Analysis of Pb in water samples with plastic scintillation resins

²¹⁰Pb is a radioactive lead isotope present in the environment as member of the ²³⁸U decay chain. Since it is a relatively long-lived radionuclide (T_1/2 = 22.2 years), its analysis is of interest in radiation protection and the geochronology of sediments and artwork. Here, we present a method for analysing ²¹⁰Pb using plastic scintillation resins (PSresins) packaged in solid-phase extraction columns (SPE cartridge). The advantages of this method are its selectivity, the low limit of detection, as well as reductions in the amount of time and reagents required for analysis and the quantity of waste generated. The PSresins used in this study were composed of a selective extractant (4′,4″(5″)-Di-tert-butyldicyclohexano-18-crown-6 in 1-octanol) covering the surface of plastic scintillation microspheres. Once the amount of extractant (1:1/4) and medium of separation (2 M HNO₃) were optimised, PSresins in SPE cartridges were calibrated with a standard solution of ²¹⁰Pb. ²¹⁰Pb could be fully separated from its daughters, ²¹⁰Bi and ²¹⁰Po, with a recovery value of 91(3)% and detection efficiency of 44(3)%. Three spiked water samples (one underground and two river water samples) were analysed in triplicates with deviations lower than 10%, demonstrating the validity of the PS resin method for ²¹⁰Pb analysis.     

Extractive scintillating resin for 99Tc quantification in aqueous solutions

A method utilizing extractive scintillating resin for ⁹⁹Tcmonitoring in aqueous solutions is presented. These extractive scintillatorscombine analyte selective uptake and scintillating properties to produce dualfunctionality analytical resins. These resins were produced by (1) co-locatedextraction chromatographic resin and plastic scintillating beads, (2) immobilizingfluors in macroporous polystyrene supports to which chains of monomethylatedpolyethylene glycol have been grafted and (3) co-immobilizing organic scintillatingfluors and a quaternary ammonium extractant (Aliquat-336) within macroporousacrylic and polystyrene supports. The first and third resins selectively extractpertechnetate ions from dilute acid whereas the second resin selectively extractspertechnetate ions from high ionic strength solutions. These resins were utilizedin ~0.20 ml pore volume columns while ⁹⁹Tc was continually monitoredwith commercially available scintillation detection systems. Manual and automatedmicrofluidics were used to deliver sample and reagent solution for loadingand elution of the ⁹⁹Tc. The detection efficiencies were determinedto be 45 and 70% for acrylic and polystyrene based resins, respectively, andindependent of extractant. Minimum detectable ⁹⁹Tc concentrationusing the Aliquat-336/acrylic-based resin was 6.2 Bq . l –1 for a 50-mlsample and 30-minute count time. The new methodology was applied towards analysisof contaminated groundwater samples and nuclear waste simulants.     

Dynamic ultrasound-assisted extraction coupled on-line with solid support derivatization and high-performance liquid chromatography for the determination of formaldehyde in textiles

An on-line method was developed for the extraction, derivatization and determination of formaldehyde in textile samples. Formaldehyde was first extracted with water by ultrasound assisted, and directly introduced into a derivatization column which was packed with a moderately sulfonated cation-exchange resin. The resin used as solid support for the derivatization was charged with 2,4-dinitrophenylhydrazine (DNPH) previously. The formaldehyde DNPH derivative was eluted with the chromatographic mobile phase into an analytical column for the separation, and then monitored by UV detector. The maximum extraction yield was achieved when the extraction vessel was located at 10mm from the ultrasonic source and 10mg textile sample was extracted with 5mL pure water at a flow rate of 1.0mLmin(-1) at 50 degrees C. The detection limit of the proposed method was 0.06mgkg(-1). This method was applied to the determination of formaldehyde in different textile samples, and compared with the state standard method (off-line spectrophotometry) used in China. The similar contents of formaldehyde were obtained for most samples by the two methods, but little higher for some samples obtained by the proposed method. The average relative standard deviation (RSD) obtained by the on-line method was 3.2% which is lower than 29.5% obtained by the standard method.     

