Simultaneous on-line preconcentration and determination of trace metals in environmental samples by flow injection combined with inductively coupled plasma mass spectrometry using a nanometer-sized alumina packed micro-column

A flow injection (FI) on-line preconcentration procedure by using a nanometer-sized alumina packed micro-column coupled to inductively coupled plasma mass spectrometry (ICP-MS) was described for simultaneous determination of trace metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in the environmental samples. The effects of pH value, sample flow rate, preconcentration time, and interfering ions on the preconcentration of analytes have been investigated. Under the optimized operating conditions, the adsorption capacity of the nanometer-sized alumina for V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb were found to be 11.7, 13.6, 15.7, 9.5, 12.2, 13.3, 17.1, 17.7 and 17.5 mg g⁻¹, respectively. With 60 s preconcentration time and 60 s elution time, an enrichment factor of 5 and the sampling frequency of 15 h⁻¹ were obtained. The proposed method has been applied to the determination of trace metals in environmental certified reference materials and natural water samples with satisfactory results.     

Several modified piezoelectric quartz crystals for determination of omethoate

A chromatographic method for the determination of transition metals in human hair samples is described. The method involves the separation of Cu, Pb, Zn, Ni, Co, Cd and Mn in a C18 column coated with sodium hexadecane-sulfonate (SHS) and spectrophotometric detection (520 nm) after post-column reaction of the eluted metals with 4-(2-pyridylazo)-resorcinol (PAR). The eluent was a 100 mM tartrate solution adjusted to pH 3.1 with a 2 M sodium hydroxide solution (flow-rate=1.0 ml min(-1)). A good separation of the eluted metals (specially for Cu/Pb and Zn/Ni) has been achieved. The detection limits, expressed as mug l(-1), were 2.2 (Cu), 8.0 (Pb), 2.8 (Zn), 1.5 (Ni), 1.5 (Co), 12.0 (Cd), and 1.4 (Mn). A microwave-assisted closed vessel acid digestion procedure with HNO(3)+HClO(4) (4+1 ml) was used for the hair samples solubilisation. Nineteen hair samples were analysed with the proposed method. The results were in good agreement with those obtained by atomic absorption spectrometry (AAS).     

Trace metals analysis in estuarine and seawater by ICP-MS using on line preconcentration and matrix elimination with chelating resin

The main difficulties of trace metals analysis in estuarine and seawater stem from their very low concentration (mug/l to sub-mug/l), and, by contrast, the high salt content (up to 38 g/l in the Mediterranean Sea). ICP-MS allows multi-elemental analysis and offers great sensitivity, but may be strongly affected by matrix effects induced by high salt contents (> 1 g/l). To perform trace metals analysis both in riverine, estuarine and seawater, we have developed a hyphenated method: ion chelation chromatography coupled on-line with ICP-MS. Iminodiacetate resin, Metpac CC-1 (Dionex), was used to concentrate most of the trace metals, and to separate them from alkaline and alkaline-earth metals. Behaviour of 17 elements (Pb, Cu, Cd, Ni, U, Cr, Mn, Al, Co, Ga, In, Zn, V, Tl, Bi, Ag and Sn) towards the resin was qualitatively investigated. A method validation, partly derived from AFNOR standard XPT 90-210, was carried out on 12 elements (Pb, Cu, Cd, Ni, U, Cr, Mn, Al, Co, Ga, Bi and In). Replicate measurements of multi-elemental standard solutions were used to check linearity, and to determine repeatability and detection limits. Method accuracy was then assessed by analysing two certified materials: a synthetic freshwater (SRM 1643d), and a natural filtered coastal seawater (NRCC CASS-3). An application assay of natural samples from the Rh?ne river (France) was eventually carried out, and the analytical results were found to be consistent with previous works.     

