Monitoring of trace amounts of heavy metals in different food and water samples by flame atomic absorption spectrophotometer after preconcentration by amine-functionalized graphene nanosheet

We are introducing graphene oxide modified with amine groups as a new solid phase for extraction of heavy metal ions including cadmium(II), copper(II), nickel(II), zinc(II), and lead(II). Effects of pH value, flow rates, type, concentration, and volume of the eluent, breakthrough volume, and the effect of potentially interfering ions were studied. Under optimized conditions, the extraction efficiency is >97 %, the limit of detections are 0.03, 0.05, 0.2, 0.1, and 1 μg L^?1 for the ions of cadmium, copper, nickel, zinc, and lead, respectively, and the adsorption capacities for these ions are 178, 142, 110, 125, and 210 mg g^?1. The amino-functionalized graphene oxide was characterized by thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectrometry. The proposed method was successfully applied in the analysis of environmental water and food samples. Good spiked recoveries over the range of 95.8–100.0 % were obtained. This work not only proposes a useful method for sample preconcentration but also reveals the great potential of modified graphene as an excellent sorbent material in analytical processes.     

Simultaneous determination of selected endocrine disrupter compounds in wastewater samples in ultra trace levels using HPLC-ES-MS/MS

An analytical procedure for the simultaneous determination of six selected endocrine disrupter compounds (EDCs: diltiazem, progesterone, benzyl butyl phthalate (BBP), estrone, carbamazepine (Cbz), acetaminophen) was developed by liquid chromatography electrospray ionization tandem mass spectrometry (HPLC-ES-MS/MS). All of the parameters for HPLC and ES-MS/MS systems including mobile phase composition, flow rate, and sample injection volume were optimized to obtain not only the best separation of species interested but also low detection limits. Reverse phase chromatography coupled to ES-MS/MS was used for the separation and detection of EDCs. Formic acid (0.10% ) and 5.0 mM ammonium formate were selected as mobile phase composition in gradient elution. Detection limits for diltiazem, progesterone, BBP, estrone, Cbz, and acetaminophen were found to be 0.13, 0.12, 0.04, 0.13, 0.12, and 0.05 ng/mL, respectively. Influent and effluents from three different wastewater treatment plants located in Ankara, i.e., rotating flat-sheet membrane unit, pilot type flat-sheet membrane unit located at METU Campus and samples from Ankara central wastewater treatment plant were analyzed for their EDCs contents under the optimum conditions.     

Methodologies for determination of antimony in terrestrial environmental samples

Methodologies for the environmental analysis of total antimony and aqueous chemical speciation are critically reviewed, including preparation techniques for aqueous and solid matrices and the determination of solid state partitioning and recommendations are given for future research directions. Concentrations of total antimony commonly present in aqueous and solid environmental samples are readily determined using present day analytical techniques. This has resulted primarily from technological advances in microwave digestion for solid matrices and the development of plasma based analyte detection systems. ICP-AES and ICP-MS techniques are both utilised for the environmental analysis of total antimony concentrations. However, ICP-MS is increasingly favoured as a result of reduced spectral interferences and the potential for analyte detection in the pg mL(-1) range. Determination of aqueous antimony speciation presents a number of complex analytical challenges and highly selective separation and identification techniques are required prior to detection. The majority of published techniques including common applications of hydride generation are insufficiently selective for the determination of intrinsic chemical speciation and often only oxidation state data are obtained. The recent in-line applications of HPLC-ICP-MS offer the potential for highly selective separations of aqueous antimony species and determination of detailed chemical speciation data. However, considerable development work is required to optimise chromatographic separations and identify uncharacterised species resident in environmental systems. Analytical techniques to aid the determination of antimony's associations with solid environmental matrices include the application of chemical extraction procedures and leaching experiments. To date, this area of analytical research has received little attention and further studies are required to elucidate this aspect of antimony's environmental chemistry.     

Preconcentration technique for the determination of trace elements in natural water samples by ICP-AES

A procedure was developed for the determination of Cd, Cu, Zn, Co, Ni, Mn, Pb and Mo in water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) after preconcentration on a morpholine dithiocarbamate (mor-DTC) supported by bagasse (Saccharam aphisinaram). The sorbed elements were subsequently eluted with 4,M HNO₃ and the acid eluates were analysed by ICP–AES. The influence of various parameters such as pH, flow rate of sample, eluent concentration, volume of the sample and volume of eluent were investigated to enhance the sensitivity of the present method. A 20,mL disposable syringe served as preconcentration column. Under the optimal conditions Cd, Cu, Zn, Co, Ni, Mn, Pb and Mo in aqueous sample was concentrated about 100-fold. The sorption recoveries of elements were higher than 99.6%. The method is also applied for the analysis of natural and spiked water samples.     

