Determination of Iodide and Iodate by Ion Chromatography with Postcolumn Reaction and UV/Visible Detection

Iodide and iodate can be determined by two new methods using anion-exchange chromatography with postcolumn reaction and UV/visible detection. Iodide is determined as IBr(2)(-) at 249 nm. Iodate is determined as I(3)(-) at 288 nm. The analyses can be run completely automatically and do not require any sample pretreatment. The detection limits for iodide and iodate are 0.1 μg/L. The methods have been successfully applied to determine iodide and iodate in several mineral waters and in drinking water as well as for the determination of iodide in table salt.     

燃烧裂解-离子色谱法测定工业废水中的可吸附有机卤素

可吸附有机卤素(AOX)是用来表征水体有机卤化物污染程度的有效指标.有机卤化物的广泛应用还会增加工业废水中AOX的残留水平,而有机卤化物往往具有高的毒性,因此需要重视工业废水中AOX的污染水平.AOX包括可吸附有机氯(AOCl)、可吸附有机溴(AOBr)和可吸附有机碘(AOI).该研究建立燃烧裂解-离子色谱法测定工业废...     

Simultaneous determination of bromide and iodide as acetone derivatives by gas chromatography and electron capture detection in natural waters and biological fluids

Oxidation of bromide and iodide ions in acidic solutions in the presence of acetone forms the corresponding acetone derivatives. Iodate was reduced with thiosulfate prior to the determination. After extraction with benzene the bromo- and iodoacetone were measured by gas chromatography using electron capture detection. The bromide and iodide contents of rainwater, drinking water, river water, seawater, oil brine, common salt, cow milk, and human blood serum were determined. The relative standard deviations for bromide at 10(-7) M and for iodide at 10(-8) M concentration were 1.9% and 3.0%, respectively, using a 10-mL sample for the determination without preconcentration.     

Improvements in LC/Electrospray Ion Trap Mass Spectrometry Performance Using an Off-Axis Nebulizer

Charged residues from the electrospray process have been hypothesized to limit the sensitivity and dynamic range of an ion trap mass spectrometry operation. Incorporation of an off-axis nebulizer (positioned 90-95° from the sampling orifice) was found to drastically reduce the detrimental effects caused by the charged particles or droplets compared to typical on-axis nebulization configurations (spraying 10-20° from sampling orifices). The off-axis nebulizer reduced total ion currents that enter the ion trap (through the reduction of charged residues) by a factor of 5-7 while resulting in an increase of analyte [M + H](+) signal by a factor of 6 compared to an on-axis sprayer at flow rates of 20 μL/min. At higher flow rates (e.g., 800 μL/min) these enhancements are more evident. At flows greater than 200 μL/min, off-axis nebulization reduced total ion current that enters the ion trap by a factor of 30 and resulted in a factor of more than 20 increase in [M + H](+) signal relative to on-axis nebulization. Incorporation of the off-axis nebulizer improved the detection limit and precision for determination of dihydroxyvitamin D(3) in plasma compared to on-axis nebulization. The LC/MS/MS detection limits obtained for the off-axis nebulizer on the ion trap was within a factor of 2 from the detection limit determined by the triple quadrupole. The relative standard deviation of the dihydroxyvitamin D(3) determination was less than 8% for both off-axis ion trap and triple-quadrupole determinations.     

Highly sensitive and selective determination of iodide and thiocyanate concentrations using surface-enhanced Raman scattering of starch-reduced gold nanoparticles

In this report, we propose a novel technique for the determination of the concentrations of iodide and thiocyanate by surface-enhanced Raman scattering (SERS) of starch-reduced gold nanoparticles. Starch-reduced gold nanoparticles show an intrinsic Raman peak at 2125 cm(-1) due to the -C≡C- stretching mode of a synthesized byproduct. Because of the high adsorptivity of iodide on a gold surface, the intensity of the SERS peak at 2125 cm(-1) decreases with an increase in the iodide concentration. Thiocyanate also strongly adsorbs on a gold surface, and a new peak appears at around 2100 cm(-1), attributed to the -C≡N stretching vibration in a SERS spectrum of starch-reduced gold nanoparticles. These two peaks were successfully used to determine the iodide and thiocyanate concentrations separately, even in their mixture system. The detection limit of this technique for iodide is 0.01 μM with a measurement range of 0.01-2.0 μM, while the detection limit of this technique for thiocyanate is 0.05 μM with a measurement range of 0.05-50 μM. This technique is highly selective for iodide and thiocyanate ions without interference from other coexisting anions such as other halides, carbonate, and sulfate.     

