Evaluation of some metals in Brazilian coffees cultivated during the process of conversion from conventional to organic agriculture

The aim of this study was to evaluate the presence of nutrients and toxic elements in coffees cultivated during the process of conversion, on organic agriculture, in southwest Bahia, Brazil. Levels of the nutrients and toxic elements were determined in samples of soils and coffee tissues from two transitional organic farms by atomic absorption spectrometry (FAAS). The metals in soil samples were extracted by Mehlich1 and USEPA-3050 procedures. Coffee samples from both farms presented relatively high levels of Cd, Zn and Cu (0.75,45.4 and 14.9 mu g g(-1). respectively), but were still below the limits specified by the Brazilian Food Legislation. The application of statistical methods showed that this finding can be attributed to the addition of high amounts of organic matter during the flowering tree period which can act on the bioavailability of metal ions in soils. (C) 2009 Elsevier Ltd. All rights reserved.

Applying sequential injection analysis (SIA) and response surface methodology for optimization of Fenton-based processes

This work presents the use of sequential injection analysis (SIA) and the response surface methodology as a tool for optimization of Fenton-based processes. Alizarin red S dye (C.I. 58005) was used as a model compound for the anthraquinones family. whose pigments have a large use in coatings industry. The following factors were considered: [H(2)O(2)]:[Alizarin] and [H(2)O(2)]:[FeSO(4)] ratios and pH. The SIA system was designed to add reagents to the reactor and to perform on-line sampling of the reaction medium, sending the samples to a flow-through spectrophotometer for monitoring the color reduction of the dye. The proposed system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 99.7% of the dye was degraded and the TOC content was reduced to 35% of the original value. Low reagents consumption and high sampling throughput were the remarkable features of the SIA system. (C) 2008 Published by Elsevier B.V.

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (lambda = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L(-1) NaCl + 0.5 mol L(-1) H(2)SO(4) solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L(-1) NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min(-1) and 0.069 min(-1), for Pt and Pt/Ti electrodes, respectively.

SnO(2)-based materials for pesticide degradation

This study presents the results of the degradation of the pesticide atrazine using electrochemical and photo-assisted electrochemical degradation techniques using SnO(2)-containing electrode of nominal composition electrodes of composition Ti/Ru(x)Sni-(x)O(2) (where X = 0.10, 0.15, 0.20, 0.25 and 0.30). The materials were characterized ex situ and in situ in order to correlate the observed atrazine removal rates with electrode morphology/composition. The results obtained demonstrate the effectiveness of the photo-assisted electrochemical degradation. Using purely electrochemical methods the rate of atrazine removal is almost zero at all the electrodes studied. However, the application of photo-assisted degradation results in almost complete atrazine removal in 1 h of electrolysis. The efficiency of atrazine degradation does not seem to be greatly affected by the electrode material or by SnO(2) content, but the overall COD removal is dependent on the SnO(2) content. Overall, the SnO(2)-containing electrodes do not reach the level of COD removal (maximum similar to 21%) seen for the Ti/Ru(0.3)Ti(0.2)O(2) electrode. An interesting correlation between the morphology factor (phi) and chemical oxygen demand removal is observed. (C) 2010 Elsevier B.V. All rights reserved.

Removal of phenol in high salinity media by a hybrid process (activated sludge plus photocatalysis)

The degradation of phenol by a hybrid process (activated sludge + photocatalysis) in a high salinity medium (50 g L-1 of chloride) has been investigated. The sludge used from a municipal wastewater facility was adapted to the high salt concentrations prior to use. The photocatalytic conditions were optimized by means of a factorial experimental design. TiO2 P25 from Degussa was used as the photocatalyst. The initial phenol concentration was approximately 200 mg L-1 and complete removal of phenol and a mineralization degree above 98% were achieved within 25 h of treatment (24 h of biological treatment and I h of photocatalysis). From HPLC analyses, five hydroxylated intermediates formed during oxidation have been identified. The main ones were catechol and hydroquinone, followed by 1,2,4-benzenetriol, 2-hydroxy- 1,4-benzoquinone, and pyrogallol, in this order. No formation of organochlorine compounds was observed. Therefore, the proposed hybrid process showed itself to be suited to treat phenol in the presence of high contents of salt. (c) 2007 Elsevier B.V. All rights reserved.