Novel solid-phase extractor based on functionalization of multi-walled carbon nano tubes with 5-aminosalicylic acid for preconcentration of Pb(II) in water samples prior to determination by ICP-OES

New solid-phase extractor (MWCNTs-5-ASA) was synthesized via covalent immobilization of 5-aminsalicylic acid onto multi-walled carbon nanotubes (MWCNs). The success of the functionalization process was confirmed using Fourier transform infrared spectroscopy, scanning electron microscope, and surface coverage determination. Batch experiments were conducted as a function of pH to explore MWCNTs-5-ASA efficiency to extract several metal ions viz., Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II). It was found that Pb(II) exhibits the highest extraction percentage with maximum adsorption capacity 32.75 mg g^?1. Its binding performance was well fitted with Langmuir sorption isotherm. On the other hand, the selective separation and preconcentration of trace Pb(II) under dynamic conditions prior to determination by inductively coupled plasma-optical emission spectrometry was investigated under different parameters. These included the rate of flow and volume of sample solution, in addition to the type of the eluate, its volume and concentration. The effect of a variety of foreign ions on the recovery percentage was also evaluated. Trace Pb(II) ions present in 500 mL aqueous solution adjusted to pH 4.0 were retained on 50 mg of MWCNTs-5-ASA and completely eluted using 4.0 mL of 2 M HNO₃. The limit of detection and the precision of the method were 0.25 ng mL^?1 and 2.8 %, respectively (N?=?5). This methodology has been applied for the determination of Pb(II) in water samples with good results.     

A new catalytic-spectrophotometric method for quantification of trace amounts of nitrite in fruit juice samples

A new kinetic method has been developed for the determination of nitrite in fruit juice samples. The method is based on the catalytic effect of nitrite with the oxidation of Nile Blue A (NBA) by KBrO₃ in the sulfuric acid medium. The optimum conditions obtained are 1.2 mM sulfuric acid, 0.034 mM of NBA, 2.8?×?10^?3 M KBrO₃, reaction temperature of 20 °C, and reaction time of 100 s at 595.5 nm. Under the optimized conditions, the method allowed the quantification of nitrite in a range of 0.2–800 μg/mL with a detection limit of 0.02 μg/mL. The method was applied to the determination of nitrite in 15 brands of fruit juice samples.     

WF-8型在线富集进样器应用于水中痕量CuPbCd测定的研究

用 WF 8型在线富集进样器与火焰原子吸收光度计联用 ,应用于水中痕量 Cu、Pb、Cd的测定 ,其富集倍数分别是 1 2 2、1 3 6和 94倍 ,测定的精密度分别是 3 7%、2 8%和 3 9% ,检出限分别是 0 4 7、1 3和 0 2 2μg L,在地表水样中的加标回收率分别为 94 2 %～ 1 0 0 %、98 8%～ 1 0 7%和 1 0 8%～ 1 2 0 % ,并对 WF 8型进样器与火焰原子吸收光度计的成功联用 ,提出了一种新操作程序。     

An online preconcentration system for the determination of uranium in water and effluent samples

Amberlite XAD-4 resin functionalized with β-nitroso-α-naphthol was applied to an online system for the preconcentration and determination of uranium. U (VI) ions were retained on the minicolumn at an appropriate pH and then desorbed with acid solution. The amount of uranium in the eluate was measured spectrophotometrically at 650 nm using Arsenazo III as a colorimetric reagent. The limit of detection and the preconcentration factor were 1.8 μg L^???1 and 10, respectively. The chemical and flow variables affecting the preconcentration were studied. The influence of several ions on the system was also investigated. The method was successfully applied for the evaluation of uranium in water and in effluent samples.     