On-line Preconcentration and Determination of Trace Metals in Water Samples by Flow Injection Combined with Flame Atomic Absorption Spectrometry via Calix[4]arene Carboxylic Acid Packed Micro-column

An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow injection( FI) micro-column preconcentration coupled with flame atomic absorption spectrometry(FAAS) determination of trace heavy metals(Cu, Pb, Co, Ni and Cd). Parameters such as the pH, loading time and flow rate of sample, and the concentration, volume and flow rate of eluent were optimized. The enrichment factors are 50.0, 56.5, 11.6, 12.1 and 19.1 for Cu, Pb, Co, Ni, and Cd, respectively, and a sample throughput of 20 h^-1 was obtained. The limits of detection for Cu, Pb, Co, Ni, and Cd were in a range of 1.56―3.91 μg/L, and the relative standard deviations(RSDs) were less than 2.76%(n=7). Furthermore, the proposed method was successfully applied to the determination of Cu, Pb, Co, Ni, and Cd in certified reference materials and various water samples.     

Determination of Cd, Co, Cu, Mn, Ni, Pb, and Zn by Inductively Coupled Plasma Mass Spectroscopy or Flame Atomic Absorption Spectrometry after On-line Preconcentration and Solvent Extraction by Flow Injection System

The concentrations of Cd, Co, Cu, Mn, Ni, Pb, and Zn in natural and sea waters are too low to be directly determined with by flame atomic absorption spectrometry (FAAS) or graphite furnace atomic absorption spectrometry (GFAAS). Specific sample preparations are requested that make possible the determination of these analytes by preconcentration or extraction. These techniques are affected by severe problems of sample contamination. In this work Cd, Co, Cu, Mn, Ni, Pb, and Zn were determined by inductively coupled plasma mass spectroscopy (ICP-MS) or by atomic absorption spectrometry, in fresh and seawater samples, after on-line preconcentration and following solvent elution with a flow injection system. Bonded silica with octadecyl functional group C₁₈, packed in a microcolumn of 100-μl capacity, was used to collect diethyldithiocarbamate complexes of the heavy metals in aqueous solutions. The metals are complexed with a chelating agent, adsorbed on the C₁₈column, and eluted with methanol directly in the flow injection system. The methanolic stream can be addressed to FAAS for direct determination of Cu, Ni, and Zn, or collected in a vial for successive analysis by GFAAS. The eluted samples can be also dried in a vacuum container and restored to a little volume with concentrated HNO₃and Milli-Q water for analysis by ICP-MS or GFAAS.     

Immobilization of 8-hydroxyquinoline onto silicone tubing for the determination of trace elements in seawater using flow injection ICP-MS

A rapid and simple on-line method is described for the preconcentration of Mn, Co, Ni, Cu, Zn, Cd and Pb from sea water using 8-hydroxyquinoline immobilized onto silicone tubing (Sil-8-HQ) via the Mannich reaction. Recoveries between 35 and 95% and limits of detection in the ppt range were obtained using a 2 m long Sil-8-HQ tube with a sample flow rate of 1.0 ml min(-1). A tube could be subjected to sample loading and elution cycles over 200 times. The capacity was 1.5 and 1.3 mug cm(-2) for Cu and Mn, respectively. Cu, Cd, Co, Pb, Mn, Zn and Ni were determined in coastal and open ocean seawater using flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Good agreement with certified values for the certified reference materials NASS-4 and CASS-3 was demonstrated when quantitation was undertaken by the method of additions.     