Online detection of radioactive iodine in aqueous systems through the use of scintillating anion exchange resin

The objective of this research was to develop a scintillating anion exchange resin selective for monitoring (129)I at concentrations at or below ~0.4 Bq/L. One of the primary long-term risk-drivers and contaminants associated with nuclear waste sites is (129)I. Synthesis of scintillating anion exchange resin consisted of diffusing a fluor, 2-(1-naphthyl)-5-phenyloxazole (α-NPO), into a polymeric resin. The resultant scintillating resin was further modified by amination with N-methyldi-n-octylamine (MDOA) to serve as an anion exchange group. Radiochromatography columns were prepared with the synthesized resin for use in a variety of flow-cell experiments utilizing a standard (129)I solution in a synthetic groundwater to determine the properties (selectivity, interferences, loading efficiency, kinetics, capacity, and detection efficiency) of the resin. Column effluents were quantified by liquid scintillation. Average loading and detection efficiencies have been measured at 91 ± 9% and 50 ± 4%, respectively. Finally, batch sorption studies indicated fast iodide sorption rates (90% loading in ~10 min) for the resin, and dynamic sorption tracer studies indicated an iodide capacity of approximately 7,800 μg/g at 10% breakthrough.     

新型液-液微萃取--气相色谱法测定海水中的有机氯农药

本文采用了一种新型的液---液两相微萃取技术作为海水样品前处理方法,对海水中的八种有机氯农药(α-BHC,β-BHC,γ-BHC,δ-BHC,p,p,-DDE,o,p,-DDT,p,p,-DDD,p,p,-DDT)进行萃取、富集和分离,采用配微池电子捕获检测器气相色谱法分析测定。对影响萃取效率的因素进行了优化。结果表明,在优化条件下,六六六、滴滴涕在1.0-100.0μg/L范围内有良好的线性关系,R≥0.9963,检测限为0.004~0.016μg/L。     

Quantum dots confined in an organic drop as luminescent probes for detection of selenium by microfluorospectrometry after hydridation: study of the quenching mechanism and analytical performance

Following a preliminary work (Costas-Mora, I.; Romero, V.; Pena-Pereira, F.; Lavilla, I.; Bendicho, C. Anal. Chem.2011, 83, 2388-2393), a quenching mechanism has been established for the selective detection of Se (as selenium hydride) by microfluorospectrometry using CdSe quantum dots (QDs) as luminescent probes stabilized with hexadecylamine and confined in an organic droplet. For this purpose, luminescence, luminescence lifetime, UV-vis absorption, total reflection X-ray fluorescence, transmission electron microscopy, and atomic force microscopy measurements were performed. The presence of stabilizing agents of QDs in the droplet was found to cause a critical effect on both extraction efficiency of selenium hydride in the drop and luminescence quenching. A self-quenching mechanism due to the aggregation of QDs is suggested. Aggregation is thought to occur as a result of the binding between selenide trapped into the organic drop as selenium hydride and Cd(2+) present in the surface of QDs, which in turn, may cause the loss of stabilizing hexadecylamine groups. After full optimization of main variables influencing the luminescent response, the analytical performance was established. A detection limit as low as 0.08 μg L(-1) Se(IV) and a repeatability expressed as relative standard deviation of 4.6% were obtained. The method was validated against CRM NWTM-27.2 lake water, and a recovery study was performed with synthetic seawater. The use of CdSe as luminescent probes in an organic drop may constitute an extremely selective, sensitive, and miniaturized assay for in situ detection of Se(IV) in water.     