Application of natural zeolites for preconcentration of arsenic species in water samples

Zeolites of the clinoptilolite type produced in Mexico and Hungary were investigated with respect to their sorption efficiency for various redox species of arsenic. Long-term experiments showed that arsenate remains stable for a long period in spiked deionised water and drinking water, as well as in the surface water of the Biela valley in Saxony, Germany. Both clinoptilolites are able to decrease the initial arsenic concentration of 200 microg l(-1) by more than 75% in deionised, drinking, ground and surface waters. In the case of the Mexican zeolite, both the arsenite and the arsenate concentrations (200 microg l(-1)) can be lowered from 200 microg l(-1) to 10 microg l(-1), which is the World Health Organisation's (WHO's) recommended maximum level. It was found that the presence of cations and anions in the natural waters of Biela, Germany, and Zimapán, Mexico, did not reduce the efficiency of the selected zeolites. The Hungarian zeolite removed 75% of the arsenate in the Zimapán water and only 50% when the sample was first acidified. This zeolite totally desorbed the fixed arsenic into a water volume that was half the volume in the adsorption experiment.     

The use of rapidly synergistic cloud point extraction for the separation and preconcentration of trace amounts of Ni (II) ions from food and water samples coupling with flame atomic absorption spectrometry determination

A novel improved preconcentration method known as rapidly synergistic cloud point extraction (RS-CPE) was established for nickel preconcentration and determination prior to its determination by flame atomic absorption spectrometry. In this work, the traditional CPE pattern was changed and greatly simplified in order to be applicable in metal extraction and detection. This method was accomplished in room temperature in 1 min. Non-ionic surfactant Triton X-114 was used as extractant. Octanol worked as cloud point revulsant and synergic reagent. The various parameters affecting the extraction and preconcentration of nickel such as sample pH, 2,2′-Furildioxime concentration, amounts of octanol, amounts of Triton X-114, type of diluting solvent, extraction time, and ionic strength were investigated and optimized. Under optimal conditions, the calibration curve showed an excellent linearity in the concentration range of 2–200 μg L^?1, and the limit of detection was 0.6 μg L^?1 for nickel. The developed method was successfully applied for the determination of nickel in food and water samples. The results showed that, the proposed method can be used as a cheap, rapid, and efficient method for the extraction and preconcentration of nickel from real samples.     

锆涂覆石墨管-无火焰原子吸收测定环境水样中微量银

用锆盐对石墨炉进行涂覆处理,同时又将其作为基体改进剂,有效提高了测定环境水样中银的灵敏度和分析精度,方法快速简便,检出限为2 8×10-12g,相对标准偏差小于6 2%。     

Development of simple and sensitive spectrophotometric method for the determination of bendiocarb in its formulations and environmental samples

Facile, selective and sensitive spectrophotometric method has been developed for the determination of bendiocarb in its insecticidal formulations, fortified water, food grains, agriculture wastewater and agriculture soil samples with prepared reagents. The method was based on alkaline hydrolysis of the bendiocarb pesticide, and the resultant hydrolysis product of bendiocarb was coupled with 2,6-dibromo-4-methylaniline to give a yellow color product with λmaxof457 nmorcouplingwith2, 6−dibromo−4−nitroanilinetoproducearedcoloredproductwithλ_max of474~nmorcouplingwith2, 4, 6−tribromoanilinetoformorangeredcoloredproducthasaλ_max of465 nm.Underoptimalconditions, Beer'slawrangefor2, 6−dibromo−4−methylaniline(DBMA)wasfoundtobe0.6−−14.0~μgmL ^-1, 0.8−−10.0 μgmL ^-1 for2, 6−dibromo−4−nitroaniline(DBNA)and0.4−−10.0 μgmL ^-1 for2, 4, 6−tribromoaniline(TBA).Themolarabsorptivityofthecolorsystemswerefoundtobe4.126~×~10⁴ lmol ^-1 cm ^-1 forDBMA, 3.254×10⁴ l~mol ^-1 cm ^-1 forDBNAand2.812×10⁴ lmol ^-1 cm ^-1 forTBA.Sandell'softhecolorreactionsare0.018 μgcm ^-2(DBMA), 0.052 μgcm ^-2(DBNA)and0.065 μgcm ^-2$ (TBA) respectively. The effect of the non-target species on the determination of bendiocarb was studied. The formation of colored derivatives with the coupling agents is instantaneous and stable for 18 h, 30 h, and 12 h. Performance of the proposed methods were compared statistically in terms Student's F and t-tests with the reported methods.     

