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.     

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.     

银离子电极法现场快速测定水中氰化物

利用银离子电极及银氰络合物的平衡指示作用,探讨了在事故现场快速测定水中氰化物的方法.试验表明方法灵敏,操作简单、快速.银离子电极对氰化物浓度从0.04～20mg/L呈线性响应.     

Solid phase extraction of Cd,Pb, Ni,Cu, and Zn in environmental samples on multiwalled carbon nanotubes

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO₃ in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L^?1, respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.     

Evaluation of a standardized method for determining soluble silver in workplace air samples

Several occupational exposure limits and guidelines exist for silver, but the values for each depend on the chemical form of the silver compound in question. In the past, it generally was not possible, without prior knowledge of the work process, to distinguish soluble silver from insoluble silver compounds collected in workplace air samples. Therefore, analytical results were historically reported as total silver. In this study, work was conducted to evaluate a method to differentiate between the quantities of water-soluble silver compounds and total silver collected on filters. The investigation entailed an evaluation of an International Organization for Standardization method to determine soluble silver in airborne particulate matter. The study design incorporated laboratory experiments to evaluate analytical figures of merit, such as selection of appropriate filter media and extraction solution, analytical recovery, and sample stability during storage. Polytetrafluoroethylene (PTFE) filters (2 microm, 37 mm) in opaque cassettes were either spiked with known amounts of silver nitrate or contained a known mass of solid silver nitrate. Results showed that over 90% of the silver was recovered from PTFE filters. Also, field studies were conducted in which workplace air samples were collected in two silver refineries. Some of these samples were analyzed only for soluble silver while others were sequentially extracted and analyzed, first, for soluble silver, then for total silver. The mass fractions of soluble silver, as compared to total silver, were approximately 2% or less. This investigation served to validate an international standard procedure for the determination of soluble silver in workplace air samples.     

Application of nanoclay for preconcentration of ultra trace amounts of palladium in environmental samples prior to its determination by ETAAS

In the present work, a batch preconcentration technique using nanoclay with 5-(4-dimethylaminobenzylidene)rhodanine coupled with electrothermal atomic absorption spectrometry was developed for the separation and determination of trace amounts of palladium. In this method, the sample solution was stirred with nanoclay as an adsorbent. Then, adsorbed palladium was subsequently eluted with HCl in acetone (1.5 mol L^?1) and, finally, this eluate was injected to electrothermal atomic absorption spectrometry. Under the optimum conditions, the limit of detection and linear dynamic range were found to be 2.6 and 10.0–133 ng L^?1 (in original solution), respectively. Furthermore, the enrichment factor and relative standard deviation of seven replicate determinations were 148 and ±5.1 %, respectively. This suggested method is simple, selective and sensitive and can be applied to the extraction and determination of palladium in water, tea leaves, synthetic sample and certified reference material with satisfactory results.     

Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

固相萃取-气相色谱法测定水中硝基氯苯类化合物

建立固相萃取-气相色谱法测定水中15种硝基氯苯类化合物的方法。选用HLB柱为固相萃取柱,选用环己烷∶丙酮(3∶1,V∶V)混合溶剂作洗脱剂,得到方法检出限为0.011～0.040μg/L。空白水样加标回收率为73.6%～119%,相对标准偏差为6.1%～13.9%,精密度和准确度良好。对成分不复杂的实际水样进行测定,加标回收率为64.1%～118%,相对标准偏差为5.8%～15.6%,该方法能够基本满足成分不复杂的环境水体中痕量硝基氯苯类化合物的测定。     

Silica glass modified with flavonoid derivatives for preconcentration of some toxic metal ions in water samples and their determination with ICP-MS

