X-ray fluorescence determination of adsorbed copper on activated charcoal after glycerin complexation

X-This work shows an alternative method to copper determination by X-Ray Fluorescence (XRF). Since copper concentration in natural waters is not enough to reach XRF detection limit, a liquid-solid preconcentration procedure was proposed. Glycerin was used to complex the metal increasing its adsorption on activated charcoal. The solid phase was used to XRF determination. Several parameters were evaluated, such as, the complexation pH, the charcoal adsorption limit and the glycerin concentration. The interferences are lead and bismuth and the sensitivities decreased in the order Cu2+, Bi3+ and Pb2+. The advantages of the method are its simplicity, low cost and low spectral interference.

Influence of the synthesis conditions on the characteristics and metal adsorption properties of the 3-(1,4-phenylenediamine)propylsilica xerogel

The hybrid 3-(1,4-phenylenediamine)propylsilica xerogel was obtained starting from two different organic precursor quantity (5 and 8 mmol) to 22 mmol of TEOS, in the synthesis. The xerogel samples were characterized by using CHN elemental analysis, N2 adsorption-desorption isotherms, infrared thermal analysis. The xerogel was used as metal sorbent for Cu2+, Cd2+ and Pb2+ in aqueous solution with concentration range of 10-3 to 10-5 mmol l-1. The quantity of organic precursor added in the synthesis influences the characteristics of the xerogel as morphology and thermal stability, as well as the metal adsorption capacity.

Extractives and energetic properties of wood and charcoal

Charcoal production stands out as a raw material for the production of renewable energy. To assess wood quality in energy terms, studies have focused more on the holocellulose and lignin content than on the role of extractives. The objective of this study was to evaluate the relationship between the extractive content in cold water, in dichloromethane and total on energy properties of wood and charcoal, from six trees species. The extractives were removed with different solvents to be recorded and gross calorific value of wood was determined. The wood was carbonized at 1.67°C/min heating rate until maximum of 450°C and residence time of 30 min. The extractive content was correlated with the gravimetric yield, apparent relative density, ash, volatile matter, fixed carbon and gross calorific value of charcoal. The removal of total extractives and extractives soluble in dichloromethane reduced the gross calorific value of wood of most species evaluated. The extractives removed in cold water did not correlate with the parameters of carbonization. The extractives content in dichloromethane correlated with volatile matter, fixed carbon and gross calorific value. Total extractive content correlated with gravimetric yield, apparent relative density and gross calorific value of charcoal.

Atrazine and picloram adsorption in organic horizon forest samples under laboratory conditions

Adsorption of two herbicides, atrazine and picloram, displaying different sorption characteristics, were evaluated for O (organic) horizon samples collected from SMZs (streamside management zones) in Piedmont (Ultisol) of Georgia, USA. Samples were randomly collected from within 5 SMZs selected for a study of surface flow in field trials. The five SMZs represented five different slope classes, 2, 5, 10, 15 and 20%. Results indicate that 0 horizons have the potential for sorbing atrazine from surface water moving through forested SMZs. Atrazine adsorption was nearly linear over a 24-hour period. Equilibrium adsorption, determined through 24-hour laboratory tests, resulted in a Freundlich coefficient of 67.5 for atrazine. For picloram, negative adsorption was observed in laboratory experiments. This seemed to be due to interference with ELISA analyses; however, this was not confirmed. The adsorption coefficient (Kd) obtained for atrazine in 0 horizons was greater than it would have been expected for mineral soil (from 1 to 4). Picloram was not sorbed in 0 horizons at any significant degree. Although there is a significant potential for the direct adsorption of soluble forms of herbicides in SMZs, the actual value of this adsorption for protecting water is likely to be limited even for relatively strongly sorbed chemicals, such as atrazine, due to relatively slow uptake kinetics.

