EXPRESS: Landmark Publications in Analytical Atomic Spectrometry: Fundamentals and Instrumentation Development.

The almost-two-centuries history of spectrochemical analysis has generated a body of literature so vast that it has become nearly intractable for experts, much less for those wishing to enter the field. Authoritative, focused reviews help to address this problem but become so granular that the overall directions of the field are lost. This broader perspective can be provided partially by general overviews but then the thinking, experimental details, theoretical underpinnings and instrumental innovations of the original work must be sacrificed. In the present compilation, this dilemma is overcome by assembling the most impactful publications in the area of analytical atomic spectrometry. Each entry was proposed by at least one current expert in the field and supported by a narrative that justifies its inclusion. The entries were then assembled into a coherent sequence and returned to contributors for a round-robin review.

Detection of capecitabine (Xeloda®) on the skin surface after oral administration.

Palmoplantar erythrodysesthesia (PPE), or hand-foot syndrome, is a cutaneous toxicity under various chemotherapeutics contributing to the most frequent side effects in patients treated with capecitabine (Xeloda®). The pathomechanism of PPE has been unclear. Here, the topical detection of capecitabine in the skin after oral application was shown in 10 patients receiving 2500 mg/m 2 /day 2500 mg/m2/day capecitabine. Sweat samples were taken prior to and one week after oral administration of capecitabine. Using high-resolution continuum source absorption spectrometry, the changes in concentrations of fluorine, which is an ingredient of capecitabine, were quantified and statistically analyzed. Here, we show an increase in fluorine concentrations from 40±10 ppb 40±10 ppb (2±0.5 pM 2±0.5 pM ) before capecitabine administration to 27.7±11.8 ppm 27.7±11.8 ppm (14.6±6.5 nM 14.6±6.5 nM ) after application, p<0.001 p<0.001 . The results show the secretion of capecitabine on the skin surface after oral administration, indicating a local toxic effect as a possible pathomechanism of PPE.

Investigations into modeling and further estimation of detection limits of the liquid electrode dielectric barrier discharge.

The liquid electrode dielectric barrier discharge (LE-DBD) is a miniaturized atmospheric pressure plasma as emission excitation source for elemental determination with pulsed behavior. Metals dissolved in liquids are detectable in flow systems with low flow rates of 20 µL min(-1) by means of optical emission spectrometry using a simple portable spectrometer. Time-resolved determination of the hydrogen excitation temperature Tαß indicates that the LE-DBD does not reach a stable state during a burning phase, whereat the maximum and minimum Tαß is independent of the flow rate. Adding dissolved metals to the liquid electrode does not influence the minimum Tαß at the end of a burning phase. With the help of measured doubly charged lanthanum lines and spatially resolved measurements, the mechanism of the liquid transfer into the plasma will be clarified. Emissions from metal oxides indicate a thermal evaporation transfer mechanism, but only an additional electrospray-like transfer mechanism can explain the observed La III emissions and nonhomogeneous spatial distribution of exited species. The reaction pathways for electrosprayed hydrated metal ions are discussed for triply and doubly charged ions. The analytical performance is evaluated for 23 elements from the categories of alkali, alkaline earth, transition, and poor metals. The achieved detection limits are between 0.016 mg L(-1) for Li and 41 mg L(-1) for Bi.

Labeling of primary human hepatocytes with micron-sized iron oxide particles in suspension culture suitable for large-scale preparation.

Labeling of hepatocytes with micron-sized iron oxide particles (MPIOs) enables cell detection using clinical magnetic resonance equipment. For clinical applications, large numbers of cells must be labeled in a simple and rapid manner and have to be applied in suspension. However, all existing protocols are based on adhesion culture labeling with subsequent resuspension, only suitable for small experimental settings. The aim of this study was to investigate the feasibility of preparing MPIO-labeled primary human hepatocytes in a temporary suspension culture. Human hepatocytes were isolated from 16 donors and labeled with MPIOs in suspension, using the Rotary Cell Culture System. Particle incorporation was investigated by light and electron microscopy. Cells were compared with adhesion culture-labeled and subsequently enzymatically resuspended cells. During a period of 5 days, hepatocyte-specific parameters of cell damage (aspartate aminotransferase and alanine aminotransferase) and metabolic activity (urea and albumin) were analyzed (n=7). Suspension cultures showed a higher outcome in cell recovery compared with the conventional labeling method. When incubated with 180 particles/viable cell for 4 h, the mean particle uptake was 28.8 particles/cell at a labeling efficiency of 95.1%. Labeling in suspension had no adverse effects on cell integrity or metabolic activity. We conclude that labeling of human hepatocytes in suspension is feasible and simple and may serve future large-scale processing of cells.