Spectrophotometeric determination of trace amounts of Al3+ ion in water samples after cloud point extraction using quinizarin as a complexing agent

In this study, cloud point extraction was used for the preconcentration of Al³⁺ ion after the complex formation with 1,4-dihydroxy-9,10-anthraquinone (Quinizarin [QUIN]), and subsequent analysis by spectrophotometeric method, using Triton X-114 as surfactant. The optimal extraction and reaction conditions were studied (i.e., pH?=?5.5, 0.1 mM QUIN, Triton X-114?=?0.1 % (w/v)), and the analytical characteristics of the method (e.g., limit of detection, linear range, preconcentration, and enrichment factors) were obtained. Linearity was obeyed in the range of 3.33–166.67 ng ml^?1 of Al³⁺ ion. The detection limit of the method was 2.09 ng ml^?1 for Al³⁺ ion. The interference effect of some anions and cations was also tested. The method was applied to determine Al³⁺ ion in water samples.     

Selective and sensitive extractive spectrophotometric determination of micro amounts of palladium(II) in spiked samples: using a new reagent N-ethyl-3-carbazolecarbaxaledehydethiosemicarbazone

N-Ethyl-3-cabazolecarboxaldehydethiosemicarbazone (ECCT) is proposed as a new, sensitive and selective complexing reagent for the separation and extractive spectrophotometric determination of palladium(II) at pH: 4.0 to form a yellowish orange colored 1:1 chelate complex, which is very well extracted in to n-butanol. The absorbance was measured at a maximum wavelength, 410 nm. This method obeys Beer’s law in the concentration range 0.0–6.6 μg mL⁻¹ and the correlation coefficient of Pd(II)-ECCT complex is 0.998, which indicates an excellent linearity between the two variables with good molar absorptivity and Sandell’s sensitivity, 1.647 × 10⁴ l mol⁻¹cm⁻¹, 6.49 × 10⁻³ μg cm⁻², respectively. The instability constant of complex calculated from Edmond’s method, 2.724 × 10⁻⁵ was in good agreement with the value calculated from Asmus’ method 2.624 × 10⁻⁵, at room temperature. The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.839. Edmond’s method was observed to be a more selective method in the presence of EDTA, oxalate and phosphate ions. The method was successfully applied for the determination of Pd(II) in water samples, synthetic mixtures and hydrogenation catalysts, employing an atomic absorption spectrometer for comparing these results.     

A highly sensitive spectrophotometric determination of micro amounts of vanadium(V) in environmental and alloy samples by using 3,4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH)

3, 4-Dihydroxybenzaldehydeisonicotinoylhydrazone was prepared, characterized with spectral analyses and used for developing a new method for the simple, sensitive and rapid spectrophotometric determination of vanadium(V) which gives maximum absorbance at wave length 360 nm. The metal ion gives a yellow colored complex with 3, 4-DHBINH in acetate buffer of pH 5.5 with 1:1 (metal:ligand) composition. The method obeys Beer's law in the range 0.5-5.3 mug mL(-1) of vanadium(V). The molar absorptivity and Sandell's sensitivity were found to be 1.29 x 10(4) L mol(-1) cm(-1) and 0.003949 mug cm(-2) respectively. The correlation co-efficient of the V(V)-3, 4-DHBINH complex was 0.992 which indicated an excellent linearity between the two variables. The repeatability of the method was checked by finding the relative standard deviation (RSD) as 0.424% (n = 5), and its detection limit 0.01677 mug mL(-1) of vanadium(V). The instability constant of the method was calculated by Asmus' method as 4.1666 x 10(-3). The interfering effect of various cations and anions were also studied. The proposed method was successfully applied to the determination of vanadium(V) in environmental samples (water and soil) tobacco leaves and alloy samples. The validity of the method was tested by comparing the results with those obtained using an atomic absorption spectrophotometer.     

环境空气中痕量挥发性有机硫监测分析方法研究

采用预浓缩系统与GC MS联用,建立了环境空气中痕量挥发性有机硫的分析方法,该法用苏玛罐或Tedlar袋采集空气样品在预浓缩系统中经液氮于-160℃冷冻浓缩后,进入GC MS进行分析。甲硫醇、乙硫醇、甲硫醚、乙硫醚、二甲二硫的最低检出限分别为2 0、1 0、1 0、1 0、0 5μg m3。经6次的重复测定,其相对标准偏差小于9 0%。该方法已用于环境空气的测定,取得了令人满意的结果。     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.