Speciation of magnesium in rat plasma using capillary electrophoresis-inductively coupled plasma-atomic emission spectrometry

A new method for speciation analysis of magnesium species and quantification of free magnesium concentrations in rat plasma was developed by on-line coupling of CE with inductively coupled plasma-atomic emission spectrometry (ICP-AES). Baseline separation of seven magnesium species was achieved by using a 120 cm (100 microm internal diameter) fused-silica capillary, a 20 kV separation voltage and a solution of 50 mmol/L NaAc-HAc (pH 5.5) as electrolyte buffer. CE-ICP-AES analysis of a rat plasma sample showed the presence of seven magnesium species, one of which was identified as free Mg2+ ion by spiking a Mg2+ standard; the migration time of the Mg2+ peak in the standard and the spiked sample matched with each other. One protein-bound magnesium species in rat plasma is associated with albumin, and the other three species are combined with globulin. The concentration of free magnesium in the plasma was 14.0 mg/L. The other six magnesium species were estimated to be 4-15 mg/L. RSDs of migration time and peak area for the magnesium species from ten replicates were less than 5%. The developed method was also applied to speciation analysis of magnesium species in spiked plasma samples. The recoveries of the free magnesium species in four samples ranged from 95.8 to 103.8%.     

毛细管电泳-电感耦合等离子体质谱法测定藻类中6种不同形态的砷化合物

建立了一种利用毛细管电泳与电感耦合等离子体质谱联用技术(CE-ICP-MS)分析检测6种不同形态砷化合物的方法。详细研究了缓冲溶液的种类、pH值和浓度,分离电压以及进样时间等因素对6种砷化合物的分离度、灵敏度和重现性等的影响。结果表明,在最佳条件下,三价砷(As3+)、一甲基砷(MMA)、二甲基砷(DMA)、五价砷(As5+)、砷胆碱(AsC)和砷甜菜碱(AsB)6种化合物在25 min内得到完全分离。6次平行测定中,6种砷化合物峰面积的相对标准偏差(RSD)为3%～5%,检出限(以As计)(3倍信噪比)为0.08～0.12 μg/L。应用该方法成功地对海带中6种砷化合物进行了分析,回收率为90%～103%。该方法具有耗时短、灵敏度高、样品消耗量少、稳定性好等优点,可用于藻类样品中不同形态砷化合物的分析。     

Speciation analysis of arsenic in Mya arenaria Linnaeus and Shrimp with capillary electrophoresis-inductively coupled plasma mass spectrometry

An improved sheath-flow interface used to couple capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) and a microwave-assisted extraction used to extract each arsenic species in seafood were developed in this work. The improved sheath-flow interface completely avoids laminar flow in CE capillary caused by the suction from ICP-MS, makes electric supply more stable in CE, and transports analyte solution to ICP-MS easily and more efficiently. CE-ICP-MS coupled with our interface have two quantitative analysis modes: continuous sample-introduction mode and collective sample-introduction mode. The collective sample-introduction technique greatly reduced the dead volume of interface to approximately zero, obviously avoided the excessive dilution of analyte, and eventually led to a much lower detection limit and a much better electrophoretic resolution. This was demonstrated by the better symmetry and narrow peak widths (10-12 s) and much lower detection limits (0.030-0.042 μg/L) of four species of arsenic determined with collective sample-introduction mode.With the help of this improved sheath-flow interface and the microwave-assisted extraction, we have successfully separated and determined four arsenic species, As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in dried Mya arenaria Linnaeus and Shrimp samples using CE-ICP-MS within 10 min with a relative standard deviation of 2-4% (peak areas, n = 6) and a recovery of 96-105%.     

Determination of fission products in nuclear samples by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS)

Determination of fission products and of their isotopic composition is of high importance for the characterisation and complete inventory of nuclear fuels. Radiometric and mass spectrometric methods, which are currently used, enable only an incomplete determination of the fission products. Radiometric methods cannot be applied to all fission products and mass spectrometric methods are hindered by the existence of isobaric interferences, therefore a previous chemical separation is required before mass spectrometric analysis. Capillary electrophoresis (CE) has been coupled with inductively coupled plasma mass spectrometry (both ICP-QMS and ICP-SFMS). Typical detection limits of 6 ng/mL and 4 pg/mL for caesium as well as 8 ng/mL and 7 pg/mL for lanthanides have been obtained by CE-ICP-QMS and CE-ICP-SFMS, respectively. In addition to these very low detection limits, the procedures present the advantages to be fast (6 min for caesium and 13 min for lanthanides, respectively), to require a low microliter range sample volume and a nanoliter range injection volume. The radiation dose for the personnel as well as the volume of nuclear liquid wastes generated during the measurements are consequently reduced.The procedures have been applied to nuclear samples from PUREX process and leachates from MOX fuels.     

