Peanut shells-derived biochars prepared from different carbonization processes: Comparison of characterization and mechanism of naproxen adsorption in water.

The ubiquitous appearance of nonsteroidal anti-inflammatory drugs (i.e., naproxen) in water bodies has raised enormous concerns among general public. Development of promising materials for eliminating such contaminants from water environment has attracted much attention in the scientific community. In this study, three (direct, post-treated and pre-treated) methods were developed to prepare biochars (800-PSB, 800-800-PSB, and 190-800-PSB, respectively) derived from the wastes of peanut shells (PS). They were thoroughly characterized by various important properties (i.e., porosity and superficial functional group) and applied to remove naproxen drug from water. Results indicated that although the pre- and post-treatments had a slight effect on the surface area of biochars (i.e., 571 m2/g for 800-PSB, 596 m2/g for 800-800-PSB, and 496 m2/g for 190-800-PSB), such treatments remarkably improved the adsorption capacity of biochar. The maximum adsorption capacity of biochar (obtained from the Langmuir model) towards naproxen in solution at 25 decreased in the following order: 800-800-PSB (324 mg/g) > 190-800-PSB (215 mg/g) > 800-PSB (105 mg/g). The thermodynamic study demonstrated that the adsorption was spontaneous and exothermic. Depending the preparation process, the contribution of each mechanism in the adsorption process was dissimilar. The overall adsorption mechanism was regarded as pore filling, π-π interaction, hydrogen bonding formations, n-π interaction, van der Waals force, and electrostatic attraction. Two methods used to identify the important role of π-π interaction were proposed herein. The possible desorption and reuse of laden-biochars were investigated by the chemical and thermal methods. The prepared biochar samples can serve as potential carbonaceous porous adsorbents for effectively removing naproxen from water media.

Separation and Preconcentration of Nickel(II) from Drinking, Spring, and Lake Water Samples with Amberlite CG-120 Resin and Determination by Flame Atomic Absorption Spectrometry.

In this study, Amberlite CG-120 adsorbent was used for the separation/preconcentration of Ni(II) ions in commercial drinking, spring and lake water samples before detection by flame atomic absorption spectrometry. Various optimization parameters for Ni(II) determination, such as pH, eluent type and concentration, sample and eluent flow rates, amount of adsorbent, were investigated to obtain better sensitivity, accuracy, precision and quantitative recovery. Furthermore, the interference effects of some ions on the recovery efficiency of Ni(II) were also investigated. The optimum experimental parameters were obtained in the case of pH 1; 5 mL of 4 mol L-1 HCl for eluent and 0.3 g for the adsorbent amount. The limit of detection was found to be 0.58 µg L-1 and linearity ranged from 5 to 50 µg L-1. The accuracy of the method was tested by the certified reference material of TMDA-70.2 Ontario Lake Water at a 95% confidence level.

A Novel Method Using Solid-Phase Extraction with Slotted Quartz Tube Atomic Absorption Spectrometry for the Determination of Manganese in Walnut Samples.

Mn(2+) was separated and preconcentrated using both solid-phase extraction (SPE) and a slotted quartz tube (SQT), and detected by a flame atomic absorption spectrometry (FAAS) system. Firstly, Mn(2+) was retained on a column filled with Amberlite CG-120 resin, and then retained Mn(2+) ions on the Amberlite CG-120 resin eluted with 5 mL of 4 mol/L HNO3. This part was called the "first preconcentration step". Furthermore, to determine the Mn(2+) in a walnut sample, the SQT device was also used after the separation and preconcentration of Mn(2+) from the Amberlite CG-120 resin so as to further improve the sensitivity of system. This part was called the "second preconcentration step" in this study. The enrichment factor and limit of detection values were found to be 360 fold and 0.22 µg/L, in turn, after a two-step preconcentration method. The good accuracy of method was confirmed with the use of standard reference material (spinach leaves, NIST-1570a).

Determination of mercury in fish otoliths by cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS).

A method based on cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS) has been developed for determination of inorganic mercury, Hg(II), and total mercury in fish otoliths. Sodium borohydride (NaBH(4)) was used as the only reducing agent and its concentration was optimized across an acidity gradient to selectively reduce Hg(II) without affecting methylmercury, CH(3)Hg(I). Inorganic Hg was quantitatively reduced to elemental mercury (Hg(0)) with 1 × 10(-4)% (m/v) NaBH(4). CH(3)Hg(I) required a minimum of 0.5% (m/v) NaBH(4) for complete reduction. Increasing the HCl concentration of solution to 5% (v/v) improved the selectivity toward Hg(II) as it decreased the signals from CH(3)Hg(I) to baseline levels. Potassium ferricyanide solution was the most effective in eliminating the memory effects of Hg compared with a number of chelating and oxidizing agents, including EDTA, gold chloride, thiourea, cerium ammonium nitrate and 2-mercaptoethylamine chloride. The relative standard deviation (RSD) was less than 5% for 1.0 µg L(-1) Hg(II) solution. The detection limits were 4.2 and 6.4 ng L(-1) (ppt) for Hg(II) and total Hg, respectively. Sample dissolution conditions and recoveries were examined with ultra-pure CaCO(3) (99.99%) spiked with Hg(II) and CH(3)HgCl. Methylmercury was stable when dissolution was performed with up to 20% (v/v) HCl at 100°C. Recoveries from spiked solutions were higher than 95% for both Hg(II) and CH(3)Hg(I). The method was applied to the determination of Hg(II) and total Hg concentrations in the otoliths of red emperor (CRM 22) and Pacific halibut. Total Hg concentration in the otoliths was 0.038 ± 0.004 µg g(-1) for the red emperor and 0.021 ± 0.003 µg g(-1) for the Pacific halibut. Inorganic Hg accounted for about 25% of total Hg indicating that Hg in the otoliths was predominantly organic mercury (e.g., methylmercury). However, as opposed to the bioaccumulation in tissues, methylmercury levels in otoliths was very low suggesting a different route of uptake, most likely through the deposition of methylmercury available in the water.

