Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L⁻¹ of mercury. Standard addition calibration curves using standards between 0 and 20 μg L⁻¹ gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L⁻¹, and from 1.1 to 1.3 μg L⁻¹, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L⁻¹). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L⁻¹ as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).     

Rapid isolation of plutonium in environmental solid samples using sequential injection anion exchange chromatography followed by detection with inductively coupled plasma mass spectrometry

This paper reports an automated analytical method for rapid determination of plutonium isotopes (²³⁹Pu and ²⁴⁰Pu) in environmental solid extracts. Anion exchange chromatographic columns were incorporated in a sequential injection (SI) system to undertake the automated separation of plutonium from matrix and interfering elements. The analytical results most distinctly demonstrated that the crosslinkage of the anion exchanger is a key parameter controlling the separation efficiency. AG 1-×4 type resin was selected as the most suitable sorbent material for analyte separation. Investigation of column size effect upon the separation efficiency revealed that small-sized (2 mL) columns sufficed to handle up to 50 g of environmental soil samples. Under the optimum conditions, chemical yields of plutonium exceeded 90% and the decontamination factors for uranium, thorium and lead ranged from 10³ to 10⁴. The determination of plutonium isotopes in three standard/certified reference materials (IAEA-375 soil, IAEA-135 sediment and NIST-4359 seaweed) and two reference samples (Irish Sea sediment and Danish soil) revealed a good agreement with reference/certified values. The SI column-separation method is straightforward and less labor intensive as compared with batch-wise anion exchange chromatographic procedures. Besides, the automated method features low consumption of ion-exchanger and reagents for column washing and elution, with the consequent decrease in the generation of acidic waste, thus bearing green chemical credentials.     

Presence of nonylphenol, octyphenol and bisphenol a in two aquifers close to agricultural, industrial and urban areas

Active endocrine disruptors (nonylphenol, octylphenol and bisphenol A) were analysed in 2 aquifers and the corresponding surface waters. They are compounds widely used in industrial processes. The objective of this study was to determine the leaching potential of these compounds in groundwaters and to eventually correlate these levels with surface water samples. The areas sampled were agricultural, close to large cities and with an important industrial activity in the surrounding area. Samples (200 mL) were extracted using off-line SPE with polymeric OASIS 60 mg cartridges. Analyses were performed by gas chromatography-mass spectrometry (GC-MS) using selected ion monitoring (SIM) and full scan for quantification and unequivocal identification, respectively. This paper reports the detection limit for the compounds studied (from 0.001 to 0.030 μg L⁻¹), and method performance as regards to linearity (0.01–1.3 μg L⁻¹), reproducibility (less than 9%) and recovery (84 to 95%). The results from a monitoring program revealed the presence of the target compounds in all samples analysed, at levels of 0.07 and 1.9 μg L⁻¹. The presence of these compounds in groundwater was attributed basically to degradation of inert ingredients present in the formulation of many pesticides or to the increasing application of sludge in agricultural practice, although the infiltration of industrial run-off and wastewater disposal cannot be disregarded.     

Cryotrapping gas chromatography-Fourier transform infrared spectrometry in environmental analysis: A pilot study

The potential applicability of cryotrapping gas chromatography-Fourier transform infrared spectrometry in environmental analysis was studied. First results of on-the-flight measurements on pesticides and polynuclear aromatic hydrocarbons show detection limits in the 100–500 pg range. The low-temperature spectra obtained appear to be closely comparable to conventionally recorded spectra. Library search procedures based on existing solid-phase spectra appear to be useful.     

Recent contributions of high resolution gas chromatography to the analysis of environmental hydrocarbons

Analyses of hydrocarbon fractions from different areas of the marine environment are described to illustrate the possibilities and limitations of high resolution gas chromatography (HRGC) in the analysis of environmental samples. Examples are given of dissolved, particulate, and sedimentary hydrocarbons and organochlorine compounds; the importance of an adequate sampling of the marine environment is stressed. HR chromatographic profiles obtained in two columns of low and high polarity (SE-52 and PEG 20M) permit the sources and transport pathways of both natural and anthropogenic hydrocarbons to be traced. Analysis of tissues of marine mammals, which metabolize or excrete many of the biogenic and petrogenic hydrocarbons present in other areas of the marine environment, may provide an opportunity to obtain relatively clean profiles of many anthropogenic compounds of interest. The plotting of mass chromatograms from data compiled by COM-GC-MS remains the most appropriate method for the conclusive indentification of these compounds.     

