Selective and sensitive fluorimetric determination of carbendazim in apple and orange after preconcentration with magnetite-molecularly imprinted polymer.

In this study, magnetite-molecularly imprinted polymer has been used for the first time as selective adsorbent before the fluorimetric determination of carbendazim. Adsorption capacity of the magnetite-molecularly imprinted polymer was found to be 2.31±0.63mgg-1 (n=3). Limit of detection (LOD) and limit of quantification (LOQ) of the method were found to be 2.3 and 7.8µgL-1, respectively. Calibration graph was linear in the range of 10-1000µgL-1. Rapidity is an important advantage of the method where re-binding and recovery processes of carbendazim can be completed within an hour. The same imprinted polymer can be used for the determination of carbendazim without any capacity loss repeatedly for at least ten times. Proposed method has been successfully applied to determine carbendazim residues in apple and orange, where the recoveries of the spiked samples were found to be in the range of 95.7-103%. Characterization of the adsorbent and the effects of some potential interferences were also evaluated. With the reasonably high capacity and reusability of the adsorbent, dynamic calibration range, rapidity, simplicity, cost-effectiveness and with suitable LOD and LOQ, the proposed method is an ideal method for the determination of carbendazim.

Use of Ni/NixB Nanoparticles as a Novel Adsorbent for the Preconcentration of Mercury Species prior to Cold Vapor-Atomic Fluorescence Spectrometric Determination.

A selective matrix separation/enrichment method, utilizing a simple batch procedure with nickel/nickel boride (Ni/NixB) nanoparticles was proposed for the determination of inorganic mercury(II), Hg(2+) and methyl mercury(I), CH3Hg(+) in waters prior to cold vapor-atomic fluorescence spectrometry (CV-AFS). The Ni/NixB nanoparticles, were synthesized by the chemical reduction of Ni(II) to Ni/NixB. The novel adsorbent was selective to Hg(2+) and CH3Hg(+) species between pH values of 4 - 10. Both of the mercury species were recovered from the adsorbent using 1.0 mol L(-1) hot HNO3 with high efficiency. It was observed that the adsorbent selectively removed Hg(2+) and CH3Hg(+) from the bulk solution in the presence of several competitor ions (As(3+), Sb(3+), Pb(2+), Zn(2+), Cu(2+), Cd(2+) and Fe(3+)) with ≥96% adsorption. The limit of detection (3σ above blank) was found to be 1.8 ng L(-1) with a preconcentration factor of 20. The validation of the method was tested through spike recovery experiments with several water samples (tap and seawater) at µg L(-1) concentration levels, and all recovery values were found to vary between 95 and 105%.

Leaching of arsenic from glazed and nonglazed potteries into foods.

Potteries are traditionally used for cooking and storing foods in Turkey, the Mediterranean, and Middle East regions. Leaching of inorganic arsenic into the traditional white bean dish cooked in pottery has been determined for the first time in the literature. Accuracy of this method was validated by the analysis of a certified reference material, commercially marketed standard solutions, and arsenic spiked solutions. Locally available potteries were examined for the leaching studies. Variation in the leachability of inorganic arsenic from the potteries by acetic acid versus the number of use was studied. The concentrations of arsenic leached by 4% acetic acid decreased by the usage number. The glazed potteries released arsenic at lower concentrations to leaching by acetic acid than the same group of nonglazed potteries. The concentrations of leached arsenic were relatively high in the white bean dish, where the leach of arsenic from the potteries to acetic acid was low. All of the potteries examined released inorganic arsenic to white bean dish in concentrations that exceed the daily BMDL0.5 (210µg/day). However, because the potteries are used only about once a month, direct application of the daily dietary intake limits is not appropriate. According to the weekly BMDL0.5, the estimated contribution from arsenic was in the range of 34-79% of BMDL0.5. The results of this study showed that the potteries are the potential sources of arsenic. Pottery oiling in ovens, which is another traditional procedure before using the potteries, reduced the leaching of arsenic to foods.

Arsenic Speciation of Waters from the Aegean Region, Turkey by Hydride Generation: Atomic Absorption Spectrometry.