Analysis of ultratrace triorganotin compounds in aquatic organisms by using capillary electrophoresis-inductively coupled plasma mass spectrometry

A microwave-assisted extraction used to extract trace triorganotin from aquatic organisms and a sensitive analytical method for the determination of ultratrace triorganotin (namely trimethyltin, triethyltin, tripropyltin and tributyltin) with capillary electrophoresis-inductively coupled plasma mass spectrometry were firstly described in this study. The extraction method is simple, effective and can be used to extract trace triorganotin in aquatic organisms within several min. The analytical method has a much lower detection limit of 0.2-0.7 ng Sn/mL for triorganotin compounds, and can be used to determine trace triorganotin in aquatic organisms directly without any derivatization and preconcentration. Using above methods, we have successfully determined trimethyltin, triethyltin, tripropyltin and tributyltin in dried Mya arenaria Linnaeus and Corbicula fluminea within 17 min with a recovery of 93-104% and a RSD (relative standard deviation, n = 6) of 2-5%. Our results showed that dried M. arenaria Linnaeus contained an extremely high tributyltin of 5.1 μg Sn/g dried weight, indicating that it may be a good biomarker for the organotin pollution in ocean.     

A new interface used to couple capillary electrophoresis with an inductively coupled plasma mass spectrometry for speciation analysis

In this work, a novel and high-efficiency interface has been developed in coupling CE with inductively coupled plasma MS (ICPMS). The interface completely avoids laminar flow in CE capillary caused by the suction of nebulizer, and can be easily and stably operated at room temperature with high analyte transport efficiency to ICPMS. The new interface has a liquid dead volume smaller than 5 nL, which was much smaller than those (65-2500 microL) reported previously for other interfaces. All above features led to a higher sensitivity and a better electrophoretic resolution for CE-ICPMS coupled with this new interface. With the help of this new interface, we have successfully separated and determined five species of arsenic, As(III), As(V), monomethylarsonic acid, dimethylarsinic acid and p-aminophenylarsonic acid using CE-ICPMS within 11 min with a detection limit of 0.046-0.075 ng/mL and an RSD of 2-6% (n=6).     

Speciation analysis of arsenic and selenium compounds in environmental and biological samples by ion chromatography-inductively coupled plasma dynamic reaction cell mass spectrometer

An inductively coupled plasma mass spectrometer (ICP-MS) was used as an ion chromatographic (IC) detector for the speciation analysis of arsenic and selenium. The arsenic and selenium species studied included arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), selenite [Se(IV)] and selenate [Se(VI)]. Gradient elution using (NH₄)₂CO₃ and methanol at pH 9 allowed the chromatographic separation of all species in less than 12 min. Effluents from the IC column were delivered to the nebulization system of ICP-DRC-MS for the determination of arsenic and selenium. The potentially interfering ³⁸Ar⁴⁰Ar⁺ and ⁴⁰Ar⁴⁰Ar⁺ at the selenium masses m/z 78 and 80 were reduced in intensity by approximately 3 orders of magnitude by using 0.6 mL min⁻¹ CH₄ as reactive cell gas in the DRC while an Rpq value of 0.3 was used. Meanwhile, arsenic was determined as the adduct ion ⁷⁵As¹²CHH⁺ at m/z 89, which is more sensitive than ⁷⁵As. The limits of detection for arsenic and selenium were in the range of 0.002–0.01 ng mL⁻¹ and 0.01–0.02 ng mL⁻¹, respectively, based on peak height. The relative standard deviation of the peak areas for five injections of 5 ng mL⁻¹ As and Se mixture was in the range of 2–4%. The concentrations of arsenic and selenium species have been determined in urine samples collected locally. The major As and Se species in urines were AsB, DMA and probably selenosugar at concentration of 20–40, 15–19 and 17–31 ng mL⁻¹, respectively. The recoveries were in the range of 94–105% for all the determinations. This method has also been applied to determine various arsenic compounds in two fish samples. In this study, a simple and rapid microwave-assisted extraction method was used for the extraction of arsenic compounds from fish. The arsenic species were quantitatively leached with an 80% v/v methanol solution in a focused microwave field during a period of 5 min.     

Iodine speciation in biological samples by capillary electrophoresis-inductively coupled plasma mass spectrometry.