β-Cyclodextrin-polyurethane polymer as solid phase extraction material for the analysis of carcinogenic aromatic amines

β-Cyclodextrin-polyurethane (β-CDPU) polymer was synthesized by the reaction of β-cyclodextrin with hexamethylene diisocyanate in dry dimethylformamide and used as a sorbent for the solid phase extraction (SPE) of carcinogenic aromatic amines from water. The polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and particle size analysis. The separation and quantification was performed by Liquid chromatography with RP-C₁₈ column and diode array detection using standard arylamines for quantification. When compared with commercially available sorbents, β-CDPU gave better recovery for the aromatic amines. From the variation of pH of the extractant from 4.0 to 8.5 recovery was highest at pH 8.5. The breakthrough volume has been ascertained to be 100 ml for 200 mg of the resin. The new SPE material offers better recovery and estimation of banned arylamines.     

金属硫蛋白异构体及亚型异构体的液相色谱分离与质谱鉴别

建立了金属硫蛋白(MT)异构体及亚型异构体的色谱分离与质谱鉴别方法。将金属硫蛋白混合物通过弱阴离子DEAE Sephadex A-25离子交换柱,结合离线电感耦合等离子体质谱(ICP-MS)对锌诱导金属硫蛋白的两个异构体MT-1和MT-2进行分离和检测;利用Sephadex G-25凝胶排阻色谱柱对得到的两个金属硫蛋白异构体进行脱盐;探索脱盐后的金属硫蛋白异构体在不同色谱条件下的C18反相色谱柱上的保留行为,进而实现各个亚型异构体的分离;通过在线电喷雾质谱检测实现了对金属硫蛋白各个亚型异构体的鉴别。结果表明,通过优化色谱条件,由离子交换色谱及凝胶排阻色谱得到的金属硫蛋白各亚型异构体在酸性条件下均得到了良好的分离,质谱检测结果与前人的文献报道结果一致。该方法可使金属硫蛋白各异构体均达到最佳的分离效果。     

Chemically modified polymeric sorbents for sample preconcentration

Solid-phase extraction is an attractive alternative in sample preparation because it overcomes many drawbacks of liquid-liquid extraction and makes on-line determination possible by hyphenation with chromatographic techniques. Driven by the need for more effective and more selective sorbents, advances in solid-phase extraction include the development of new materials. This paper describes different types of chemically modified sorbents for the solid-phase extraction of compounds from aqueous samples. Chemical introduction of different functional groups into a polymeric resin improves the efficiency of solid-phase extraction by providing better surface contact with the aqueous samples; also, these sorbents have a greater capacity than the typical solid-phase materials for polar compounds have. The most important new sorbents are the chemically modified resins based on styrene-divinylbenzene copolymers. Preparation of these new sorbents is described, and advantages and drawbacks of off-line procedures and on-line procedures are also discussed. Applications for off-line and on-line chromatographic determinations of polar compounds are presented.     

Improved high-performance liquid chromatographic procedure for the determination of chlormethiazole levels following solid-phase extraction from plasma

An improved high-performance liquid chromatographic method for the determination of chlormethiazole levels in plasma is described. The drug is extracted from plasma using commercially available reversed-phase extraction columns; recovery values obtained using Sep-Pak C18 and Bond Elut C1, C2, C4, C6, C8, C18 columns are compared. Separation was achieved by reversed-phase chromatography, using a mobile phase consisting of 0.025 M sodium acetate buffer, pH 4.5-acetonitrile (67:33) at a flow-rate of 1.6 ml/min in conjunction with a 15-cm Jones Chromatography Apex ODS column. The analytical column was protected by a Waters Assoc. Guard-Pak module containing a Guard-Pak CN insert. Using ultraviolet detection at 254 nm chlormethiazole levels in the region of 50 ng/ml can be measured with only 500 microliter of plasma.     

High-performance liquid chromatographic analysis of 2',3'-dideoxyinosine in biological samples

A high-performance liquid chromatographic analysis for the anti-AIDS drug 2',3'-dideoxyinosine (ddI) in rat plasma and urine, with a limit of detection of 0.2 microgram/ml and requiring a sample size of 100 microliters is described. Diluted plasma or urine samples were extracted using a C18 solid-phase extraction column. Retention of ddI on more polar solid-phase extraction columns was insufficient for sample clean-up. This method is useful for pharmacokinetic studies of ddI in small rodents.     