Simultaneous on-line pre-concentration and determination of trace metals in environmental samples by flow injection combined with inductively coupled plasma mass spectrometry using silica gel modified with niobium(V) oxide

This work presents the development of an on-line pre-concentration system for simultaneous determination of Cd, Cu, Ni, V, Zn, Co and Pb in aqueous environmental samples and detection by inductively coupled plasma mass spectrometry. The system is based on cationic retention of the analytes onto a mini-column filled with silica gel modified with niobium(V) oxide. The effects of chemicals and flow variables have been investigated. The optimized operating conditions, selected as a compromise between sensitivity and analytical frequency were: sample pH 7.0, sample flow rate of 6.0mL min(-1), eluent flow rate of 2.0mL min(-1), and eluent (HNO(3)) concentration of 2.5mol L(-1). The relative standard deviation (n=7), enrichment factor and linear working range were 0.8-4.5%, 23.3-37.2 and 0.05-25.0microg L(-1), respectively. Limits of detection were between 0.01 and 0.03microg L(-1). The accuracy of the proposed method was checked with certified materials (NASS-4, NASS-5, CASS-4 and SRM 1643e). Values obtained were in accordance with those reported for the certified materials. Recovery was found to be in the range of 90-110% for a suit of water samples with variable matrices (seawater, tap water and ground water) collected in Florianopolis, Brazil.     

Micro-scale flow system for on-line multielement preconcentration from saliva digests and determination by inductively coupled plasma optical emission spectrometry

A micro-scale flow system is proposed for on-line preconcentration of Cd, Cu, Mn, Ni and Pb in saliva samples and their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). A small column containing 8 μl of AG50W-X8 resin was inserted into the flow system, assembled with capillary tubes and connected to a micro-concentric nebulizer. The elution of the analytes was performed with 3 mol l⁻¹ HCl at a flow rate of 82 μl min⁻¹. The ICP-OES signal acquisition program permits measurements for 5 s in the concentrated portion of the transient elution peaks. A sample volume of 1 ml was required to obtain enrichment factors of 46, 23, 17, 18 and 44 for Cd, Cu, Mn, Ni and Pb, respectively. The relative standard deviations for a 50-μg l⁻¹ multi-analyte solution were ≤6.5%. The recoveries for Cd, Cu, Mn, Ni and Pb in digested human saliva samples were between 86 and 111%. The sample throughput was 24 h⁻¹.     

Flow injection dual-syringe sorbent extraction platform for metal determination in environmental matrices utilizing a new strong cation exchange sorbent micro-cartridge and flame atomic absorption spectrometry

A novel dual-syringe flow injection (DSFI) on-line column preconcentration system coupled to flame atomic absorption spectrometry (FAAS) has been developed for automatic trace metal determination in natural waters and biological samples. The proposed method was based on the on-line retention of Cd(II), Pb(II), Cu(II), Co(II) and Ni(II) ions onto the surface of a strong cation exchanger resin named HyperSepSCX, in a readily exchangeable micro-cartridge format and subsequent elution with HCl (2?mol?L^?1) prior to flame atomization. The sorbent and the micro-cartridge exhibited high long term chemical and mechanical stability with fast kinetics for all analytes. All main chemical and hydrodynamic factors affecting the performance of the proposed method were studied thoroughly. For 15.0?mL sample volume, the enhancement factors were calculated as 92, 97, 93, 99 and 77 for Cd(II), Pb(II), Cu(II), Co(II) and Ni(II) respectively and the detection limits (3?s) were in the range between 0.14 and 2.1?µg?L^?1. The precision (RSD) obtained was lower than 3.3% for all five metal ions with a sample throughput of 12?h^?1. The developed method was evaluated by analyzing certified reference materials and spiked environmental natural water samples.     

Certification of the contents of some heavy metals (Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn) in three types of sewage sludge

Summary The element contents of Cd, Co, Cu, Mn, Hg, Ni, Pb and Zn of three different types of sewage sludge were certified. The preparation, the homogeneity and the stability are reported. The certified contents as well as values for Cr and Se and for the aqua regia soluble contents of Cd, Cr, Co, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn) in drei Klärschlammproben

Zusammenfassung In drei verschiedenen Klärschlammproben wurden die Elementgehalte an Cd, Co, Cu, Mn, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Herstellung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt von Cr, Se und der Gehalt an königswasserlöslichem Cd, Cr, Co, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

微晶蒽分离富集测定痕量铜(II)