Organic acid adsorption and mineralization in oxisols with different textures

Organic acids play an important role in the nutritional conditions of plants. Their relevance is related to their formation dynamics, mineralization rate and adsorption by soil colloids. This study was carried out to evaluate the dynamics of mineralization and adsorption of organic acid (acetic acid - AA, citric acid - CA and humic acid - HA) applied to the soil. Samples of two Oxisols were used: Rhodic Haplustox (LV) and Typic Haplustox (LVA). The mineralization experiment was arranged in a 2 x 3 x 5 factorial design, based on the factors: two soils (LV and LVA) x three organic acid (OA) types (AA, CA and HA) x five OA rates (0, 1, 2, 4, and 8 mmol dm-3). Organic carbon mineralization in samples was measured by the C-CO2 efflux, produced by the microbial activity, in a 30-day (measurements after 4, 8, 12, 21, and 30 days) and in a 4-day experiment (measured after 24, 48, 72 and 96 h). Organic acid adsorption was tested in a 2 x 2 x 5 x 4 factorial design, with the factors and levels: two Oxisols; two organic acids (AA and CA); five OA rates (0, 1, 2, 4, and 8 mmol dm-3) and four adsorption periods (6, 24, 48, and 72 h). The C-CO2 production of soil treated with CA was highest. In the adsorption experiment, the affinity of CA to soil adsorption sites was greatest. The adsorption of organic acids to soils may be an important mechanism by which bioavailability and thus mineralization capacity by microbial activity are reduced.

Adsorption of glyphosate in chilean soils and its relationship with unoccupied phosphate binding sites

The objective of this work was to investigate glyphosate adsorption by soils and its relationship with unoccupied binding sites for phosphate adsorption. Soil samples of three Chilean soils series - Valdivia (Andisol), Clarillo (Inceptisol) and Chicureo (Vertisol) - were incubated with different herbicide concentrations. Glyphosate remaining in solution was determined by adjusting a HPLC method with a UV detector. Experimental maximum adsorption capacity were 15,000, 14,300 and 4,700 mg g¹ for Valdivia, Clarillo, and Chicureo soils, respectively. Linear, Freundlich, and Langmuir models were used to describe glyphosate adsorption. Isotherms describing glyphosate adsorption differed among soils. Maximum adjusted adsorption capacity with the Langmuir model was 231,884, 17,874 and 5,670 mg g-1 for Valdivia, Clarillo, and Chicureo soils, respectively. Glyphosate adsorption on the Valdivia soil showed a linear behavior at the range of concentrations used and none of the adjusted models became asymptotic. The high glyphosate adsorption capacity of the Valdivia soil was probably a result of its high exchangeable Al, extractable Fe, and alophan and imogolite clay type. Adsorption was very much related to phosphate dynamics in the Valdivia soil, which showed the larger unoccupied phosphate binding sites. However relationship between unoccupied phosphate binding sites and glyphosate adsorption in the other two soils (Clarillo and Chicureo) was not clear.

Immersion enthalpy variation of surface-modified mineral activated carbon in lead (II) aqueous solution adsorption: the relation between immersion enthalpy and adsorption capacity

An activated carbon was obtained by chemical activation with phosphoric acid, CM, from a mineral carbon. Afterwards, the carbon was modified with 2 and 5 molL-1, CMox2 and CMox5 nitric acid solutions to increase the surface acid group contents. Immersion enthalpy at pH 4 values and Pb2+ adsorption isotherms were determined by immersing activated carbons in aqueous solution. The surface area values of the adsorbents and total pore volume were approximately 560 m².g-1 and 0.36 cm³g-1, respectively. As regards chemical characteristics, activated carbons had higher acid sites content, 0.92-2.42 meq g-1, than basic sites, 0.63-0.12 meq g-1. pH values were between 7.4 and 4.5 at the point of zero charge, pH PZC. The adsorbed quantity of Pb2+ and the immersion enthalpy in solution of different pH values for CM activated carbon showed that the values are the highest for pH 4, 15.7 mgg-1 and 27.6 Jg-1 respectively. Pb2+ adsorption isotherms and immersion enthalpy were determined for modified activated carbons and the highest values were obtained for the activated carbon that showed the highest content of total acid sites on the surface.

Relationship between soil oxidizable carbon and physical, chemical and mineralogical properties of umbric ferralsols