A hyphenation of capillary electrophoresis (CE) to inductively coupled plasma mass spectrometry (ICP-MS) was employed for the speciation of iodine. The separation method used a buffer sandwich of phosphate (pH 2.3), NaOH, sodium dodecyl sulfate (SDS) and borate buffer (pH 8.3) for stacking, aiming at sufficient separation of iodide, iodate, thyroxine (T4) and triiodothyronine (T3). These four iodine species were separated within 15 min and subsequently detected during a pressure-driven detection step (baseline-separated) at 19.5, 29.1, 36.6 and 42.2 s. The detection limits were determined at 0.08 microg I/L (iodide), 0.3 microg I/L (iodate), 3.5 microg I/L (thyroxine) and 2.5 microg I/L (triiodothyronine). This method was applied on iodine speciation in human serum ("healthy" and after thyroid gland operation) and urine. The serum from the healthy person contained iodide (13 microg I/L), T4 (61 microg I/L) and T3 (7.5 microg I/L), whereas the serum from the thyroid-operated person lacked T3. As no "free" I-hormones are known in serum, the role of the thyroid hormone binding globulin (TBG) was investigated. We found that spiked T4 or T3 immediately bound to TBG. Investigations on human urine showed only a peak for iodide.     

Determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry

The determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS) was investigated. Both capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) modes of operation were studied. The optimal separation of four cobalamin species (cyanocobalamin, hydroxocobalamin, methylcobalamin, and 5′-deoxyadenosylcobalamin) and a potentially harmful corrinoid analogue (cobinamide dicyanide) was obtained using CZE at a pH of 2.5. Both 20 mM phosphate and 20 mM formate buffers were used with success, although the formate buffer provided improved resolution. The CZE-ICP-MS method was used to quantify cyanocobalamin in a vitamin supplement and the analytical results were in good agreement (±5%) with values obtained by ICP-MS for total Co levels. The solution detection limits for cobalamins using CZE-ICP-MS were approximately 50 ng/ml. MEKC was found to be useful for the screening of vitamin preparations because it provided a rapid means of distinguishing cyanocobalamin (the form most commonly used in vitamin preparations) from free cobalt. The separation of free cobalt and cyanocobalamin using MEKC was achieved in less than 10 min.     

Speciation of oxidation states of elements by capillary electrophoresis

Progress made in the last five years in the application of capillary electrophoresis methods to chemical speciation of elements is reported on the basis of over 100 literature references. The main trends observed include development of new on‐ and off‐capillary derivatization methods, application of new detection methods, and especially coupling of CE separation systems to powerful atomic spectroscopy and mass spectrometry instruments with various ionization techniques, providing either a sensitive element‐specific detection method or a third dimension for high performance separation. Besides numerous CZE and MEKC capillary electrophoresis methods only very few examples of CE speciation with capillary electrochromatography can be found. Concerning the chemical forms of elements determined, the new procedures developed are mostly focused on redox speciation of various oxidation states of elements, metal‐bound high molecular compounds, and organometallic species.     

微波辅助萃取-液质联用技术测底泥砷、硒的化学形态

建立了用反相离子对色谱和电感耦合等离子体质谱的联用技术同时测定As（Ⅲ）、 As（Ⅴ）、 MMA、 DMA、 Se（Ⅳ）、 Se（Ⅵ）、 SeMet和SeCys的砷、硒化学形态分析方法. 分别从流动相pH值、离子对试剂的浓度、甲醇量和流速4个方面进行了分离测定条件的优化. 利用碰撞池技术（CCT）较好地解决了^40Ar^35Cl^＋复合离子对^75As的干扰, 并使^80Se的测定成为可能, 有效地提高了灵敏度. 将该方法应用于上海市苏州河底泥样品的微波辅助萃取液的形态分析中, 砷和硒的检出限分别达到0.4～1.3 和0.5～1.9 μg/L.     

Speciation of halogenides and oxyhalogens by ion chromatography-inductively coupled plasma mass spectrometry

A speciation method utilizing ion chromatography coupled with inductively coupled plasma mass spectrometry is described for simultaneous analysis of eight halogenides and oxyhalogens: chloride, chlorite, chlorate, perchlorate, bromide, bromate, iodide and iodate. The method was applied for the analysis of drinking water samples collected from water treatment plants in areas in Finland, which are known to have high bromine concentrations in ground water. Water samples collected before and after disinfection were analyzed to get information about potential species conversion as a result of purification. Chloride and chlorate were the chlorine species found in these water samples, and iodine existed as both iodate and iodide. In the case of bromine, species conversion had taken place, since total bromine concentrations were increased during disinfection but bromide concentrations were decreased. No bromate was observed in the samples. The detection limits for all the chlorine species studied were 500 μg/l, for bromine species studied 10 μg/l, for iodide 0.1 μg/l and for iodate 0.2 μg/l.     