Indium determination using slotted quartz tube-atom trap-flame atomic absorption spectrometry and interference studies.

Sensitivity enhancement of indium determination by flame atomic absorption spectrometry (FAAS) was achieved; using a slotted quartz tube (SQT-FAAS) and slotted quartz tube atom trap (SQT-AT-FAAS). SQT was used as an atom trap (AT) where the analyte is accumulated in its inner wall prior to re-atomization. The signal is formed after re-atomization of analyte on the trap surface by introduction of 10 µL of isobutyl methyl ketone (IBMK). Sensitivity was improved 400 times using SQT-AT-FAAS system with respect to conventional FAAS and 279 times with respect to SQT-FAAS without any collection. Characteristic concentration (C(0)) and limit of detection values were found to be 3.63 ng mL(-1) and 2.60 ng mL(-1), respectively, using a sample flow rate of 7.0 mL min(-1) and a collection period of 5.0 min. In addition, interference effects of some elements on indium signal were studied. In order to characterize indium species trapped, X-ray Photoelectron Spectrometry (XPS) was utilized and it was found that indium was collected on the inner surface of SQT as In(2)O(3). The accuracy of the procedure was checked to determine indium in the standard reference material (Montana Soil, SRM 2710).

Determination and interference studies of bismuth by tungsten trap hydride generation atomic absorption spectrometry.

The determination of bismuth requires sufficiently sensitive procedures for detection at the microg L(-1) level or lower. W-coil was used for on-line trapping of volatile bismuth species using HGAAS (hydride generation atomic absorption spectrometry); atom trapping using a W-coil consists of three steps. Initially BiH(3) gas is formed by hydride generation procedure. The analyte species in vapor form are transported through the W-coil trap held at 289 degrees C where trapping takes place. Following the preconcentration step, the W-coil is heated to 1348 degrees C; analyte species are released and transported to flame-heated quartz atom cell where the atomic signal is formed. In our study, interferences have been investigated in detail during Bi determination by hydride generation, both with and without trap in the same HGAAS system. Interferent/analyte (mass/mass) ratio was kept at 1, 10 and 100. Experiments were designed for carrier solutions having 1.0M HNO(3). Interferents such as Fe, Mn, Zn, Ni, Cu, As, Se, Cd, Pb, Au, Na, Mg, Ca, chloride, sulfate and phosphate were examined. The calibration plot for an 8.0 mL sampling volume was linear between 0.10 microg L(-1) and 10.0 microg L(-1) of Bi. The detection limit (3s/m) was 25 ng L(-1). The enhancement factor for the characteristic concentration (C(o)) was found to be 21 when compared with the regular system without trap, by using peak height values. The validation of the procedure was performed by the analysis of the certified water reference material and the result was found to be in good agreement with the certified values at the 95% confidence level.

Penicillium digitatum immobilized on pumice stone as a new solid phase extractor for preconcentration and/or separation of trace metals in environmental samples.

This study presents a column solid phase extraction procedure based on column biosorption of Cu(II), Zn(II) and Pb(II) ions on Penicillium digitatum immobilized on pumice stone. The analytes were determined by flame atomic absorption spectrometry (FAAS). The optimum conditions such as: pH values, amount of solid phase, elution solution and flow rate of sample solution were evaluated for the quantitative recovery of the analytes. The effect of interfering ions on the recovery of the analytes has also been investigated. The recoveries of copper, zinc and lead under the optimum conditions were found to be 97+/-2, 98+/-2 and 98+/-2%, respectively, at 95% confidence level. For the analytes, 50-fold preconcentration was obtained. The analytical detection limits for Cu(II), Zn(II) and Pb(II) were 1.8, 1.3 and 5.8 ng mL(-1), respectively. The proposed procedure was applied for the determination of copper, zinc and lead in dam water, waste water, spring water, parsley and carrot. The accuracy of the procedure was checked by determining copper, zinc and lead in standard reference tea samples (GBW-07605).

Separation and preconcentration of trace manganese from various samples with Amberlyst 36 column and determination by flame atomic absorption spectrometry.