Arsenic in drinking water is a serious problem for human health. Since the toxicity of arsenic species As(III) and As(V) is different, it is important to determine the concentrations separately. Therefore, it is necessary to develop an accurate and sensitive method for the speciation of arsenic. It was intended with this work to determine the concentrations of arsenic species in water samples collected from Izmir, Manisa and nearby areas. A batch type hydride generation atomic absorption spectrometer was used. As(V) gave no signal under the optimal measurement conditions of As(III). A certified reference drinking water was analyzed by the method and the results showed excellent agreement with the reported values. The procedure was applied to 34 water samples. Eleven tap water, two spring water, 19 artesian well water and two thermal water samples were analyzed under the optimal conditions.

Investigation of heavy metal content of Turkish tobacco leaves, cigarette butt, ash, and smoke.

A procedure for the determination of cadmium, copper, manganese, and zinc in Turkish tobaccos, which were of different origins, years, and grades, and in the butt, ash, and smoke, which were obtained by smoking the cigarettes that were prepared manually from the said tobaccos in a smoking apparatus, was devised as proposed. The collected samples were digested by wet ashing technique by using HNO3-HClO4 and were analyzed by flame atomic absorption spectrometry with satisfactory recoveries (94% to 98%). The regression coefficients were above 0.99, and the detection limits were in the range of 0.03-0.12 mg/L(-1). The performance and accuracy of the method was tested by analyzing "Certified Reference Material GBW 08501-Peach Leaves." The determined values were in agreement with the standard values for the heavy metals analyzed. Thus, it was concluded that the developed method could offer a wide range of application for establishing a relationship between the makeup and composition of tobacco plant, products, ash, smoke, and smoking.

Determination of essential and non-essential elements in various tea leaves and tea infusions consumed in Turkey.

Tea is one of the most popular beverages in the world. Thus, the chemical components in tea are of great interest, especially in relation to health. In this study, 12 tea samples (10 black, 1 white and 1 green) and 5 herbal tea samples were purchased from supermarkets in Izmir, Turkey. Sample preparation has been performed using wet and microwave digestion procedures. The elemental content (Fe, Zn, Cu, Mn, Ni, Na and K) in the digests and infusions has been analysed. Generally, elemental contents in tea leaves were found to be higher than those in tea infusions. The accuracy of the method was checked and confirmed by standard reference material analyses. The comparison of wet and microwave digestion has not shown significantly different results. Therefore, the microwave digestion procedure was preferred because it is less laborious. The elemental intake related to tea consumption has also been studied.

Determination of mercury(II) in the presence of methylmercury after preconcentration using poly(acrylamide) grafted onto cross-linked poly(4-vinyl pyridine): application to mercury speciation.

The applicability of poly(acrylamide) grafted onto cross-linked poly(4-vinyl pyridine) (P4-VP-g-PAm) has been investigated for the separation, preconcentration and speciation of Hg(II) and MeHg(I). In batch experiments, Hg(II) was quantitatively retained (≥95%) in the pH range of 1.0-8.0, whereas the sorption of MeHg(I) was insignificant in the pH range of 1.0-2.0. Freundlich and Langmuir isotherm models were investigated in order to characterize the sorption, and the capacity of the sorbent was found to be 817 mg Hg(II) g(-1). The limit of detection (3δ above blank) was 2 ng L(-1). The sorbent has excellent selectivity for Hg(II) in the presence of Pb(II), Zn(II), Cu(II), Cd(II) and Fe(III) ions. The method was successfully applied to the determination of Hg(II) and MeHg(I) in seawater and estuarine water. The sorbent can remove Hg(II) at pH 2.0, and therefore makes the determination of MeHg(I) possible, even if the sample contains a high amount of Hg(II).

Study of arsenic(III) and arsenic(V) removal from waters using ferric hydroxide supported on silica gel prepared at low pH.

Removal of As(III) and As(V) species using ferric hydroxide supported on silica gel was studied. Laboratory reagent quality silica gel was used as to avoid uncertainties that may be caused by impurities. Ferric hydroxide precipitation was realized at various pH values and a relatively low pH 6.0 was chosen because, at this pH, the highest arsenic removal capacity and removal efficiency were obtained and clear supernatant solution was observed. It was also shown by arsenic speciation analysis at trace level that As(III) is adsorbed onto ferric hydroxide partly without oxidation to As(V); this has been a controversial point in the literature. The effects on arsenic removal of some parameters such as pH, flow rate and matrix ions were investigated. In the batch method, initial pH change of the solution did not significantly affect the arsenic removal efficiencies for As(III) and As(V) in the pH range of 3.1-9.7. This was attributed to the decreases of the initial pH values to around 5 at equilibrium. The column capacities of 1.32 mg As(III)/g sorbent and 1.21 mg As(V)/g sorbent were found for initial concentration of 1.00 mg/L arsenic. Batch capacities were 16.2 mg As(III)/g sorbent and 17.7 mg As(V)/g sorbent for initial arsenic concentration of 100 mg/L. The method was applied successfully to the removal of As(III) and As(V) from drinking water, geothermal water and mineral water.