Speciation analysis of mercury by dispersive solid‐phase extraction coupled with capillary electrophoresis

A pretreatment method of dispersive solid‐phase extraction (DSPE) along with back‐extraction followed by CE‐UV detector was developed for the determination of mercury species in water samples. Sulfhydryl‐functionalized SiO₂ microspheres (SiO₂−SH) were synthesized and used as DSPE adsorbents for selective extraction and enrichment of three organic mercury species namely ethylmercury (EtHg), methylmercury (MeHg), and phenylmercury (PhHg), along with L‐cysteine (L‐cys) containing hydrochloric acid as back‐extraction solvent. Several main extraction parameters were systematically investigated including sample pH, amount of adsorbent, extraction and back‐extraction time, volume of eluent, and concentration of hydrochloric acid. Under optimal conditions, good linearity was achieved with correlation coefficients over 0.9990, in the range of 4−200 μg/L for EtHg, and 2−200 μg/L for MeHg and PhHg. The LODs were obtained of 1.07, 0.34, and 0.24 μg/L for EtHg, MeHg, and PhHg, respectively, as well as the LOQs were 3.57, 1.13, and 0.79 μg/L, respectively, with enrichment factors ranging from 109 to 184. Recoveries were attained with tap and lake water samples in a range of 62.3−107.2%, with relative standard deviations of 3.5–10.1%. The results proved that the method of SiO₂−SH based DSPE coupled with CE‐UV was a simple, rapid, cost‐effective, and eco‐friendly alternative for the determination of mercury species in water samples.     

Speciation of selenium compounds by open tubular capillary electrochromatography-inductively coupled plasma mass spectrometry

We introduce a T-type interface and a crossflow nebulizer to find ways to combine CEC with inductively coupled plasma MS (ICP-MS) detection for selenium speciation. For CEC separation, we employed a macrocyclic polyamine-bonded phase capillary as the separation column and a bare fused-silica capillary filled with the make-up liquid (0.05 M HNO3). The effect of nebulizer gas flow rate, make-up liquid flow, type, concentration and pH of the mobile phase on the separation have been studied. Tris buffer of 50 mM at pH 8.50 gave the best performance for selenium speciation. The reproducibility of the retention time indicated that sample injection by electrokinetic and nebulizer gas flow was better than that by self-aspiration alone. The detection limits for selenate, selenite, selenocystine and selenomethionine were found to be 2.40, 3.53, 12.86 and 11.25 ng/mL, respectively. Due to the high sensitivity and element-specific detection, as well as the high selectivity of the bonded phase, quantitative analysis of selenium speciation in urine was also achieved.     

Inorganic selenium speciation in environmental samples using selective electrodeposition coupled with electrothermal atomic absorption spectrometry

Speciation analyses are of increasing interest in the environmental, toxicological and analytical fields, because the toxicity and reactivity of trace elements depend strongly on the chemical forms in which they are present. A simple electrodeposition–electrothermal atomic absorption spectrometry method for speciation analysis of some organic and inorganic selenium species in typical environmental water and agricultural soil samples has been developed. The method is based on the selective reduction of water-soluble Se(IV) and selenocystine (Se–Cys) species by an uncontrolled applied potential (1.8 V) on a mercury-coated electrode. In acidic media (1.0 M HCl solution) the only inorganic selenium species electrodeposited was Se(IV), and, of the water-soluble organic selenium species Se–Cys and Se–Met only Se–Cys was electrodeposited onto the mercury electrode surface. The proposed methodology was successfully applied to the speciation and determination of selenium in a few environmental samples. The spiked recovery value varied between 91% and 99%. The suggested method has been shown to have a characteristic mass (m₀) of 25 pg, a limit of detection (LOD) of 1.0 μg L^− 1 and a relative standard deviation (RSD%) of 3.5% for 6 measurements at a concentration of 100 μg L^− 1 Se(VI).     

