série Guamium, em função da adição de 200 e 400 ppm de N nas formas de uréia e sulfato de amônio, em presença e ausência de Ca(OH)2 por um período de 30 dias. Os resultados obtidos mostraram que o pH decresceu com o sulfato de amônio e aumentou com a uréia. As variações foram observadas mesmo empresença de Ca(0H)2. A produção de nitrato aumentou com o pH, considerando o mesmo nível e fonte de nitrogênio. Não foi observado no conjunto uma relação entre pH e produção de nitrato.

Efeito do pH na adsorção-dessorção de chumbo em Latossolos brasileiros

Reações de adsorção-dessorção de chumbo em solos são influenciadas por atributos de superfície dos colóides dos solos e pela composição da solução do meio. Este estudo avaliou o efeito do pH sobre a adsorção-dessorção de chumbo em Latossolos brasileiros. Amostras do horizonte A de cada solo, suspensas em Ca(NO3)2 5 mmol L-1, foram tituladas com HNO3 7 mmol L-1 ou solução saturada de Ca(OH)2, para que fosse atingido o valor de pH estipulado em cada experimento (4,5, 5,5 e 6,5). Atingido o pH de equilíbrio, as amostras foram equilibradas com Pb(NO3)2, com vistas em obter uma concentração final de 0,15 mmol L-1 (relação solo:solução 1:100; força iônica 15 mmol L-1), por um período de 72 h. A dessorção foi realizada em Ca(NO3)2 5 mmol L-1, pH 5,5. O aumento do pH de 4,5 para 6,5 causou aumento da adsorção de até 16,7 vezes, um aumento médio de 2,9 vezes de pH 4,5 para 5,5; 1,4 vez de pH 5,5 para 6,5 e 4,2 vezes de pH 4,5 para 6,5. A relação Pb adsorvido/Pb adicionado foi, em média, de 0,33 para pH 4,5; 0,75 para pH 5,5 e 0,94 para pH 6,5. A fração média de Pb dessorvido (Pb dessorvido/Pb adsorvido) decresceu de 0,36 a pH 4,5, para < 0,06 a pH 6,5. O efeito dos atributos do solo sobre a adsorção-dessorção de chumbo decresceu quando o pH aumentou, evidenciado por uma maior diferenciação na quantidade adsorvida pelos solos em valores mais baixos de pH. A adsorção de Pb foi positivamente correlacionada (e geralmente a fração dessorvida foi negativamente correlacionada) com área superficial específica, CTC a pH 7,0, teores de caulinita, hematita, Fe2O3 extraídos pelo ditionito-citrato-bicarbonato de sódio e oxalato ácido de amônio e SiO2 e Fe2O3 extraídos pelo ataque sulfúrico. O fato de considerável fração de chumbo permanecer adsorvida em pH 4,5 mostra a reduzida disponibilidade deste metal em Latossolos, mesmo em baixos valores de pH.

Doses de gesso em cafeeiro: influência nos teores de cálcio, magnésio, potássio e ph na solução de um latossolo vermelho distrófico