高效液相色谱法定量分析化妆品中对羟基苯甲酸酯

建立了用高效液相色谱测定化妆品中对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯和对羟基苯甲酸丁酯4种防腐剂的方法。以甲醇与水作为流动相,DAD检测器的检测波长254nm,流速为1．0mL／min,柱温30℃。方法检出限分别为对羟基苯甲酸甲酯0．18μg、对羟基苯甲酸乙酯0．20μg、对羟基苯甲酸丙酯0．20μg、对羟基苯甲酸丁酯0．21μg。4种防腐剂在0～100mg／L呈现良好的线性关系。样品的加标回收率为101.3％～102.5％,相对标准偏差为0．13％～O．21％     

Microemulsion extraction separation and determination of aluminium species by spectrofluorimetry

A simple and sensitive microemulsion extraction separation method was developed for the speciation of aluminium in tea samples by spectrofluorimetry. With 8-hydroxyquinoline (8-HQ) as the chelating agent and Triton X-100 Winsor II microemulsion as the extractant, separation of aluminium species in different pH solutions was achieved by microemulsion extraction. The formation of microemulsion, the conditions of extraction and determination of aluminium species were studied. The results showed that, the contents of aluminium species in tea leaves and infusions samples, such as total aluminium, total soluble aluminium, total granular aluminium, inorganic aluminium except Al-F, and (Al-F+Al-org), were obtained successfully under the optimal conditions. The limit of detection was 0.23 μg L(-1) in pH 9.5 solution, and 0.59 μg L(-1) in pH 6.0 solution respectively; the precision (RSD) for 11 replicate measurements of 10 μg L(-1) aluminium was 2.1% in pH 9.5 solution, and 2.8% in pH 6.0 solution respectively; the recoveries for the spiked samples were 96.8-103.5%. The proposed method is simple and efficient, which has been applied to the speciation of aluminium in tea samples with satisfactory results.     

Simultaneous determination of ultratrace lead and cadmium by square wave stripping voltammetry with in situ depositing bismuth at Nafion-medical stone doped disposable electrode

An ultrasensitive electrochemical method for simultaneous determination of lead and cadmium was first developed using the novel bismuth-Nafion-medical stone doped disposable electrode (an improved wax-impregnated graphite electrode). Through the synergistic sensitization effect of the resulting composite material, the disposable electrode showed remarkable electrochemical responses to lead and cadmium. The oxidation of the two metals produced two well-defined and separated square wave peaks at about -0.62 V for Pb(2+) and -0.85 V for Cd(2+), respectively. The effects of the amount of medical stone, concentration of Nafion, thickness of bismuth, pH of buffer solution, deposition potential, accumulation time, voltammetric measurement and possible interferences were investigated in detail. Under the optimal conditions, the fabricated electrode exhibited linear ranges from 2.0 to 12.0 μg L(-1) with detection limit of 0.07 μg L(-1) for lead and 2.0-12.0 μg L(-1) with detection limit of 0.47 μg L(-1) for cadmium. The assay results of heavy metals in wastewater with the proposed method were in acceptable agreement with the atomic absorption spectroscopy method.     

Determination of boron by flow injection analysis using a conductivity detector

A flow injection method for the determination of boron using a conductivity detector has been described. Boric acid injected into the flow system reacts with mannitol (0.3 M) in the mobile phase and an equivalent amount of H(+) is liberated in the stream. The increase in the conductance of the mobile phase due to the liberated H(+) has been equated to the boron concentration in the sample. A linear calibration for light- and heavy-water samples containing 0-20 μg/mL boron was obtained. Boron concentrations in the samples of light and heavy water and lithium pentaborate solution have been measured. The interferences due to various ions such as Na(+), Li(+), Cu(2+), Ni(2+), Co(2+), Fe(3+), Al(3+), SO(4)(2-), NO(3)(-), F(-), and Cl(-) could be eliminated by adopting a two-step sample pretreatment procedure. In the first step, all the anions were converted to Cl(-) by treating the sample solution with a strong anion-exchange resin. In the second step, the solution obtained from the first step was passed through a silver-guard cartridge to remove interfering cations and Cl(-). The relative standard deviation was ±0.25% for the determination of 1 μg of boron in light water, and the limit of detection was 0.01 μg present in an injection volume of 100 μL. The corresponding values for heavy water were ±0.38% and 0.1 μg, respectively.     