Photo-assisted electrochemical degradation of the commercial herbicide atrazine

This paper presents a degradation study of the pesticide atrazine using photo-assisted electrochemical methods at a dimensionally stable anode (DSA (R)) of nominal composition Ti/Ru(0.3)Ti(0.7)O(2) in a prototype reactor. The effects of current density, electrolyte flow-rate, as well as the use of different atrazine concentrations are reported. The results indicate that the energy consumption is substantially reduced for the combined photochemical and electrochemical processes when compared to the isolated systems. It is observed that complete atrazine removal is achieved at low current densities when using the combined method, thus reducing the energy required to operate the electrochemical system. The results also include the investigation of the phytotoxicity of the treated solutions.

Heterogeneous photocatalytic degradation of reactive dyes in aqueous TiO(2) suspensions: Decolorization kinetics

This work assesses the photocatalytic (TiO(2)/UV) degradation of a simulated reactive dye bath (Black 5, Red 239, Yellow 17, and auxiliary chemicals). Color removal was monitored by spectrophotometry. Mineralization was determined by DOC analyses. Photocatalytic, photolytic, and adsorption experiments were performed, showing that adsorption was negligible. After 30 min of irradiation, it was achieved 97% and 40% of color removal with photocatalysis and photolysis, respectively. No mineralization occurred within 30 min. A kinetic model composed of two, first-order in-series reactions was used. The first photocatalytic decolorization rate constant was k(1) = 2.6 min(-1) and the second k(2) = 0.011 min(-1). The fast decolorization of Reactive Black 5 dye is an indication that the number of azo and vinylsulfone groups in the dye molecule maybe a determining factor for the increased photolytic and photocatalytic color removal and degradation rates. (C) 2008 Elsevier B.V. All rights reserved.

A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

A comparative study of two different conductive carbon-black pigments, Vulcan XC-72 R and Printex L6, for the electrogeneration of hydrogen peroxide (H(2)O(2)) by reducing dissolved oxygen in an alkaline solution was performed. The materials were physically characterized by X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). XRD shows the presence of SO(2) and ATR-FTIR technique indicates a difference in NO and SO(2) functional groups between the two carbon pigments. XPS indicated presence of SO and NO and more oxygenated acid species on Printex L6. A rotating ring-disk electrode was used for electrochemical analysis of the oxygen reduction reaction (ORR). The results showed that the Printex L6 was better than Vulcan XC-72 R for H(2)O(2) production. Results also indicate that the number of electrons transferred in the ORR for Printex L6 and Vulcan XC-72 R were 2.2 and 2.9, respectively, while the percentages of H(2)O(2) formed were 88% and 51%. Scanning electrochemistry microscopy images confirmed the higher amount of H(2)O(2) formed in the Printex L6 pigment. Printex L6 was shown to be a more promising for H(2)O(2) production than Vulcan XC-72 R, while the latter was shown to have more potential for fuel cells. (C) 2011 Elsevier Ltd. All rights reserved.

An Environmental Friendly Procedure for Photometric Determination of Hypochlorite in Tap Water Employing a Miniaturized Multicommuted Flow Analysis Setup

A photometric procedure for the determination of ClO(-) in tap water employing a miniaturized multicommuted flow analysis setup and an LED-based photometer is described. The analytical procedure was implemented using leucocrystal violet (LCV; 4,4', 4 ''-methylidynetris (N, N-dimethylaniline), C(25)H(31)N(3)) as a chromogenic reagent. Solenoid micropumps employed for solutions propelling were assembled together with the photometer in order to compose a compact unit of small dimensions. After control variables optimization, the system was applied for the determination of ClO(-) in samples of tap water, and aiming accuracy assessment samples were also analyzed using an independent method. Applying the paired t-test between results obtained using both methods, no significant difference at the 95% confidence level was observed. Other useful features include low reagent consumption, 2.4 mu g of LCV per determination, a linear response ranging from 0.02 up to 2.0 mg L(-1) ClO(-), a relative standard deviation of 1.0% (n = 11) for samples containing 0.2 mg L(-1) ClO(-), a detection limit of 6.0 mu g L(-1) ClO(-), a sampling throughput of 84 determinations per hour, and a waste generation of 432 mu L per determination.