建立了一种利用微晶蒽吸附分离富集环境水样中痕量Cu(Ⅱ)的新方法。 研究表明,pH=3.0时, Cu(Ⅱ)与1-(2-吡啶偶氮)-2-萘酚形成红棕色螯合物被微晶蒽定量吸附,而Pb(Ⅱ)、Mn(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cd(Ⅱ)、Zn(Ⅱ)、Fe(Ⅲ)和Al(Ⅲ)等完全留在溶液中,从而实现Cu(Ⅱ)与它们的分离。 该方法可直接用于1 L水样中痕量Cu(Ⅱ)的分离与富集,富集倍数达200倍,回收率91.0%~104.0%, 最低检出限为0.026 μg/L;应用于不同水样中Cu(Ⅱ)的测定,结果令人满意。     

Certification of the contents of some heavy metals (Cd, Cu, Hg, Ni, Pb and Zn) in three types of soils

Summary The element contents of Cd, Cu, Hg, Ni, Pb and Zn of three types of soil were certified. The preparation, homogeneity and stability are reported. The certified contents as well as values for Co, Cr, Mn and Se and for the aqua regia soluble contents Cd, Cr, Cu, Mn, Ni, Pb and Zn are given.

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Zertifizierung von Schwermetallspuren (Cd, Cu, Hg, Ni, Pb und Zn) in drei Bodenproben

Zusammenfassung In drei verschiedenen Bodenproben wurden die Elementgehalte an Cd, Cu, Hg, Ni, Pb und Zn zertifiziert. Es wird berichtet über die Bereitung, Homogenität und Stabilität. Die zertifizierten Gehalte sowie der Gehalt an Cr, Co, Mn und Se und der Gehalt an königswasserlöslichem Cd, Cr, Cu, Mn, Ni, Pb und Zn werden angegeben.

     

Determination of some trace metals in waters by flame atomic absorption spectrometry after preconcentration on Amberlite XAD-16 resin with sodium tetraborate

A method was described for the determination of the elements Cr, Mn, Fe, Co, Ni, Cu, Cd, Pb, and Bi in waters by flame atomic absorption spectrometry (FAAS) after separation and preconcentration on Amberlite XAD-16 resin with sodium tetraborate using a chromatographic column. Parameters influencing the analytical performance, including pH and the volume of sample, amount of analyte and interfering effect of co-existing ions, were studied in detail. The recovery values were quantitative (> or = 95%), and the relative standard deviation (RSD) and detection limit (DL) varied in the range of 1.1-2.4% (n=10) and 0.002-0.177 microg m(-1) (3s, n=20), respectively. After being optimized, the proposed method was applied to the drinking water, waste water and artificial sea water samples. Recovery values of the elements investigated, were quantitative for tap water and synthetic sea water, except for Mn, Co and Ni (including also Cd for synthetic sea water). Recovery values of Cd, Pb, Cu and Co were found to be 95, 102, < or = 87, and < or = 83%, respectively, for the waste water samples.     

Multielemental analysis in small amounts of environmental reference materials with inductively coupled plasma mass spectrometry

The lowest possible sample weight for performing multielemental trace element analysis on environmental and biological samples by ICP-MS has been investigated. The certified reference materials Bovine Liver NIST SRM 1577b, Human Hair NCS DC 73347 and Oriental Tobacco Leaves CTA-OTL-1 were applied at sample weights (1, 5, 20 and 50 mg aliquots, n = 10) which were significantly lower than those recommended with most recoveries in the range of 95-110%. Samples were digested in a mixture of nitric acid, hydrogen peroxide and hydrogen fluoride by closed-vessel microwave digestion. Multielemental analysis was performed with an optimized ICP-QMS method. Aqueous standard solutions were applied for external calibration with rhodium as the internal standard element. The detection limits varied between 0.02-0.38 microg/g for Li, Na, Cr, Mn, Ni, Cu, Zn, Sr, Cd, Ba and Pb, and up to 1.92 microg/g for Mg, Al, Ca, Fe and Ni. Digested human plasma samples were spiked with multielemental solution (0.5-10 microg/L) to test the analytical method and the recoveries were 95-105% for most analytes. Our results show that in the case of homogeneous SRMs it is possible to use them in very low amounts (1-5 mg) for method development and quality control.     