The occurrence of Umbric Ferralsols with thick umbric epipedons (> 100 cm thickness) in humid Tropical and Subtropical areas is a paradox since the processes of organic matter decomposition in these environments are very efficient. Nevertheless, this soil type has been reported in areas in the Southeast and South of Brazil, and at some places in the Northeast. Aspects of the genesis and paleoenvironmental significance of these Ferralsols still need a better understanding. The processes that made the umbric horizons so thick and dark and contributed to the preservation of organic carbon (OC) at considerable depths in these soils are of special interest. In this study, eight Ferralsols with a thick umbric horizon (UF) under different vegetation types were sampled (tropical rain forest, tropical seasonal forest and savanna woodland) and their macromorphological, physical, chemical and mineralogical properties studied to detect soil characteristics that could explain the preservation of high carbon amounts at considerable depths. The studied UF are clayey to very clayey, strongly acidic, dystrophic, and Al-saturated and charcoal fragments are often scattered in the soil matrix. Kaolinites are the main clay minerals in the A and B horizons, followed by abundant gibbsite and hydroxyl-interlayered vermiculite. The latter was only found in UFs derived from basalt rock in the South of the country. Total carbon (TC) ranged from 5 to 101 g kg-1 in the umbric epipedon. Dichromate-oxidizable organic carbon represented nearly 75 % of TC in the thick A horizons, while non-oxidizable C, which includes recalcitrant C (e.g., charcoal), contributed to the remaining 25 % of TC. Carbon contents were not related to most of the inorganic soil variables studied, except for oxalate-extractable Al, which individually explained 69 % (P < 0.001) of the variability of TC in the umbric epipedon. Clay content was not suited as predictor of TC or of the other studied C forms. Bulk density, exchangeable Al3+, Al saturation, ECEC and other parameters obtained by selective extraction were not suitable as predictors of TC and other C forms. Interactions between organic matter and poorly crystalline minerals, as indicated by oxalate-extractable Al, appear to be one of the possible organic matter protection mechanisms of these soils.

Accumulation of phosphorus fractions and contamination potential in vineyard soils in the southern region of the state of Santa Catarina, Brazil

In vineyards, if phosphate is applied both before planting and at intervals during growth without consideration of technical criteria, the soil P fractions may be increased and their proportions altered. This study was carried out to evaluate the accumulation of P fractions and the parameters of the adsorption isotherm in a sandy Typic Hapludalf soil in vineyards with a history of successive and excessive phosphate fertilization. In December 2010, two vineyards were selected, one 4 and the other 15 years old, in Urussanga, State of Santa Catarina (Brazil). Three trenches were dug in each area and soil was collected from the 0-5, 5-10 and 10-20 cm depth ranges. The soil samples were dried in a forced-air oven, sieved and subjected to chemical analyses, P chemical fractionation and P adsorption isotherms. Excessive phosphate fertilization, before and during cultivation, particularly in the older vineyard and, consequently, with a longer history of phosphate fertilization, increased the inorganic P concentrations to the depth of 20 cm, especially in labile fractions extracted by anion exchange resin and NaHCO3 in the non-labile fraction, as well as in the non-labile fraction extracted by 1.0 mol L-1 HCl. The application of phosphate fertilizers and the long cultivation period increased the P levels in the organic labile fraction extracted by 0.5 mol L-1 NaHCO3, and especially in the moderately labile fraction extracted by 0.1 and 0.5 mol L-1 NaOH. Phosphate fertilization of older vineyards, i.e., cultivated for 15 years, increased the amounts of P desorbed in water, indicating a risk of contamination of surface waters and groundwater. The phosphate fertilization before planting, without considering the results of soil analysis, and during cultivation, disregarding the results of soil analysis, leaf analysis and expected yield, led to a reduction in the maximum P adsorption capacity in the 0-5 cm layer of vineyard 2, indicating saturation of part of the reactive particle adsorption sites.

Quantification of permanent and variable charges in reference soils of the State of Pernambuco, Brazil

The electrical charges in soil particles are divided into structural or permanent charges and variable charges. Permanent charges develop on the soil particle surface by isomorphic substitution. Variable charges arise from dissociation and association of protons (H+), protonation or deprotonation, and specific adsorption of cations and anions. The aim of this study was to quantify the permanent charges and variable charges of Reference Soils of the State of Pernambuco, Brazil. To do so, 24 subsurface profiles from different regions (nine in the Zona da Mata, eight in the Agreste, and seven in the Sertão) were sampled, representing approximately 80 % of the total area of the state. Measurements were performed using cesium chloride solution. Determination was made of the permanent charges and the charges in regard to the hydroxyl functional groups through selective ion exchange of Cs+ by Li+ and Cs+ by NH4+, respectively. All the soils analyzed exhibited variable cation exchange capacity, with proportions from 0.16 to 0.60 and an average of 0.40 when related to total cation exchange capacity.