Chromatography of bis-(3-sulfopropyl) disulfide and its breakdown products by HPLC coupled with electrochemical detection

A chromatographic method for the detection of bis-(3-sulfopropyl) disulfide (SPS), a common additive in acidic copper plating baths, and its breakdown products is demonstrated. The detection scheme involves a combination of solid-phase extraction for sample pre-treatment, C(18) reversed-phase high-performance liquid chromatography column for separation, and electrochemical sensor for detection of all non-fully oxidized sulfur-containing compounds. We were able to achieve an effective separation and accurately assign chromatographic peaks to all detectable species. Owing to a high sensitivity of the utilized electrochemical detector, detection in low parts per billion range was possible. This can prove crucial for plating bath control, since minute amounts of certain by-products significantly affect the bath performance.     

New SPE column packing material: Retention assessment method and its application for the radionuclide chromatographic separation

The preparation of the OASIS?-HLB sorbent based solid phase extraction (SPE) resins and their application for the ¹⁷⁷Lu radioisotope separation were investigated. Di-(2-ethylhexyl) orthophosphoric acid (HDEHP) impregnated OASIS-HLB sorbent based SPE resins (OASIS-HDEHP) were successfully developed from this investigation. The wettable porosity structure of the moderately extractant impregnated OASIS-HDEHP resins is favorable for the effective diffusion of polar and ionic solutes giving good separation performance. Its good wetting ability offers ease of packing into conventional chromatographic columns. Their off-gassing-free operation makes OASIS-HDEHP columns good for long term use with highly consistent elution dynamics (several dozens of separations perfectly achievable on the same column). The simple method for the capacity factor (k’) evaluation was developed to facilitate the characterization of the SPE chromatographic resin column. A competent procedure using OASIS-E30RS resin (one member of the OASIS-HDEHP resin group) for the separation of no-carrier added (n.c.a) ¹⁷⁷Lu from the bulk amount of Yb target was developed. This separation procedure has showed very good performance with several prominent advantages such as the much shorter separation time (5–6 hours) and high reproducibility. Its high adsorption capacity for Yb and Lu makes it ideal for the separation of the bulky sample (50 mg Yb target for the 20 g weight resin column) for the production of the several Ci of ¹⁷⁷Lu radioactivity.     

A microplate solid scintillation counter as a radioactivity detector for high performance liquid chromatography in drug metabolism: validation and applications

Sensitive radioactivity detection following high performance liquid chromatography (HPLC) separation remains a challenge in many drug metabolism studies with radiolabeled compounds. In this work, solid scintillation counting (SSC) after fraction collection into 96-well plates was evaluated as an off-line radioactivity detection method, in comparison with conventional liquid scintillation counting (LSC). The impact of counting time and biological matrix on the quantification of radiolabeled metabolites and parent drug in samples from animal and human absorption, distribution, metabolism and excretion (ADME) studies was investigated. Three different approaches were used to test whether reliable quantification by off-line SSC detection, which requires an approximately constant counting yield during the entire chromatographic run, can be realized: (i) the measurement of radioactivity-spiked biological blank samples without HPLC separation as an extreme case of biological background, (ii) the measurement of radioactivity-spiked HPLC fractions of biological blank samples and (iii) the comparison of radiochromatograms obtained by off-line SSC and LSC of real samples from ADME studies with radiolabeled compounds. Situations in which variations in SSC yield during an HPLC run are likely to lead to significant errors in quantitation were identified and are discussed. However, examples from a number of animal or human ADME studies showed that in the majority of cases off-line SSC provides very similar quantitative data, compared with the reference method of off-line LSC radioactivity detection. Approaches for validation of the off-line SSC approach in critical cases are discussed. The main advantages of off-line SSC, compared with off-line LSC, are lower detection limits and a substantially higher throughput. Several applications of off-line SSC detection in ADME studies are shown.     

One-step SFE-plus-C(18) selective extraction of low-polarity compounds,with lipid removal,from smoked fish and bovine milk