O desbalanço entre Ca2+, Mg2+ e K+ no solo como consequência das aplicações elevadas de gesso deve-se às relações de tamanho (raio iônico) e densidades de cargas (relação carga/raio) de cada espécie iônica. Quanto maior a densidade de carga, mais intensa será a ligação iônica do cátion com íons de cargas opostas como OH- e SO4-2. Dessa maneira, o uso excessivo de gesso agrícola, sem considerar o balanço de cargas das partículas do solo; o equilíbrio iônico; e a CTC podem resultar em expressiva lixiviação ao longo do perfil do solo. O objetivo deste estudo foi avaliar o efeito de elevadas doses de gesso (0, 7 e 56 t ha-1) nos teores de Ca2+, Mg2+, K+ e pH na solução de um Latossolo Vermelho distrófico cultivado com cafeeiro, obtida pelo método adaptado do extrato aquoso. O solo foi amostrado nas profundidades de 0,15-0,25; 0,35-0,45; 0,75-0,85; 1,15-1,25 e 2,35-2,45 m na linha de plantio, em quatro tratamentos: G-0 - gesso no preparo (aplicação ocorreu em setembro de 2008, distribuído a lanço, na quantidade de 2 t ha-1) e sem gesso na linha de plantio; G-7 - gesso adicionado durante a preparação do solo (2 t ha-1), na mesma condição do G-0 e 7,0 t ha-1 de gesso na linha de plantio; G-56 - gesso adicionado durante a preparação do solo (2 t ha-1), na mesma condição do G-0 e 56 t ha-1 de gesso na linha de plantio (nessas parcelas experimentais as entrelinhas de plantio foram cobertas com braquiária); e CV-7: ausência de braquiária na entrelinha, com gesso no preparo e 7 t ha-1 de gesso na linha, com três repetições distribuídas em blocos ao acaso, totalizando 60 amostras. Após 16 meses da adição de gesso, observou-se redução do pH na solução do solo nas profundidades de 0,15-0,25; 0,35-0,45 e 0,75-0,85 m. A aplicação de gesso agrícola foi eficiente na melhoria do ambiente radicular no subsolo, aumentou a concentração de Mg2+ e Ca2+ na solução do solo, mas reduziu o K+ em profundidade, a partir de 0,85 m. Os teores de Ca2+ e Mg2+ trocáveis na solução do solo estiveram acima do nível crítico; entretanto, os teores de K+ trocável se mantiveram na faixa do valor crítico, indicado para o desenvolvimento da cultura.

Synthèse de brosses de polyélectrolytes par polymérisation initiée depuis une surface de mica et étude de leur réponse en fonction du pH et de la force ionique

Cette thèse rapporte le greffage chimique de brosses de polymères neutres de poly(acrylate de tert-butyle) (PtBA) et de brosses chargées d’acide polyacrylique (PAA) sur des substrats de mica afin d’étudier leur conformation en fonction de la densité de greffage, du pH et de la force ionique. Le greffage est réalisé par polymérisation contrôlée par transfert d’atome (ATRP) initiée depuis la surface de mica afin de contrôler la croissance du polymère et sa densité de greffage. L’étude de la conformation des brosses de PtBA et de PAA a été menée avec la technique AFM en mesurant les épaisseurs des films à sec et gonflés sous différentes conditions de solvant, de pH et de force ionique. Une monocouche d’amorceurs est tout d’abord greffée sur du mica porteur de groupes hydroxyles créés par plasma (Ar/H2O). Cette couche a été caractérisée par des mesures d’angle de contact et par la technique TOF-SIMS. L’amorceur greffé a ensuite permis d’initier l’ATRP directement depuis la surface pour former des brosses neutres de PtBA liés de façon covalente au mica. La croissance linéaire de l’épaisseur du film avec la masse molaire du polymère en solution et le taux de conversion montre que la polymérisation est contrôlée. De plus, la ré-initiation des chaînes greffées atteste du caractère vivant de la polymérisation. L’hydrolyse des brosses de PtBA, confirmée par des mesures d’angle de contact, d’épaisseur et par FT-IR, conduit à des brosses de PAA. Les différentes couches greffées sont stables à l’air, en milieu organique et en milieu aqueux et leur gonflement est réversible. Le degreffage de la couche de PAA est observé suite à une longue exposition à pH basique. Cette étude représente le premier exemple de brosses greffées chimiquement sur du mica par polymérisation initiée depuis la surface. La variation des paramètres de la réaction de greffage de l’amorceur, tels que la concentration et la durée de réaction, a permis de contrôler le taux de recouvrement de l’amorceur et la densité de greffage du polymère. Une grande gamme de taux de recouvrement de l’amorceur est accessible et se traduit par un intervalle de densités de greffage allant de faibles à élevées (e.g. 0,04 chaîne/nm2 à 0,5 chaîne/nm2). L’étude de la conformation des chaînes de PtBA dans le DMF montre que cet intervalle de densités recouvre le régime crêpe au régime brosse. Le gonflement de brosses de PAA et la variation de la hauteur de la brosse L ont été étudiés en fonction de la densité de greffage, du pH et du sel ajouté cs (NaCl). Une transition brusque de collapsée à étirée est observée avec l’augmentation du pH, indépendamment de la densité de greffage. A pH neutre, les brosses sont collapsées et se comportent comme des brosses neutres en mauvais solvant. A pH basique, les brosses sont gonflées et chargées et se trouvent dans un régime de Pincus caractéristique des polyélectrolytes forts. En présence de sel, les charges sont partiellement écrantées et les répulsions électrostatiques dominent toujours dans la brosse. Cette étude contribue à une meilleure compréhension du comportement complexe des brosses de polyélectrolytes faibles et apporte un soutien expérimental à la théorie sur le comportement de ces brosses.