Determination of Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb in natural waters, alkali and alkaline earth salts by electrothermal atomic absorption spectrometry after preconcentration by column solid phase extraction

Methods are described for the determination of trace and ultra trace amounts of Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb in natural waters, alkali and alkaline earth salts. Separation and preconcentration of trace metals is achieved by a column solid phase extraction procedure using silica gel modified with derivatives of dithiocarbamates — Na-DDTC (sodium diethyldithio-carbamate and HMDTC (ammonium hexamethylene-dithiocarbamate) as column packing material. The influence of the sorbent preparation procedure on the degree of sorption of the trace analytes is examined for different pH values of the sample solution. Isobutylmethyl ketone (IBMK) is proposed as an effective eluent for quantitative elution of retained metal ions. Optimal instrumental parameters for ETAAS determination of preconcentrated elements in organic eluate are presented. Practical application of sorbents in analysis of natural waters and alkali and alkaline earth salts is demonstrated. Proposed preconcentration procedure combined with ETAAS determination of trace analytes allows the determination of 0.04 g l^–1 Cd, 0.1 g l^–1 Cr, Cu, and Mn and 0.3 g l^–1 Co, Fe, Ni and Pb in natural waters and 1.10^–7% Cd, 3.10^–7% Cr and Mn, 7.10^–7% Co, Ni and Pb and 2.10^–6% Cu and Fe in alkali and alkaline earth salts.     

Novel Chelating Resin for Solid-Phase Extraction of Metals in Certified Reference Materials and Waters

A new chelating resin, poly(diacetonitrile methacrylamide-co-divinylbenzene-co-vinylimidazole), was synthesized and characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and elemental analysis. The novel resin was used for the first time as a chelating adsorbent for the preconcentration of Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn from various samples by flame atomic absorption spectrometry. The adsorption capacities of the resin were 29.3, 31.6, 29.3, 27.3, 35.5, 31.7, 39.8, and 32.3?mg?g^?1 for Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn, respectively. The detection limits of the metal ions were from 0.42 to 3.21?µg?L^?1. A preconcentration factor of 30 for all metal ions was obtained. The precision of the method as the relative standard deviation was less than or equal to 2.6%. The described method was validated with certified reference materials and fortified real samples. The method was used for the determination of the analytes in well water and wastewater.     

A multielement masking method using magnesium hydroxide coprecipitation for the selective determination of lead in water samples by differential pulse anodic stripping voltammetry.

We present a new multielement masking method using magnesium hydroxide coprecipitation for the selective determination of Pb by differential pulse anodic stripping voltammetry (DPASV). The recovery of Pb in the masking method was over 95%, while interfering ions (Cd(2+), Co(2+), Cu(2+), Fe(3+), Mn(2+), and Ni(2+)) could be removed at 100% from the analytical sample. A linear regression was obtained in the Pb concentration from 10 to 1000 microg kg(-1) in the existence of 100 microg kg(-1) of the interfering ions. When this method was applied to the determination of Pb in a natural water-standard reference material (NIST 1640), the determined value for Pb in this work (25.4 +/- 4.1 microg kg(-1)) almost agreed with the certified value (27.89 +/- 0.14 microg kg(-1)).     