This work assesses the potential of a new adsorptive material, Amberlyst 36, for the separation and preconcentration of trace manganese(II) from various media. It is based on the sorption of manganese(II) ions onto a column filled with Amberlyst 36 cation exchange resin, followed by the elution with 5mL of 3mol/L nitric acid and determination by flame atomic absorption spectrometry (FAAS) without interference of the matrix. Different factors including pH of sample solution, sample volume, amount of resin, flow rate of sample solution, volume and concentration of eluent, and matrix effects for preconcentration were investigated. Good relative standard deviation (3%) and high recovery (>95%) at 100mug/L and high enrichment factor (200) and low analytical detection limit (0.245mug/L) were obtained. The adsorption equilibrium was described well by the Langmuir isotherm model with maximum adsorption capacity of 88mg/g of manganese on the resin. The method was applied for the manganese determination by FAAS in tap water, commercial natural drinking water, commercial treated drinking water and commercial tea bag sample. The accuracy of the method is confirmed by analyzing the certified reference material (tea leaves GBW 07605). The results demonstrated good agreement with the certified values.

Optimization of a new resin, Amberlyst 36, as a solid-phase extractor and determination of copper(II) in drinking water and tea samples by flame atomic absorption spectrometry.

A new simple and reliable method has been developed to separate and preconcentrate trace copper ion in drinking water and tea samples for subsequent measurement by flame atomic absorption spectrometry (FAAS). The copper ions are adsorbed quantitatively during passage of aqueous solutions through Amberlyst 36 cation exchange resin. After the separation and preconcentration stage, the analyte was eluted with a potassium cyanide solution and determined by FAAS. Different factors including pH of sample solution, sample volume, amount of resin, flow rate of aqueous solution, volume and concentration of eluent, and matrix effects for preconcentration were examined. The analytical figures of merit for the determination of copper are as follows: analytical detection limit (3 sigma), 0.26 microg/L; precision (RSD), 3.1% for 100 microg/L; enrichment factor, 200 (using 1000 mL of sample solution and 5 mL of eluent); time of analysis, 3.5 h (for obtaining enrichment factor of 200); capacity of resin, 125 mg/g. The method was applied for copper determination by FAAS in tap water, commercial natural spring water, commercial treated drinking water, and commercial tea bag sample. The accuracy of the method is confirmed by analyzing tea leaves (GBW 07605). The results demonstrated good agreement with the certified values.

Determination of trace cadmium in waters by flame atomic absorption spectrophotometry after preconcentration with 1-nitroso-2-naphthol-3,6-disulfonic acid on Ambersorb 572.

A procedure for the determination of trace amount of cadmium after adsorption of its 1-nitroso-2-naphthol-3,6-disulfonic acid chelate on Ambersorb 572 has been proposed. This chelate is adsorbed on the adsorbent in the pH range 3-8 from large volumes of aqueous solution of water samples with a preconcentration factor of 200. After being sorbed, cadmium was eluted by 5 mL of 2.0 mol L(-1) nitric acid solution and determined directly by flame atomic absorption spectrophotometery (FAAS). The detection limit (3sigma) of cadmium was 0.32 microg L(-1). The precision of the proposed procedure, calculated as the relative standard deviation of recovery in sample solution (100 mL) containing 5 microg of cadmium was satisfactory (1.9%). The adsorption of cadmium onto adsorbent can formally be described by a Langmuir equation with a maximum adsorption capacity of 19.6 mg g(-1) and a binding constant of 6.5 x 10(-3) L mg(-1). Various parameters, such as the effect of pH and the interference of a number of metal ions on the determination of cadmium, have been studied in detail to optimize the conditions for the preconcentration and determination of cadmium in water samples. This procedure was applied to the determination of cadmium in tap and river water samples.

Determination of iron, manganese and zinc in water samples by flame atomic absorption spectrophotometry after preconcentration with solid-phase extraction onto Ambersorb 572.

A solid-phase extraction method for the preconcentration of Fe, Mn and Zn on a column containing Ambersorb 572 has been developed, and the determination of Fe, Mn and Zn in water using a flame atomic absorption spectrophotometer (FAAS) has been performed. The optimum preconcentration parameters of the procedure have been determined. The effect of the pH, complexing agent, amount of adsorbent, flow rate, concentration and volume of the elution solution and interfering ions on the recovery of the analytes were investigated. The recoveries of Fe, Mn and Zn were 99 +/- 3%, 98 +/- 3% and 99 +/- 3% at the 95% confidence level, respectively, under the optimum conditions. Fe, Mn and Zn were preconcentrated up to 50, 100, 200, respectively. The limits of detection of Fe, Mn and Zn are 2.5, 0.68 and 0.24 micrograms l-1, respectively. The adsorption capacity of the adsorbent was found to be 10.9, 13.1 and 21.5 mg g-1 for Fe, Mn and Zn, respectively. The method has been applied to the determination of these metal ions in tap-water and river-water samples. The precision and the accuracy of the method is very good. The relative standard deviation and the relative error are lower than 4%.