Effect of pH on the development of acidic sites in clayey and sandy loam Oxisol from the Cerrado Region, Brazil

Titration curves were determined for soil from horizon samples of a clayey and a sandy loam Oxisol by (a) adding NaOH to soil suspensions and (b) incubating moist soils with Ca(OH)(2). The organic fraction was primarily responsible for buffering in both soils. Humic acids were more important than fulvic acids in buffering against NaOH additions. With Ca(OH)(2), greater buffer capacities were found due to carboxyl sites, primarily on fulvic acids, becoming complexed with Ca2+ so that in the clay soil humic and fulvic acids were equally important as buffering components while fulvic acids were more important in the sandy loam soil. The buffer capacity of organic matter against Ca(OH)(2) additions was 1.1 mol(c) kg(-1) pH(-1). In the incubated soils, exchangeable cations were also determined and changes in the amounts of exchangeable and non-exchangeable Ca2+ acidity and effective cation exchange capacity were calculated. Up to half the added Ca2+ became complexed and was nonexchangeable. Aluminum complexed by organic matter appears to be an important buffering component, together with non exchangeable H+. With the increase of pH the dissociated sites from the carboxyl groups could complex Ca2+. (c) 2005 Elsevier B.V. All rights reserved.

pH and calcium ion release evaluation of pure and calcium hydroxide-containing Epiphany for use in retrograde filling

Objective: Hydroxyl (OH(-)) and calcium (Ca(++)) ion release was evaluated in six materials: G1) Sealer 26, G2) White mineral trioxide aggregate (MTA), G3) Epiphany, G4) Epiphany + 10% calcium hydroxide (CH), G5) Epiphany + 20% CH, and G6) zinc oxide and eugenol. Material and Methods: Specimens were placed in polyethylene tubes and immersed in distilled water. After 3, 6, 12, 24, and 48 h, 7, 14, and 28 days, the water was assessed for pH with a pH meter and for Ca++ release by atomic absorption spectrophotometry. Results: G1, G2, G4, and G5 had the highest pH until 14 days (p < 0.05). G1 presented the highest Ca(++) release until 6 h, and G4 and G5, from 12 h through 14 days. Ca(++) release was greater for G1 and G2 at 28 days. G6 released the least Ca(++). Conclusions: MTA, Sealer 26, Epiphany, and Epiphany + CH release OH-and Ca(++) ions. Epiphany + CH may be an alternative as retrofilling material.

Análise do MTA e do Ca(OH)2 no interior dos tecidos após o processo de reabsorção radicular externa em reimplante dentário tardio

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

New method to assess the pozzolanic reactivity of mineral admixtures by means of pH and electrical conductivity measurements in lime:pozzolan suspensions

A very simple method based on electrical conductivity and pH measurements was proposed for assessing reactivity of pozzolans. Calcium hydroxide: pozzolan water suspensions were monitored by means of measurements of electrical conductivity and pH values. In these suspensions, Ca(OH)(2) in solid state was initially present, being them, thus, saturated in this reagent. Three testing temperatures were selected (40, 50 and 60 degrees C). In the experiments carried out, calcium hydroxide was suspended in deionized water for yielding a lime saturated suspension. The addition of siliceous pozzolan (two types of rice husk ash RHA and two types of densified silica fume DSF were tested) to the saturated lime suspension can produce the unsaturation of the system, depending on the testing time, testing temperature and reactivity of pozzolan. When unsaturation was reached, the loss of electrical conductivity was higher than 30% and the variation of pH was higher than 0.15 units. These threshold values were selected for characterizing the reactivity of pozzolans by means of a proposed template, classifying the pozzolan in three different reactivity levels.