Intra and interannual variability in the Madeira River water chemistry and sediment load

Concentrations of cations (Na(+), Ca(2+), Mg(2+), K(+), NH(4) (+)), anions (HCO(3) (-), Cl(-), NO(3) (-), SO(4) (2-), PO(4) (3-)) and suspended sediments in the Madeira River water were determined near the city of Porto Velho (RO), in order to assess variation in water chemistry from 2004 to 2007. Calcium and bicarbonate were the dominant cation and anion, respectively. Significant seasonal differences were found, with highest concentrations occurring during the dry season, as expected from the drainage of Andean carbonate-rich substratum. Interannual variations were also observed, but became significant only when annual average discharge was 25% less than normal. Under this atypical discharge condition, bicarbonate was replaced by sulfate, and higher suspended sediment concentrations and loads were also observed. Compared to previously published studies, it appears that no significant changes in water chemistry have occurred during the last 20-30 years, although differences in approaches and sampling designs among this and previous studies may not allow detection of modest changes. The calculated suspended sediment load reported here is close to the values presented elsewhere, reinforcing the relative importance of this river as a sediment supplier for the Amazon Basin. Seasonality has a significant control on the chemistry of Madeira River waters, and severe decrease in discharge due to anthropogenic changes, such as construction of reservoirs or the occurrence of drier years-a plausible consequence of global climate change-may lead to modification in the chemical composition as well in the sediment deliver to the Amazon River.

A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

Green Chemistry-Sensitive Analytical Procedure for Photometric Determination of Orthophosphate in River and Tap Water by Use of a Simple LED-Based Photometer

In the current work a Green Analytical Chemistry (GAC) procedure for photometric determination of orthophosphate in river water at mu g L-1 concentration level is described. The flow system module and the LED-based photometer were assembled together to constitute a compact unit in order to allow that a flow cell with optical path-length of 100mm was coupled to them. The photometric procedure based on the molybdenum blue method was implemented employing the multicommuted flow injection analysis approach, which provided facilities to allow reduction of reagent consumption and as well as waste generation. Aiming to prove the usefulness of the system, orthophosphate in river and tap waters was determined. Accuracy was ascertained by spiking samples with orthophosphate solution yielding recoveries ranging from 96% up to 107%. Other profitable features such as a wide linear response range between 10 to 800 mu g L-1 [image omitted]; a detection limit (3 sigma criterion) of 2.4 mu g L-1 [image omitted]; a relative standard deviation (n=7) of 2% using a typical water sample with concentration of 120 mu g L-1 [image omitted]; reagent consumption of 3.0mg ammonium molybdate, 0.3mg hydrazine sulfate, and 0.03mg stannous chloride per determination; a waste generation of 2.4mL per determination; and a sampling throughput of 20 determination per hours were also achieved.

Determination of Cr, Fe, Co, Ni, Cu, Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 mu L) was dried on a 6.35 mu m thickness Mylar film at 60 degrees C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from (19)K to (92)U simultaneously.

Concretes and mortars recycled with water treatment sludge and construction and demolition rubble

There are about 7500 water treatment plants in Brazil. The wastes these plants generate in their decantation tanks and filters are discharged directly into the same brooks and rivers that supply water for treatment. Another serious environmental problem is the unregulated disposal of construction and demolition rubble, which increases the expenditure of public resources by degrading the urban environment and contributing to aggravate flooding and the proliferation of vectors harmful to public health. In this study, an evaluation was made of the possibility of recycling water treatment sludge in construction and demolition waste recycling plants. The axial compressive strength and water absorption of concretes and mortars produced with the exclusive and joint addition of these two types of waste was also determined. The ecoefficiency of this recycling was evaluated by determining the concentration of aluminum in the leached extract resulting from the solubilization of the recycled products. The production of concretes and mortars with the joint addition of water treatment sludge and recycled concrete rubble aggregates proved to be a viable recycling alternative from the standpoint of axial compression strength, modulus of elasticity, water absorption and tensile strength by the Brazilian test method. (C) 2008 Elsevier Ltd. All rights reserved.

Mechanical properties of concrete produced with a composite of water treatment sludge and sawdust

In developing countries such as Brazil, the wastes generated in the decanters and filters of water treatment plants are discharged directly into the same rivers and streams that supply water for treatment. Another environmental problem is the unregulated discard of wood wastes. The lumber and wood products industry generates large quantities of this waste, from logging to the manufacture of the end product. Brazil has few biomass plants and therefore only a minor part of these wastes are reused. This paper presents the results of the first study involving a novel scientific and technological approach to evaluate the possibility of combining these two types of wastes in the production of a light-weight composite for concrete. The concrete produced with cement:sand:composite:water mass ratios of 1:2.5:0.67:0.6 displayed an axial compressive strength of 11.1 MPa, a compressive and diametral tensile strength of 1.2 MPa, water absorption of 8.8%, and a specific mass of 1.847 kg/m(3). The mechanical properties obtained with this concrete render it suitable for application in non-structural elements. (C) 2010 Elsevier Ltd. All rights reserved.