Co-extraction of lipid materials is the major source of interference in determinations of low-polarity compounds in many biological matrixes. "SFE-plus-C(18)", a recently developed supercritical fluid extraction method employing C(18) adsorbent in the extraction chamber, can enable selective extraction of low-polarity compounds in lipid-rich biological matrixes without a cleanup step. This study reports the application of the SFE-plus-C(18) method to the quantification of: 1. polycyclic aromatic hydrocarbons (PAH) in commercially purchased smoked fish; and 2. anti-cancer agents cyclophosphamide (CP) and suberoylanilide hydroxamic acid (SAHA) spiked into homogenized whole bovine milk.Over the course of SFE-plus-C(18)extraction, indigenous lipids are preferentially retained on the C(18) adsorbent. Compared with the conventional method, only 8-15% of the lipids in the smoked fish sample, and only 6-18% of the lipids in the milk sample, were co-extracted by SFE-plus-C(18). This reduction in the quantity of background lipids significantly improved chromatographic separations, retarded deterioration of the column, and dramatically improved the ability to quantify PAH present at trace levels in smoked fish by GC-MS. Using the SFE-plus-C(18) method, ten targeted PAH were detected in the range 9.5-13.5 ng g(-1) in the smoked fish sample. Compared with these levels, PAH extractions by use of conventional SFE gave values that were lower by 38-86%. Recoveries of CP and SAHA spiked into milk were close to 100% in both SFE-plus-C(18)and conventional SFE, where the lipid background during the chromatographic elution of CP and SAHA was not so severe.     

Ion chromatographic analysis of cyanate in gold processing samples containing large concentrations of copper(I) and other metallocyanide complexes

An ion chromatographic (IC) method was developed for the determination of cyanate in gold cyanidation samples containing large concentrations of metallo-cyanide complexes. The analysis was performed on a Waters HC IC-Pak A anion-exchange column with an anthranilic acid eluent, with detection achieved using indirect UV at 355 nm. Two procedures were developed for removal of the metallo-cyanide complexes prior to the IC analysis. The first was a manual off-line method which used solid-phase extraction cartridges containing a strong anion-exchange resin to trap the complexes and to then enable determination of cyanate without interference. In the second approach, an automated on-line method was developed which used an anion-exchange guard column to trap the complexes and a column switching valve to allow backflushing of the cyanate from the guard column. This enabled the total analysis to be performed in a time of 10–14 min, depending on the sample composition. Finally, a comparison of results obtained by the standard Kjeldahl nitrogen method for cyanate and the IC method revealed an interference in the Kjeldahl method for samples containing large concentrations of Cu(I)-cyanide complexes.     

Flow-Injection Determination of Trace Antimony in Natural Waters with Extraction–Chromatographic Preconcentration

A procedure was developed for the flow-injection spectrophotometric determination of trace antimony in natural waters. The flow extraction preconcentration step involved the extraction of antimony(V) complex associates with basic dyes in an extraction–chromatographic column and the chromatomembrane separation of the extract from the aqueous phase. The detection limit was 1 g/L for a 20-mL sample using a (1 : 5) methyl isobutyl ketone–carbon tetrachloride mixture as an extractant.     

Investigation on the extraction of strontium ions from aqueous phase using crown ether-ionic liquid systems

The extraction of strontium ions using DCH18C6 as the extractant and various ionic liquids (ILs) as solvents has been investigated. The distribution ratio of Sr²⁺ can reach as high as 10³ under certain conditions, much larger than that in DCH18C6/n-octanol system. The extraction capacity depends greatly on the structure of ionic liquids. In IIs-based extraction systems, the extraction efficiency of strontium ions is reduced by increasing the concentration of nitric acid and can also be influenced directly by the presence of Na⁺ and K⁺ in the aqueous phase. It is confirmed that the extraction proceeds mainly via a cation-exchange mechanism.     

The application of novel extraction chromatographic materials to the characterization of radioactive waste solutions

A simple method for the separation and preconcentration of radiostrontium from acidic nuclear waste solutions for subsequent determination is described. The method involves passage of the waste solution, acidified to at least 2M with nitric acid, through an extraction chromatographic column consisting of a 1M solution of bis-4,4(5)[(t-butyl)cyclohexano]-18-crown-6 in 1-octanol sorbed on an inert polymeric substrate, which preferentially retains strontium. The strontium may then be stripped from the column with a small volume of either dilute (0.05M) nitric acid or water. Actinides present are removed quantitatively prior to strontium separation by passage of the sample through an actinide-specific extraction chromatographic column.Work performed under the auspices of the Office of Basic Energy Sciences, Division of Chemical Sciences, U. S. Department of Energy, under contract number W-31-109-ENG-38.     

EXAFS investigations of strontium complexation by a polymer-supported crown ether

Extended X-ray absorption fine-structure (EXAFS) measurements have been used to probe the coordination environment of strontium ion sorbed from aqueous nitric acid solutions on an extraction chromatographic resin comprising a macrocyclic polyether dispersed on a polymeric support. The strontium EXAFS of the metal ions sorbed onto the resin are consistent with a 1:1:2 strontium:crown ether:nitrate stoichiometry in which the strontium is enveloped in the crown ether ring and both nitrate anions are coordinated to the strontium as bidentate ligands. This is the same structure and stoichiometry observed for complexes in liquid-liquid extraction when the macrocyclic polyether is dissolved in a diluent with low water miscibility like 1-octanol.     