High-throughput quantification of palladium in water samples by ion pair based-surfactant assisted microextraction

A novel method for the determination of palladium as a metal ion model was developed by ion pair based surfactant-assisted microextraction (IP-SAME) and inductively coupled plasma-optical detection (ICP-OES). In this methodology, a cationic surfactant was used in extraction process. It has two fundamental functions: (1) the formation of an emulsified phase and (2) the ion pair formation with Pd(II) in the presence of iodide ions and making PdI₄²⁻$\text{Pd}{{\text{I}}_4}^{2-}$ extractable into organic phase (active microextraction). The effective parameters on the extraction recovery such as the types of extraction solvent and the surfactant, surfactant concentration, KI amount and HCl concentration of the sample were investigated and optimized. In the proposed approach, tetradecyl trimethyl ammonium bromide (TTAB) was used as emulsifier and ion pairing agent, and 1-octanol was selected as extraction solvent. Under the optimum conditions, the enhancement factor as large as 146 was obtained. The detection limit for palladium was 0.2 μg L⁻¹, and the relative standard deviation (RSD) was 4.1% (n = 5, C = 10.0 μg L⁻¹). The proposed method was applied for extraction and determination of palladium in different water samples.     

Determination of Four Nitrofuran Metabolites and Chloramphenicolin Biological Samples Using Enzyme-Linked Immunosorbent Assay

A pretreatment method was developed for the determination of four nitrofuran metabolites and chloramphenicol in pork, chicken, fish, and shrimp. Homogenized samples were hydrolyzed and derivatized with 2-nitrobenzaldehyde. Extraction was performed using ethyl acetate followed by purification of the extract by hexane. Lastly, the ethyl acetate was dried under nitrogen and the residue was redissolved for analysis. The performance of the method was satisfactory for all drugs tested at contamination levels close to or below the relevant European Union maximum levels permitted. The limits of detection (LODs) of the method were 0.025–0.13 ng/g. Recoveries higher than 72.0% were obtained for all drugs tested, and the coefficient of variation was less than 15%. Results from analysis of unknown samples by the developed ELISA were similar to those obtained by a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method.     

Determination of maize and grain herbicides and their transformation products in soil by use of soil column extraction then liquid chromatography with tandem mass spectrometry

Summary A multiresidue method has been developed for identification and quantitation of the herbicides most commonly used in cultivation of maize and grain, and of their transformation products, in soil samples. The analytes were isolated by soil column extraction (SCE) and the extracts were purified by use of a Carbograph-1 cartridge. Analysis was performed by liquid chromatography coupled with tandem mass spectrometric detection (LC-TISP-MS-MS) in negative-ion mode. To optimize the extraction conditions affecting the performance of SCE, e.g. the extracting solvent used, temperature, extracting volume, and solvent flow rate, were studied. To evaluate the matrix effect in SCE, recovery experiments were performed on soil samples, with different physical and chemical characteristics, fortified with the 100 ng g⁻¹ of the target compounds. Recovery data were satisfactory and the method detection limits were between 3 and 100 ng g⁻¹, depending on the compound.     

导数原子吸收光谱法直接测定水中痕量元素

提出了导数原子吸收光谱法直接测定水中痕量元素的方法,它是基于测定导数原子吸收值,即吸光度随时间的变化率来提高原子吸收分析灵敏度的一种新技术。方法具有简单快速,灵敏度高,检出限低的优点,可直接用于水质的常规分析。     

低温吹扫捕集-气相色谱-火焰光度法测定南极水样中的甲基锡形态

:建立了低温吹扫捕集 -气相色谱 -火焰光度法快速测定甲基锡形态的新方法。在 p H 5的 HAc- Na Ac缓冲溶液中 ,加入 1 m L浓度为 30 g/L的硼氢化钾 ,一甲基锡 ,二甲基锡和三甲基锡分别转化成相应的氢化物 ,直接被低温吹扫捕集到冷阱毛细管中 ,经过气相色谱分离 ,用火焰光度检测器检测。方法的最低检出限分别为一甲基锡 1 8ng·L-1,二甲基锡 1 2 ng· L-1,三甲基锡 3ng·L-1,相对标准偏差小于 3%。方法已用于测定南极水样中的甲基锡形态。