Hyphenation of capillary electrophoresis to inductively coupled plasma mass spectrometry as an element-specific detection method for metal speciation

A stepwise development for the use of capillary electrophoresis and inductively coupled plasma mass spectrometry (ICP-MS) for speciation investigations is presented. The high resolution power of CE is used for the separation of metal species, whereas ICP-MS is taken for element-specific detection with low detection limits. This contribution starts with an off-line combination of both instruments. Separation and identification of species in model solutions and real samples are shown by scanning UV detection at the CE unit with subsequent metal quantification in peak related fractions, applying electrothermal vaporization ICP-MS. Finally, first separations are demonstrated, using the on-line hyphenation with a laboratory-made nebulizer. Here, standard solutions are separated and monitored by UV and ICP-MS. Stability of electrical current during nebulization was checked and a possibly interfering suction flow was estimated. After optimization sufficient electropherograms were obtained. Advantages and problems are discussed for both modes.     

Arsenic speciation by coupling capillary zone electrophoresis with mass spectrometry

Summary Capillary zone electrophoresis (CZE) has been coupled with mass spectrometry to enable the identification of mineral and organometallic compounds of arsenic in speciation studies. The electrophoretic effluent was introduced through a concentric interface into the mass spectrometer. Make-up liquid was added to enable electric contact at the outlet of the separation capillary and to assist the electronebulization process. After ionization, the ions were analyzed and quantified with an ion-trap detector. Optimization of the coupling conditions (geometry of the concentric interface, composition and flow rate of the sheath liquid, electronebulization and detection conditions) is described. The results show that the geometry of the concentric interface and the positioning of the outlet of the separation capillary have a critical effect on stability and sensitivity. Programming the electronebulization and detection conditions throughout the analysis enabled identification and quantification of the seven arsenic compounds of interest (neutral, and positively or negatively charged species) in less than 20 min at the ppm level. Limits of detection ranged from 0.5 to 3.3 mg L⁻¹, corresponding to amounts injected ranging from 15 to 60 pg. The linear dependence of mass spectrometric response on arsenic concentration was verified for concentrations ranging from 5 to 200 mgL⁻¹. For the two positively charged species, arsenobetaine and arsenocholine, an on-line preconcentration technique (field-amplified sample injection) enabled reduction of the detection limits by approximately one order of magnitude to 110 and 160 μgL⁻¹, respectively.     

Quantification of phosphorus in DNA using capillary electrophoresis hyphenated with inductively coupled plasma mass spectrometry

We have analyzed phosphorus in an enzymatically digested DNA molecule using capillary electrophoresis (CE) hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). The DNA concentration was quantified by the phosphorus value obtained in the CE-ICP-MS analysis. The CE-ICP-MS measurement, for which the interface device AIF-01 equipped three layered nebulizer was adopted, was achieved with limited μL/min nebulizing without loss of sample in the vaporizing chamber. The samples of nucleotides and free phosphate were separated well in the CE-ICP-MS measurement, and the calibration curve (0.1-10μg/mL) of the phosphorus showed a linear (R(2)=0.999) increase in intensity. After digestion of the 100-bp double-strand DNA sample to deoxyribonucleotide-5'-monophosphates (dNMPs) by phosphodiesterase-I, phosphorus was detected by CE-ICP-MS without further purification steps. In this study, we applied two calculation schemes of DNA analysis using a dNMP concentration obtained from CE-ICP-MS. Comparative CE-ICP-MS analysis with DNA digested to dNMPs showed that the assay gave an equal value obtained from the total DNA quantification using fluorescence detection. The detection limits of the DNA sample obtained from these species and phosphorus in nucleotides using CE-ICP-MS were 3.1-26ng/mL. These LOD values were equal to the conventional fluorescence determination of DNA.     

Speciation analysis of inorganic arsenic by microchip capillary electrophoresis coupled with hydride generation atomic fluorescence spectrometry

A novel method for speciation analysis of inorganic arsenic was developed by on-line hyphenating microchip capillary electrophoresis (chip-CE) with hydride generation atomic fluorescence spectrometry (HG-AFS). Baseline separation of As(III) and As(V) was achieved within 54 s by the chip-CE in a 90 mm long channel at 2500 V using a mixture of 25 mmol l(-1) H3BO3 and 0.4 mmol l(-1) CTAB (pH 8.9) as electrolyte buffer. The precisions (RSD, n=5) ranged from 1.9 to 1.4% for migration time, 2.1 to 2.7% for peak area, and 1.8 to 2.3% for peak height for the two arsenic species at 3.0 mg l(-1) (as As) level. The detection limits (3sigma) for As(III) and As(V) based on peak height measurement were 76 and 112 microg l(-1) (as As), respectively. The recoveries of the spikes (1 mg l(-1) (as As) of As(III) and As(V)) in four locally collected water samples ranged from 93.7 to 106%.