Determination of arsenic leaching from glazed and non-glazed Turkish traditional earthenware.

Glazed and non-glazed earthenware is traditionally and widely used in Turkey and most of the Mediterranean and the Middle East countries for cooking and conservation of foodstuff. Acid-leaching tests have been carried out to determine whether the use of glazed and non-glazed earthenware may constitute a human health hazard risk to the consumers. Earthenware was leached with 4% acetic acid and 1% citric acid solutions, and arsenic in the leachates was measured using hydride generation atomic absorption spectrometry. Arsenic concentrations in the leach solution of non-glazed potteries varied from 30.9 to 800 µg L⁻¹, while the glazed potteries varied generally from below the limit of detection (0.5 µg L⁻¹) to 30.6 µg L⁻¹, but in one poorly glazed series it reached to 110 µg L⁻¹. Therefore, the risk of arsenic poisoning by poorly glazed and non-glazed potteries is high enough to be of concern. It appears that this is the first study reporting arsenic release from earthenware into food.

Highly sensitive sensing of zinc(II) by development and characterization of a PVC-based fluorescent chemical sensor.

A sensor membrane with excellent performance based on 1-methyl-1-phenyl-3-[1-hydroxyimino-2-(succinimido)ethyl]cyclobutane has been developed for the determination of zinc(II) ions. The sensing membrane is capable of determining zinc(II) with an outstanding high selectivity over a dynamic range between 8.0×10(-8) and 1.6×10(-4) mol L(-1) with a limit of detection of 2.5×10(-8) mol L(-1) (1.6 µg L(-1)). It can be easily and completely regenerated by using 0.1 mol L(-1) EDTA solution. The optical sensor developed here was found to be stable, cost effective, easy to prepare, and has unique selectivity towards Zn(2+) ion with respect to common metal ions. The proposed sensor was then applied for the determination of zinc in tap water and hair samples with satisfactory results.

Application of a wool column for flow injection online preconcentration of inorganic mercury(II) and methyl mercury species prior to atomic fluorescence measurement.

The use of an unmodified native sheep wool packed minicolumn for the online preconcentration of Hg(II) and methyl mercury species prior to the determination of mercury by atomic fluorescence spectrometry was investigated. Experimental conditions, such as pH, desorbing agents, volume of solution were optimized. 0.5M thioglycolic acid was found to be a successful eluting agent for both mercury species. Breakthrough and total capacities were determined. The method is simple and rapidly applicable for the determination of Hg(II) and methyl mercury in tap water. The accuracy of the method was examined by the analysis of a peach leaves standard reference material. Recoveries of spiked mercury species in tap water were 105.8% for Hg(II) and 98.8% for methyl mercury.

Fiber optic sodium and potassium sensing by using a newly synthesized squaraine dye in PVC matrix.

In recent years squarines received attention as fluorescent labels. Their very promising spectral properties such as long wavelength absorption and emission, high extinction coefficients and quantum yields could lead novel sensing technologies. In this work newly synthesized fluoroinophores named bis[4-N-(1-aza-4,7,10,13-tetraoxacyclopentadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-1 and 2 bis[4-N-(1-aza-4,7,10,13,16-pentaoxacyclooctadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-2 have been used for sodium and potassium sensing in plasticized PVC matrix. The squaraine derivatives exhibited fluorescence emission based optical responses to sodium and potassium with a detection limit of 1.10(-9) M. The sensor compositions exhibited wide response ranges between 10(-9) and 10(-5) M Na(+)or K(+), and, therefore, may be an alternative method to flame emission spectroscopy. The sensor is fully reversible within the dynamic range and the response time is 3 min under batch conditions. Cross sensitivity to pH is negligible in the pH range of 6.2-7.3. Throughout fiber optic based studies a relative signal change of 54-56% has been achieved. The azacrown dyes have the advantage that they can be excited with long wavelength light and, are, therefore, LED compatible. The cross sensitivity of azacrown-1 and -2 to Ba(2+), Ca(2+) and NH(4)(+)were also tested in separate solutions.