Quantification of cell labeling with micron-sized iron oxide particles using continuum source atomic absorption spectrometry.

Detection of cells after transplantation is necessary for quality control in regenerative medicine. Labeling with micron-sized iron oxide particles enables noninvasive detection of single cells by magnetic resonance imaging. However, techniques for evaluation of the particle uptake are challenging. The aim of this study was to investigate continuum source atomic absorption spectrometry (CSAAS) for this purpose. Porcine liver cells were labeled with micron-sized iron oxide particles, and the iron concentration of the cell samples was investigated by a CSAAS spectrometer equipped with a Perkin-Elmer THGA graphite furnace. The weak iron line at 305.754 nm provides only about 1/600 sensitivity of the iron resonance line at 248.327 nm and was used for CSAAS measurements. Iron concentrations measured from labeled cells ranged from 5.8 +/- 0.3 to 25.8 +/- 0.9 pg Fe/cell, correlating to an uptake of 8.2 +/- 0.5 to 25.7 +/- 0.8 particles/cell. The results were verified by standardized morphometric evaluation. CSAAS enabled rapid quantification of particle load from small quantities of cells without extensive preparation steps. Thereby, CSAAS could be used for quality control in a clinical setting of cell transplantation.

Determination of sulfur forms in wine including free and total sulfur dioxide based on molecular absorption of carbon monosulfide in the air-acetylene flame.

A new method for the determination of sulfur forms in wine, i.e., free SO(2), total SO(2), bound SO(2), total S, and sulfate, is presented. The method is based on the measurement of the carbon monosulfide (CS) molecular absorption produced in a conventional air-acetylene flame using high-resolution continuum source absorption spectrometry. Individual sulfur forms can be distinguished because of the different sensitivities of the corresponding CS molecular absorption. The sensitivity of free SO(2) is about three times higher than the value for bound SO(2) and sulfate. The method makes use of procedures similar to those used in classic reference methods. Its performance is verified by analyzing six wine samples. Relative standard deviations are between 5 and 13% for free SO(2) and between 1 and 3% for total SO(2). For the validation of the accuracy of the new method, the results are compared with those of reference methods. The agreement of the values for total SO(2) with values of the classic method is satisfactory: five out of six samples show deviations less than 16%. Due to the instability of free SO(2) in wine and the known problems of the used reference method, serious deviations of the free SO(2) results are found for three samples. The evaluation of the limits of detection focuses on the value for free SO(2), which is the sulfur form having by far the lowest concentration in wine. Here, the achievable limit of detection is 1.8 mg L(-1). [figure: see text] Detection of non-metal elements using continuum source flame absorption spectrometry.

Direct determination of total sulfur in wine using a continuum-source atomic-absorption spectrometer and an air-acetylene flame.

Determination of sulfur in wine is an important analytical task, particularly with regard to food safety legislation, wine trade, and oenology. Hitherto existing methods for sulfur determination all have specific drawbacks, for example high cost and time consumption, poor precision or selectivity, or matrix effects. In this paper a new method, with low running costs, is introduced for direct, reliable, rapid, and accurate determination of the total sulfur content of wine samples. The method is based on measurement of the molecular absorption of carbon monosulfide (CS) in an ordinary air-acetylene flame by using a high-resolution continuum-source atomic-absorption spectrometer including a novel high-intensity short-arc xenon lamp. First results for total sulfur concentrations in different wine samples were compared with data from comparative ICP-MS measurements. Very good agreement within a few percent was obtained.

Microanalysis by laser-induced plasma spectroscopy in the vacuum ultraviolet.

A new setup for microanalysis by laser-induced plasma spectroscopy in the VUV range is presented and described in detail. The system features an integrated ablation and detection module with a newly designed VUV echelle system. The echelle permits a full spectral coverage between 150 and 300 nm with a resolving power lambda/Deltalambda between 11,000 and 15,000. At present, the ablation module permits a microanalysis with a crater size of 25 microm and a nominal depth resolution with an ablation rate of 150 nm/pulse. The VUV performance was demonstrated for bulk analysis of steel; detection limits for sulfur, carbon, and phosphorus were in the lower milligram per kilogram range. The VUV scanning and mapping performance for heterogeneous matrixes was illustrated for mineral bottom ash samples from a waste incineration process.