Optimization of the Simultaneous Determination of Cr(III) and Cr(VI) by Ion Chromatography with Chemiluminescence Detection

An optimized method for the simultaneous determination of Cr(III) and Cr(VI) in aqueous solutions using ion chromatography with chemiluminescence detection is described. Excellent resolution of the two chromium species was obtained using a single mixed-bed ion-exchange column with continuous elution. After postcolumn reduction of Cr(VI) to Cr(III), the light emitted during the Cr(III)-catalyzed oxidation of luminol with hydrogen peroxide was measured. Parameters affecting the postcolumn reactions such as reductant concentration, reductant mixing, point of luminol introduction, and luminol flow rate were optimized. The calibration curves in the range tested (0.01-50 μg L(-)(1)) were linear, and detection limits of 0.002 μg L(-)(1) for both Cr(III) and Cr(VI) were obtained. The results of the analyses of the water reference materials LGC CRM6010 and NIST SRM1643d with certified chromium values of 49 ± 4 and 18.53 ± 0.20 μg L(-)(1) and found to contain only Cr(III) were 49.2 ± 1.8 and 19.0 ± 1.5 μg L(-)(1), respectively. Values of 10.6 ± 0.5 and 10.1 ± 0.5 μg L(-)(1) were obtained when a simulated water sample containing 10 μg L(-)(1) Cr(III) and Cr(VI) was analyzed.     

Trace Determination of Glycols by HPLC with UV and Electrospray Ionization Mass Spectrometric Detections

A high-performance liquid chromatography/mass spectrometry (HPLC/MS) method is developed for trace determination of glycols (ethylene glycol, 1,2- and 1,3-propylene glycols, and 2,3-butylene glycol) in water after derivatization with benzoyl chloride. Benzoyl esters of glycols are separated by microcolumn reversed-phase HPLC. Sensitivity and linearity of UV detection at 237 nm is compared with electrospray ionization mass spectrometric (ESI-MS) detection using selected ion monitoring. Limits of detection (LOD) and quantitation (LOQ) for UV detection are 1 and 2 mg/L, respectively. For ESI-MS detection, LOD and LOQ are in the ranges 10-25 and 20-50 μg/L, respectively. LOD obtained by ESI-MS for the determination of glycols is improved by 2-3 orders of magnitude in comparison to previously published methods. The effect of the structure of isomeric glycols on their electrospray mass spectra is discussed. The method has been applied for the determination of glycols in aqueous matrixes containing high concentrations of salts occurring in nuclear waste disposal treatment.     

Low Blank Preconcentration Technique for the Determination of Lead, Copper, and Cadmium in Small-Volume Seawater Samples by Isotope Dilution ICPMS

A simple low-blank method is described for the analysis of Pb, Cu, and Cd in seawater using Mg(OH)(2) coprecipitation and isotope dilution inductively coupled plasma mass spectrometry (ICPMS). Here, 20-40 μL of 9 M aqueous NH(3) is mixed into a 1.3 mL seawater sample spiked with enriched isotopes of Pb, Cu, and Cd. After centrifugation, the supernatant is discarded and the Mg(OH)(2) precipitate dissolved in 100 μL of 5% HNO(3) for ICPMS analysis. This method is simple, accurate, and precise, with detection limits of Pb = 1.3 pM, Cu = 39 pM, and Cd = 5.0 pM and blanks of Pb = 0.62 pM, Cu = 27 pM, and Cd = 6.0 pM. The method is demonstrated by oceanographically consistent profiles of these trace metals at an ocean station in the eastern North Atlantic.     

Quantitative RP-HPLC Determination of Some Aldehydes and Hydroxyaldehydes as Their 2,4-Dinitrophenylhydrazone Derivatives

A high-performance liquid chromatographic (HPLC) method is described for the quantitative determination of some aliphatic aldehydes and β-hydroxyaldehydes as their 2,4-dinitrophenylhydrazone derivatives. A method is described for the preparation of derivatives for those β-hydroxyaldehydes where no reference compounds of known purity are available. The detection limit of the method was 4.3-21.0 μg/L, depending on the aldehyde.     