Automatic in-tube SPME and fast liquid chromatography: a cost-effective method for the estimation of dibuthyl and di-2-ethylhexyl phthalates in environmental water samples

A 80-cm length commercially available capillary coated with 95% polydimethylsiloxane and 5% polydiphenylsiloxane (TBR-5) was employed to carry out on-line extraction and preconcentration of dibuthyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) in the chromatographic system. The coated capillary was placed between the sample injection loop and the injection needle of an autosampler. Variables affecting the automatic in-tube solid-phase microextraction (SPME) were optimized. A Genesis C₁₈ (5 cm × 4.6 mm i.d., 4 μm particle size) was employed as analytical column. The achieved limits of detection by use of diode array detection were 1 and 2.5 μg L⁻¹, respectively. The proposed conditions have been applied to determine those compounds at low ppb levels (≤250 μg L⁻¹) in aqueous samples. No matrix effect was found, and recoveries between 85 and 115% were obtained. The precision of the method was good, and the achieved intra- and inter-day variation coefficients were between 5 and 20%. The analysis time per sample was 20 min and any off-line pre-treatment of the samples was needed. The taken sample volume was 100 μL. Data on the application of the described method to the analysis of different water samples are presented.     

液-液萃取气相色谱法测定地表水中痕量苯酚

建立了液-液萃取气相色谱法测定地表水中痕量苯酚的方法。用盐酸调节水样至pH2左右,以二氯乙烷-乙酸乙酯(体积比为2∶1)混合溶液为萃取剂,以CD-5色谱柱进行分离,氢火焰离子化检测器检测苯酚的含量。苯酚的质量浓度在1.00~20.0μg/L范围内与其色谱峰面积呈良好的线性关系,线性相关系数r=0.999 3,检出限为0.03μg/L。样品加标回收率为93.0%~97.0%,测定结果的相对标准偏差小于2%(n=7)。该方法检出限低,精密度和准确度高,操作简便,适用于地表水中微量苯酚的分析。     

Determination of benzo[a]pyrene tetrols by column-switching capillary liquid chromatography with fluorescence and micro-electrospray ionization mass spectrometric detection

The present work displays capillary liquid chromatographic column switching methodology tailored for determination of benzo[a]pyrene tetrol isomers in biological matrices using on-line fluorescence and micro-electrospray ionization mass spectrometric detection. A well-established off-line crude solid phase extraction procedure was used in order to make the method compatible with several biological matrices. The solid phase extraction eluates were evaporated to dryness, redissolved in 1.0 ml methanol:water (10:90, v/v), loaded onto a 0.32 mm I.D. x 40 mm 5 microm Kromasil C(18) pre-column for analyte enrichment and back-flushed elution onto a 0.30 mm I.D. x 150 mm 3.5 microm Kromasil C(18) analytical column. The samples were loaded with a flow rate of 50 microl min(-1) and the tetrols were separated at a flow rate of 4 microl min(-1) with an acetonitrile:10 mM ammonium acetate gradient from 10 to 90%. A sample loading flow rate up to 50 microl min(-1) was allowed. The fluorescence excitation and emission were set to 342 and 385 nm, respectively, while mass spectrometric detection of the benzo[a]pyrene tetrols was obtained by monitoring their [M - H](-) molecular ions at m/z 319. The method was validated over the concentration range 0.1-50 ng ml(-1) benzo[a]pyrene tetrols in a cell culture medium with 100 microl injection volume, fluorescence detection and the first eluting tetrol isomer as model compound, resulting in a correlation coefficient of 0.993. The within-assay (n= 6) and between-assay (n= 6) precisions were determined to 2.6-8.6% and 3.8-9.6%, respectively, and the recoveries were determined to 97.9-102.4% within the investigated concentration range. The mass limit of detection (by fluorescence) was 3 pg for all the tetrol isomers, corresponding to a concentration limit of detection of 30 pg ml(-1) cell culture medium. The corresponding mass spectrometric mass limits of detection were 4-10 pg, corresponding to concentration limits of detection of 40-100 pg ml(-1) cell culture medium.