Quercetin (3,3^′,4^′,5,7-pentahydroxyflavone) chemically bonded through pyran rearrangement on modified controlled pore silica glass (QCPSG) with a capacity 0.213 mmol/g was used for solid phase extraction of some toxic metal and metalloid ions. The newly designed QCPSG quantitatively sorbs As(V), Cd(II), Hg(II), and Pb(II) at the pH range 7.5–8.5 after 10 min of stirring. HCl (1 mol L^???1) instantaneously elutes all the metal ions. The sorption capacity of the ion collector is 0.42, 0.46, 0.53, and 0.49 mmol g^???1 for As(V), Cd(II), Hg(II), and Pb(II), respectively, whereas the preconcentration factor is 200. The effect of NaCl, Na₂SO₄, NaF, NaBr, Na₃PO₄, and other interfering salts on the sorption of metal ions (50 μg L^???1) was reported. Analytical detection limits of As(V), Cd(II), Hg(II), and Pb(II) were 4.18, 2.44, 15.86, and 25.00 pg mL^???1, respectively. QCPSG was used in the separation of the investigated metal ions from some natural water samples collected from diverse origins followed by determination by inductively coupled plasma–mass spectrometry. The data were compared with those obtained by the standard methods of determination using atomic absorption (hydride generation, HGAAS and after solvent extraction with ammonium pyrolidine dithiocarbamate/methyl isobutyl ketone). The suggested solid phase extraction method was found accurate with no random error.     

A rapid extractive spectrophotometric determination of copper(II) in environmental samples, alloys, complexes and pharmaceutical samples using 4-N,N(dimethyl)amino]benzaldehyde thiosemicarbazone

Composite samples of septage discharging at the Khirbit As-Samra municipal wastewater treatment plant were analyzed during the period from February to the end of October 2007. Septage showed difference in concentrations of pollutants between summer and winter. The average total chemical oxygen demand (COD) of 6,425 mg/L during summer was 2.16 times greater than that in winter, which is 2,969 mg/L. The total biochemical oxygen demand (5 d) represented 45% of total COD in both winter and summer. Anaerobic biodegradability was 75% after 81 d of digestion at 35°C with a biodegradation rate constant (k) of 0.024 d^???1, which was lower compared with 0.103 d^???1 calculated for wastewater with domestic origin in Jordan. Aerobic biodegradability for septage was 48%??COD basis??after 7 d of digestion at 35°C. The lower anaerobic biodegradation rate of septage compared with that of raw wastewater of domestic origin suggested that septage could have a negative effect on the performance of a domestic wastewater treatment plant if septage discharges are not taken into account in the original design of the treatment plant.     

Leaching potential of silver from nanosilver-treated textile products

The use of nanosilver as an antibacterial agent for various products has increased, especially so, in textiles. This study aims to investigate the potential of Ag to leach from commercial products which contain nano-Ag by using the toxicity characteristic leaching procedure (TCLP) test in accordance with USEPA method 1311. Eight nano-Ag products were purchased from the market. Only those products that are likely to be disposed of in a landfill after end use were selected. Nano-Ag fabrics of different concentrations were also prepared at the laboratory scale, and the TCLP test was performed on them as well. The current study assumes that the new products were discarded without use. The Ag content was quantified by inductively coupled plasma–mass spectroscopy (ICP-MS) and ranged from 0.95 to 2.82 μg/g of the product in the commercial products and from 1.49 to 350 μg/g of the product in the lab-prepared fabrics. In the TCLP test results, Ag concentrations ranged from 4.3 to 64.9 μg/L in the commercial products and from 28.9 to 28,381 μg/L in the lab-prepared fabrics. The results also indicate that the amount of Ag released depends on the type of the fabrics. Additionally, the size of the nano-Ag released in percentage is different for each prepared fabric. This study can help in understanding the amount of Ag released during the disposal phase of a product in a landfill.     

液-液微萃取气相色谱法测定小量水样中痕量硝基苯

使用 FID检测器和 DB-1大口径毛细柱不需要对有机相进行干燥处理。借助 1 0 ml容量瓶和自制的玻璃吸管 ,不必进行两相分离操作 ,萃取和取样操作均可在容量瓶中一次完成。利用有溶剂效应的柱温程序提高了柱效和检测灵敏度。 1 0 ml水样可获得 0 .5 μg/ L的检测下限。方法的精密度优于 4 % ,回收率大于 95 %。     

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.     

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.     

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。     

固相萃取-GC/MS法测定地表水中3-甲基吲哚

采用微球硅胶键合C_(18)固相萃取柱萃取水样中的3-甲基吲哚,并用气质联用法测定,方法在0 mg/L~10.0 mg/L范围内线性良好,方法检出限为0.2μg/L。空白水样3个质量浓度水平的加标回收率为89%~94%,7次测定结果的RSD为2.3%~6.9%。用该方法测定7个实际地表水样品,其中4个地表水样品检出3-甲基吲哚,地表水样的加标回收率为81.5%~97.0%。