Remaining phosphorus and sodium fluoride pH in soils with different clay contents and clay mineralogies

The remaining phosphorus (Prem) has been used for estimating the phosphorus buffer capacity (PBC) of soils of some Brazilian regions. Furthermore, the remaining phosphorus can also be used for estimating P, S and Zn soil critical levels determined with PBC-sensible extractants and for defining P and S levels to be used not only in P and S adsorption studies but also for the establishment of P and S response curves. The objective of this work was to evaluate the effects of soil clay content and clay mineralogy on Prem and its relationship with pH values measured in saturated NaF solution (pH NaF). Ammonium-oxalate-extractable aluminum exerts the major impacts on both Prem and pH NaF, which, in turn, are less dependent on soil clay content. Although Prem and pH NaF have consistent correlation, the former has a soil-PBC discriminatory capacity much greater than pH NaF.

Screening of Brazilian soybean genotypes with high potential for somatic embryogenesis and plant regeneration

The aim of this work was to identify Brazilian soybean (Glycine max) genotypes with potential to respond to in vitro culture stimuli for primary somatic embryo induction, secondary embryo proliferation and plant regeneration. Differences among eight tested cultivars were observed at each stage. Two cultivars, IAS-5 and BRSMG 68 Vencedora, were selected for the evaluation of the capacity for embryo differentiation and plant regeneration. These cultivars had high embryo induction frequencies, repetitive embryogenic proliferation, and low precocious embryo germination in the initial experiment. The effect of abscisic acid (ABA) and charcoal addition on plant regeneration was investigated. The addition of ABA to proliferation medium and of ABA and activated charcoal to maturation medium increased embryo differentiation rates, which resulted in a higher number of regenerated plants. The BRSMG 68 Vencedora cultivar was found to have a high potential for embryo induction, embryo proliferation and plant regeneration. The potential of this cultivar for somatic embryogenesis was similar to that observed for cultivar IAS-5, which is currently used for soybean transformation in Brazil. BRSMG 68 Vencedora may be a good alternative genotype for soybean genetic engineering via somatic embryogenesis protocols.

Mass and energy balance of the carbonization of babassu nutshell as affected by temperature

The objective of this work was to evaluate the carbonization yield of babassu nutshell as affected by final temperature, as well as the energy losses involved in the process. Three layers constituting the babassu nut, that is, the epicarp, mesocarp and endocarp, were used together. The material was carbonized, considering the following final temperatures: 450, 550, 650, 750, and 850ºC. The following were evaluated: energy and charcoal yields, pyroligneous liquid, non-condensable gases, and fixed carbon. The use of babassu nutshell can be highly feasible for charcoal production. The yield of charcoal from babassu nutshell carbonization was higher than that reported in the literature for Eucalyptus wood carbonization, considering the final temperature of 450ºC. Charcoal and energy yields decreased more sharply at lower temperatures, with a tendency to stabilize at higher temperatures. The energy yields obtained can be considered satisfactory, with losses between 45 and 52% (based on higher heating value) and between 43 and 49% (based on lower heating value) at temperatures ranging from 450 to 850ºC, respectively. Yields in fixed carbon and pyroligneous liquid are not affected by the final carbonization temperature.

Estudo da capacidade de complexação e sua relação com algumas variáveis ambientais em cinco represas do Rio Tietê/Brasil

The copper and cadmium complexation properties in natural sediment suspensions of reservoirs of the Tietê River were studied using the solid membrane copper and cadmium ion-selective electrodes. The complexation and the average conditional stability constants were determined under equilibrium conditions at pH=6.00 ± 0.05 in a medium of 1.0 mol L-1 sodium nitrate, using the Scatchard method. The copper and cadmium electrodes presented Nernstian behavior from 1x10-6 to 1x10-3 mol L-1 of total metal concentration. Scatchard graphs suggest two classes of binding sites for both metals. A multivariate study was done to correlate the reservoirs and the variables: complexation properties, size, total organic carbon, volatile acid sulfide, E II and pH.

Estimation of surface area and pore volume of activated carbons by methylene blue and iodine numbers

Data of methylene blue number and iodine number of activated carbons samples were calibrated against the respective surface area, micropore volume and total pore volume using multiple regression. The models obtained from the calibrations were used in predicting these physical properties of a test group of activated carbon samples produced from several raw materials. In all cases, the predicted values were in good agreement with the expected values. The method allows extracting more information from the methylene blue and iodine adsorption studies than normally obtained with this type of material.