Henryk Matusiewicz

Potential release of in vivo trace metals from metallic medical implants in the human body: From ions to nanoparticles – A systematic analytical review

Metal ion release from metallic materials, e.g. metallic alloys and pure metals, implanted into the human body in dental and orthopedic surgery is becoming a major cause for concern. This review briefly provides an overview of both metallic alloys and pure metals used in implant materials in dental and orthopedic surgery. Additionally, a short section is dedicated to important biomaterials and their corrosive behavior in both real solutions and various types of media that model human biological fluids and tissues. The present review gives an overview of analytical methods, techniques and different approaches applied to the measurement of in vivo trace metals released into body fluids and tissues from patients carrying metal-on-metal prostheses and metal dental implants. Reference levels of ion concentrations in body fluids and tissues that have been determined by a host of studies are compiled, reviewed and presented in this paper. Finally, a collection of published clinical data on in vivo released trace metals from metallic medical implants is included.

Atom trapping and in situ preconcentration techniques for flame atomic absorption spectrometry

Abstract The historical development of the in situ preconcentration technique in atomic absorption spectrometry based on a conventional flame coupled with an atom trapping tube and collection of the analyte atoms is presented. The current state of the art, including advantages and limitations of this approach, is discussed.

A novel microwave plasma cavity assembly for atomic emission spectrometry

Abstract The design approach that leads to a simple new cavity structure for a microwave discharge used for analytical chemistry is outlined. The design and construction of a totally new and efficient microwave cavity assembly, namely an integrated microwave generator/cavity combination, operated at 2.45 GHz, and preliminary operating conditions that exceed certain operational capabilities of the existing Beenakker and surfatron arrangements are described. The feasibility of operating such a microwave plasma cavity arrangement to form plasma discharges in argon, helium, nitrogen, air and oxygen at atmospheric pressure for atomic emission spectrometry has been demonstrated. The generation of an oxygen microwave induced plasma (MIP) discharge with conventional tubes used routinely in the argon or helium MIP suggests its application in spectrochemical analysis. The introduction of wet aerosols, because of the excellent resistance to detuning caused by changes in plasma density, can be accomplished by using direct solution nebulization with no desolvation system and with a typical inductively coupled plasma nebulizer-spray chamber.

Trace element analysis of biological material following pressure digestion with nitric acid-hydrogen peroxide and microwave heating

A commercial microwave acid-digestion system employing three types of closed vessels, a pressure-relief PFA-Teflon bomb (A), a pressure-relief Berghof all PTEE bomb (B) and a completely closed Parr microwave acid digestion bomb (C), was evaluated for sample digestion prior to the determination of trace elements in a biological tissue. The digestion procedure was based on sample dissolution with an HNO3-H2O2 mixture using microwave heating. The resulting solutions, analysed by flame and graphite furnace atomic absorption spectrometry, showed good agreement for all three closed-vessel techniques. Sample preparation time was approximately 10 min for vessels B and C, and 15 min for vessel A (including subsequent cooling time and preparation of the final solution).

Determination of cadmium in environmental samples by hydride generation with in situ concentration and atomic absorption detection.

A volatile Cd species (presumed to be the hydride) was generated from aqueous solutions by merging sample and tetrahydroborate reductant in a continuous-flow system. The gaseous analyte was transferred onto the inner wall of a graphite tube furnace for in situ preconcentration at 200 degrees C. Calibration was achieved via the method of standard additions. An absolute detection limit (3 sigma blank) of 10 pg was obtained using KBH4 as reductant. The precision of the determination was 12% (RSD) for a Cd concentration of 0.2 ng ml-1 using KBH4. The method was successfully applied to the determination of Cd in several certified environmental reference materials (soil, sediment, sea-water, biological samples) following pressure digestion of the samples by microwave heating in a mixture of acids.

Vapour-phase acid digestion of inorganic and organic matrices for trace element analysis using a microwave heated bomb

A vapour-phase microwave pressure digestion technique employing a special polytetrafluoroethylene-based microsampling device was evaluated for the acid digestion of marine sediment and biological tissue samples prior to the determination of their trace and minor element content. Inorganic and organic constituents are almost completely solubilized by vapour-phase attack (with an HNO3–HF mixture for the marine sediment and HNO3 for the marine biological tissue) in a perfluoroalkoxy-Teflon pressure bomb. The residue was taken up in 0.5 mol dm–3 HNO3 and analysed by flame and electrothermal atomic absorption spectrometry. Good agreement between the results and certified values for 15 elements was found. The sample preparation time was approximately 45 min for the biological tissue and 90 min for the sediment (including the subsequent cooling time and preparation of the final solution).

Determination of total antimony and inorganic antimony species by hydride generation in situ trapping flame atomic absorption spectrometry: a new way to (ultra)trace speciation analysis