Sol-gel zirconia coating capillary microextraction on-line hyphenated with inductively coupled plasma mass spectrometry for the determination of Cr, Cu, Cd and Pb in biological samples

A sol-gel zirconia coating was developed for the preconcentration/separation of trace Cr, Cu, Cd and Pb by capillary microextraction, and the adsorbed analytes were on-line eluted for detection using inductively coupled plasma mass spectrometry (ICP-MS). By immobilizing sol-gel zirconia on the inner surface of a fused-silica capillary, the sol-gel zirconia coating was simply prepared. Its adsorption properties, stability and the factors affecting the adsorption behaviors of Cr, Cu, Cd and Pb were investigated in detail. In the pH range from 7.8 to 10, the zirconia-coated capillary (35 cm x 0.15 mm) is selective towards Cr, Cu, Cd and Pb, and the analyzed ions could be desorbed quantitatively with 0.2 mL of 0.5 mol/L HNO(3) at a rate of 0.2 mL/min. With a consumption of 1.25 mL sample solution, an enrichment factor of 6.25, and detection limits (3sigma) of 9.9 pg/mL Cr, 17.9 pg/mL Cu, 4.5 pg/mL Cd and 3.7 pg/mL Pb were obtained. The precisions for nine replicate measurements of 1 ng/mL Cr, Cu, Cd and Pb were 4.9% Cr, 2.2% Cu, 2.0% Cd and 3.2% Pb (RSD), respectively. The proposed procedure has been applied to the determination of Cr, Cu, Cd and Pb in human urine, which was subjected to microwave-assisted digestion prior to analysis, and the recoveries for these elements were 89.2-101.8%. In order to validate the developed procedure, a NIES No.10-a Rice Flour-Unpolished certified reference material and a BCR No. 184 Bovine Muscle certified reference material were analyzed, and the results are in good agreement with the certified values.     

Improved detection of transition and rare earth elements in marine samples with the CETAC DSX-100 preconcentration/matrix elimination system and ICP-MS

A new method for detection of trace metals in saline samples is described using batch preconcentration with subsequent ICP-MS analyses after direct sample insertion of the analyte loaded chelating resin. The samples were prepared using a CETAC DSX-100 system, which preconcentrates analytes and removes matrix components by a suspended particulate reagent (SPR). The SPR is consisting of polymeric beads of 0.2 μm size that selectively binds the trace metals by iminodiacetic chelating groups. The beads with bound analytes are then nebulized directly into the ICP-MS. The enrichment factors lay between 40 and 48 due to the enrichment of 120 mL suspension to 2.5–3.0 mL eluate. The method was applied and validated to the successful determination of traces of the transition metals Mn, Fe, Ni, Co, Cu, Zn, Cd, and Pb in the Open Ocean Seawater certified reference material NASS-4 and the Coastal Seawater certified reference material CASS-3. In addition to the certified constituents the rare earth elements La, Ce, Eu, Gd, Yb, and Lu were determined. Received: 15 Oktober 1999 / Revised: 1 February 2000 / Accepted: 3 February 2000     

Improved detection of transition and rare earth elements in marine samples with the CETAC DSX-100 preconcentration/matrix elimination system and ICP-MS

A new method for detection of trace metals in saline samples is described using batch preconcentration with subsequent ICP-MS analyses after direct sample insertion of the analyte loaded chelating resin. The samples were prepared using a CETAC DSX-100 system, which preconcentrates analytes and removes matrix components by a suspended particulate reagent (SPR). The SPR is consisting of polymeric beads of 0.2 μm size that selectively binds the trace metals by iminodiacetic chelating groups. The beads with bound analytes are then nebulized directly into the ICP-MS. The enrichment factors lay between 40 and 48 due to the enrichment of 120 mL suspension to 2.5–3.0 mL eluate. The method was applied and validated to the successful determination of traces of the transition metals Mn, Fe, Ni, Co, Cu, Zn, Cd, and Pb in the Open Ocean Seawater certified reference material NASS-4 and the Coastal Seawater certified reference material CASS-3. In addition to the certified constituents the rare earth elements La, Ce, Eu, Gd, Yb, and Lu were determined. Received: 15 Oktober 1999 / Revised: 1 February 2000 / Accepted: 3 February 2000