Characterization of aluminum hydroxide (Al(OH)(3)) for use as a porogenic agent in castable ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photoelectrochemical reduction of CO2 on Cu/Cu2O films: Product distribution and pH effects

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development and characterization of fluorescent pH sensors based on porous silica and hydrogel support matrices

The hydrogen ion activity (pH) is a very important parameter in environment monitoring, biomedical research and other applications. Optical pH sensors have several advantages over traditional potentiometric pH measurement, such as high sensitivity, no need of constant calibration, easy for miniaturization and possibility for remote sensing. Several pH indicators has been successfully immobilized in three different solid porous materials to use as pH sensing probes. The fluorescent pH indicator fluorescein-5-isothiocyanate (FITC) was covalently bound onto the internal surface of porous silica (pore size ~10 nm) and retained its pH sensitivity. The excited state pK* a of FITC in porous silica (5.58) was slightly smaller than in solution (5.68) due to the free silanol groups (Si-OH) on the silica surface. The pH sensitive range for this probe is pH 4.5 - 7.0 with an error less than 0.1 pH units. The probe response was reproducible and stable for at least four month, stored in DI water, but exhibit a long equilibrium of up to 100 minutes. Sol-gel based pH sensors were developed with immobilization of two fluorescent pH indicators fluorescein-5-(and-6)-sulfonic acid, trisodium salt (FS) and 8-hydroxypyrene- 1,3,6-trisulfonic acid (HPTS) through physical entrapment. Prior to immobilization, the indicators were ion-paired with a common surfactant hexadecyltrimethylammonium bromide (CTAB) in order to prevent leaching. The sol-gel films were synthesized through the hydrolysis of two different precursors, ethyltriethoxysilane (ETEOS) and 3- glycidoxypropyltrimethoxysilane (GPTMS) and deposited on a quartz slide through spin coating. The pK a of the indicators immobilized in sol-gel films was much smaller than in solutions due to silanol groups on the inner surface of the sol-gel films and ammonium groups from the surrounding surfactants. Unlike in solution, the apparent pK a of the indicators in sol-gel films increased with increasing ionic strength. The equilibrium time for these sensors was within 5 minutes (with film thickness of ~470 nm). Polyethylene glycol (PEG) hydrogel was of interest for optical pH sensor development because it is highly proton permeable, transparent and easy to synthesize. pH indicators can be immobilized in hydrogel through physical entrapment and copolymerization. FS and HPTS ion-pairs were physically entrapped in hydrogel matrix synthesized via free radical initiation. For covalent immobilization, three indicators, 6,8-dihydroxypyrene-1,3- disulfonic acid (DHPDS), 2,7-dihydroxynaphthalene-3,6-disulfonic acid (DHNDS) and cresol red were first reacted with methacrylic anhydride (MA) to form methacryloylanalogs for copolymerization. These hydrogels were synthesized in aqueous solution with a redox initiation system. The thickness of the hydrogel film is controlled as ~ 0.5 cm and the porosity can be adjusted with the percentage of polyethylene glycol in the precursor solutions. The pK a of the indicators immobilized in the hydrogel both physically and covalently were higher than in solution due to the medium effect. The sensors are stable and reproducible with a short equilibrium time (less than 4 minutes). In addition, the color change of cresol red immobilized hydrogel is vivid from yellow (acidic condition) to purple (basic condition). Due to covalently binding, cresol red was not leaching out from the hydrogel, making it a good candidate of reusable "pH paper".

Biogenic and environmental fluctuations of temperature and pH in a novel mesocosm concept ("Kiel Outdoor Benthocosms") April 2013 to September 2014

The Kiel Outdoor Benthocosm infrastructure (Kiel, Germany,N 54°19.8'; E 010°09.0') allows combining natural in-situ fluctuations on all environmental variables with the controlled manipulation of treatment factors. The environmental fluctuations are admitted by a continuous flow-through of fjord water. The treatment is applied by delta-treatments which shift the mean of target variables (temperature and pH in this case) while maintaining the frequency and amplitude of natural fluctuations. The data presented here show the treatment levels and the continuously logged temperature and pH conditions in the experimental tanks. The dynamics of temperature and pH are driven by (i) in situ variability, (ii) the treatments imposed and (iii) the biology of the biota in the tanks. These contained macroalgal communities with associated mesograzers, mussels, and sea stars. The data set comprised 5 experimental runs: spring experiment (4.4.-19.6.2013), summer experiment 1 (4.7.-17.9.2013), autumn experiment (10.10-17.12.2013), winter experiment (16.1. - 1.4.2014), summer experiment 2 (10.7. - 26.9.2014).