The analytical performance of non-chromatographic coupled hydride generation, integrated atom trap (HG-IAT) atomizer flame absorption spectrometry (FAAS) systems were evaluated for the speciation analysis of antimony in environmental samples. Antimony, using formation of stibine (SbH3) vapors were atomized in an air–acetylene flame-heated IAT. A new design of HG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangements (a water-cooled single silica tube, double-slotted quartz tube or an “integrated trap”) was investigated. For the estimation of Sb(III) and Sb(V) concentrations in samples, the difference between the analytical sensitivities of the absorbance signals obtained for antimony hydride without and with previous treatment of samples with L-cysteine can be used. The concentration of Sb(V) was calculated by the difference between total Sbtot and Sb(III). A dramatic improvement in detection limit was achieved compared with that obtained using either of the atom trapping techniques, presented above, separately. This novel approach decreases the detection limit down to low pg mL–1 levels. The concentration detection limit, defined as 3 times the blank standard deviation (3sigma), was 0.2 ng mL–1. For a 120 s in situ pre-concentration time (sample volume of 2 mL), sensitivity enhancement compared to flame AAS, was 550 fold for Sb, using hydride generation-atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision, expressed by RSD, was 8.0% (n = 6) for Sb. The designs studied include slotted tube, water-cooled single silica tube and integrated atom traps. Reference and real sample materials were analyzed. The accuracy of the method was verified by the use of certified reference materials (NIST SRM 2704 Buffalo River Sediment, SRM 2710 Montana Soil, SRM 1633a Coal Fly Ash, SRM 1575 Pine Needles, SRM 1643e Trace Elements in Water) and by aqueous standard calibration technique (solutions). The measured Sb content, in reference materials, were in satisfactory agreement with the certified values. The hyphenated technique was applied for antimony determinations in soil, sediment, coal fly ash, sewage and river water.

Hydride generation from slurry samples after ultrasonication and ozonation for the direct determination of trace amounts of As(III) and total inorganic arsenic by their in situ trapping followed by graphite furnace atomic absorption spectrometry

A slurry sampling hydride generation method for As(III) and total inorganic As, without total sample digestion, has been developed using a continuous flow mode generation system coupled with atomic absorption spectrometric determination from environmental (marine sediment, soil, rock salt, waste water) and biological (human hair and urine, lobster, liver, muscle, beer and wort, tablets) samples. It involves trapping of the arsenic vapor on a pre-heated graphite furnace inner wall at 300 °C, treated with 150 µg of iridium as chemical permanent modifier, and determination by graphite furnace atomic absorption spectrometry (GF-AAS). The same graphite tube could be used for at least 200 cycles without any re-treatment. It was shown that this relatively simple and nearly direct procedure could give total arsenic concentrations very close to those obtained by analytical procedures requiring total sample decomposition and dissolution of organic and inorganic matter prior to the determination of analyte. Pretreatment of samples (slurried in HCl with addition of ozone) by ultrasonic agitation enabled the extraction of more than a 95% confidence level of the total arsenic from the certificate or close to the information value of the reference materials investigated. For the estimation of As(III) and As(V) concentrations in samples, the difference between the analytical sensitivities of the absorbance signals obtained for arsenic hydride without and with previous treatment of samples with thiourea can be used. The concentration of arsenate (As(V)) was calculated by the difference between total As and As(III). Reference and real sample materials were analyzed. The accuracy of the developed slurry sampling hydride generation method has been verified by analyzing several certified reference materials (TORT-1, DOLT-2, LUTS-1, DORM-1, BCSS-1, GBW 07601, NIST SRM 2709, LKSD-2, NIES CRM No. 18). The good agreement with the certified value confirms the validity of such a method for As determination instead of wet digestion procedures. The advantage of the method was that only a minimum of reagents and sample handling were required, reducing the risks of contamination and/or analyte loss and that non-chromatographic speciation approaches have been developed. However, the calibration was achieved via the technique of standard additions. In optimized conditions by Simplex the method shows an absolute detection limit (3σblank) of 1.5 ng, obtained with a 60 s trapping time using NaBH4 as reductant with Ir modifier, which corresponds to an LOD (10σ) of 4.8 ng g−1 As in sample. The relative standard deviation (RSD) of 7.8% was obtained for As concentration at the level of 20 ng g−1. The overall efficiency of the volatile species generation and trapping process estimated for arsenic was 89%. A particle size less than 20 µm is adequate to obtain total vapor generation of As content in the acidic slurry particles.

Methods for Improving the Sensitivity in Atom Trapping Flame Atomic Absorption Spectrometry: Analytical Scheme for the Direct Determination of Trace Elements in Beer

A method is described for the atomic absorption (AA) determination of Ag, Cd, Cu, Fe, In, Mn, Pb, Tl and Zn in beer using an ‘integrated atom trap’ system mounted on a standard AA air–acetylene flame burner. A new design of atom trapping technique that would exceed the operational capabilities of existing arrangements (a water-cooled single or dual silica tube or a double-slotted quartz tube) and permit construction of an ‘integrated trap’ was investigated. A significant improvement in detection limit was achieved compared with that obtained using either of the above atom trapping techniques separately. Rapid, accurate analyses can be achieved using continuous aspiration. The concentration detection limits were 3.0, 5.0, 1.2, 4.0 and 0.1 ng ml–1 for Cu, Fe, Mn, Pb and Zn, respectively, using a 2 min in situ preconcentration time. The relative standard deviations are of the order of 3.0–6.0% for this technique. Basic analytical performance characteristics are also given for Ag, Cd, In and Tl using various designs of atom trap. The designs studied include both slotted tube and single silica tube water-cooled atom traps.

Continuous-flow microwave-assisted digestion of environmental samples using atomic spectrometric detection

A continuous-flow microwave-assisted digestion technique was tested with a view to the evaluation of its effectiveness for decomposition of environmental samples. A CEM SpectroPrep system was used at moderate powers and pressures of up to 2413 kPa to perform on-line digestion of slurried samples of biological tissues (0.5% m/v) and marine sediment (1% m/v). The efficiency of oxidation of biological matrices, as characterized by the residual carbon content of the solutions, was 64%. Recovery of trace elements averaged 90±1% and was accommodated with the use of suitable internal standards. Accuracy was verified by analysis of certified reference materials from the National Research Council of Canada, marine sediment BCSS-1 and lobster hepatopancreas tissue LUTS-1. Precision of measurement, as reflected in the determination of the trace metal content in replicate solutions, using a variety of atomic spectrometric techniques, was better than 1% RSD (relative standard deviation).