Preconcentration and separation of copper, nickel and zinc in aqueous samples by flame atomic absorption spectrometry after column solid-phase extraction onto MWCNTs impregnated with D2EHPA-TOPO mixture

A solid phase extraction method has been developed for the determination of copper, nickel and zinc ions in natural water samples. This method is based on the adsorption of copper, nickel and zinc on multiwalled carbon nanotubes (MWCNTs) impregnated with di-(2-ethyl hexyl phosphoric acid) (D2EHPA) and tri-n-octyl phosphine oxide (TOPO). The influence of parameters such as pH of the aqueous solution, amount of adsorbent, flow rates of the sample and eluent, matrix effects and D2EHPA-TOPO concentration have been investigated. Desorption studies have been carried out with 2 mol L(-1) HNO(3). The copper, nickel and zinc concentrations were determined by flame atomic absorption spectrometry. The results indicated that the maximum adsorption of copper, nickel and zinc is at pH 5.0 with 500 mg of MWCNTs. The detection limits by three sigma were 50 μg L(-1) for copper, 40 μg L(-1) for nickel and 60 μg L(-1) zinc. The highest enrichment factors were found to be 25. The adsorption capacity of MWCNTs-D2EHPA-TOPO was found to be 4.90 mg g(-1) for copper, 4.78 mg g(-1) for nickel and 4.82 mg g(-1) for zinc. The developed method was applied for the determination of copper, nickel and zinc in electroplating wastewater and real water sample with satisfactory results (R.S.D.'s <10%).     

石墨炉原子吸收光谱法直接测定纺织品萃取汗液中砷

本文采用石墨炉原子吸收光谱法直接测定纺织品萃取液中砷。通过在样品萃取液中加入基体改进剂,并对石墨炉原子化工作条件和基体改进剂用量进行优化。结果表明,加入4μL 50g/L硝酸镍基体改进剂,可以有效降低高浓度氯化钠基体的影响,样品检出限可达到0.05mg/kg,相对标准偏差为为1.65~3.44%,实际纺织品样品加标回收率为93.8%~103%。该方法具有快速、准确、灵敏度高等优点,适用于测定纺织品萃取汗液中砷含量的检测。     

Trace analyses of arsenic in drinking water by inductively coupled plasma mass spectrometry: high resolution versus hydride generation

A magnetic sector inductively coupled plasma mass spectrometer (ICPMS) was applied to the determination of arsenic in drinking water samples using standard liquid sample introduction in the high-resolution mode (M/delta M = 7800) and hydride generation in the low-resolution mode (M/delta M = 300). Although high mass resolution ICPMS allowed the spectral separation of the argon chloride interference, the accompanying reduction in sensitivity at high resolution compromised detection and determination limits to 0.3 and 0.7 microgram/L, respectively. Therefore, a hydride generation sample introduction method, utilizing a new membrane gas-liquid separator design, was developed to overcome the chloride interference. Due to the high transport efficiency and the 50-100 times higher sensitivity at M/delta M = 300, the HG-ICPMS method resulted in an over 2000-fold increase in relative sensitivity. The routine detection and quantification limits were 0.3 and 0.5 ng/L, respectively. The results for both methods applied to the analysis of over 400 drinking water samples showed very good agreement at concentrations above 1 microgram/L. For concentrations between 0.01 and 1 microgram/L, only HG-ICPMS provided accurate quantitative results. Membrane desolvation, mixed-gas plasmas, and the addition of organic solvents for the reduction of the ArCl+ interference were also investigated and evaluated for trace As determination.     

Determination of cobalt in seawater by catalytic adsorptive cathodic stripping voltammetry

A new procedure for the direct determination of picomolar levels of cobalt in seawater is presented. Cathodic stripping voltammetry is preceded by adsorptive accumulation of the cobalt-nioxime (cyclohexane-1,2-dione dioxime) complex from seawater containing 6 μM nioxime and 80 mM ammonia at pH 9.1, onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is catalytically enhanced by the presence of 0.5 M nitrite. Optimized conditions for cobalt include a 30 s adsorption period at -0.7 V and a voltammetric scan using differential pulse modulation. According to the proposed reaction mechanism, dissolved Co(II) is oxidized to Co(III) upon addition of nioxime and high concentrations of ammonia and nitrite; a mixed Co(III)-ammonia-nitrite complex is adsorbed on the electrode surface; the Co(III) is reduced to Co(II) (complexed by nioxime) during the voltammetric scan, followed by its chemical reoxidation by the nitrite, initiating a catalytically enhanced current. A detection limit of 3 pM cobalt (at an adsorption period of 60 s) enables the detection of this metal in uncontaminated seawater using a very short adsorption time. UV digestion of seawater is essential, as part of the cobalt may occur strongly complexed by organic matter and rendered nonlabile. The method was applied successfully to the determination of the distribution of cobalt in the water column of the Mediterranean.