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.

Tracing isotopically labeled selenium nanoparticles in plants via single-particle ICP-mass spectrometry.

Agronomic biofortification using selenium nanoparticles (SeNPs) shows potential for addressing selenium deficiency but further research on SeNPs-plants interaction is required before it can be effectively used to improve nutritional quality. In this work, single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) was used for tracing isotopically labeled SeNPs (82SeNPs) in Oryza sativa L. tissues. For this purpose, SeNPs with natural isotopic abundance and 82SeNPs were synthesized by a chemical method. The NPs characterization by transmission electron microscopy (TEM) confirmed that enriched NPs maintained the basic properties of unlabeled NPs, showing spherical shape, monodispersity, and sizes in the nano-range (82.8 ± 6.6 nm and 73.2 ± 4.4 nm for SeNPs and 82SeNPs, respectively). The use of 82SeNPs resulted in an 11-fold enhancement in the detection power for ICP-MS analysis, accompanied by an improvement in the signal-to-background ratio and a reduction of the size limits of detection from 89.9 to 39.9 nm in SP-ICP-MS analysis. This enabled 82SeNPs to be tracked in O. sativa L. plants cultivated under foliar application of 82SeNPs. Tracing studies combining SP-ICP-MS and TEM-energy-dispersive X-ray spectroscopy data confirmed the uptake of intact 82SeNPs by rice leaves, with most NPs remaining in the leaves and very few particles translocated to shoots and roots. Translocation of Se from leaves to roots and shoots was found to be lower when applied as NPs compared to selenite application. From the size distributions, as obtained by SP-ICP-MS, it can be concluded that a fraction of the 82SeNPs remained within the same size range as that of the applied NP suspension, while other fraction underwent an agglomeration process in the leaves, as confirmed by TEM images. This illustrates the potential of SP-ICP-MS analysis of isotopically enriched 82SeNPs for tracing NPs in the presence of background elements within complex plant matrices, providing important information about the uptake, accumulation, and biotransformation of SeNPs in rice plants.

Isotope Dilution Analysis for Particle Mass Determination Using Single-Particle Inductively Coupled Plasma Time-of-Flight Mass Spectrometry: Application to Size Determination of Silver Nanoparticles.

This paper describes methodology based on the application of isotope dilution (ID) in single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-ToFMS) mode for the mass determination (and sizing) of silver nanoparticles (AgNPs). For this purpose, and considering that the analytical signal in spICP-MS shows a transient nature, an isotope dilution equation used for online work was adapted and used for the mass determination of individual NPs. The method proposed measures NP isotope ratios in a particle-to-particle approach, which allows for the characterization of NP mass (and size) distributions and not only the mean size of the distribution. For the best results to be obtained, our method development (undertaken through the analysis of the reference material NIST RM 8017) included the optimization of the working conditions for the best precision and accuracy in isotope ratios of individual NPs, which had been only reported to date with multicollector instruments. It is shown that the precision of the measurement of these ratios is limited by the magnitude of the signals obtained for each NP in the mass analyzer (counting statistics). However, the uncertainty obtained for the sizing of NPs in this approach can be improved by careful method optimization, where the most important parameters are shown to be the selection of the spike isotopic composition and concentration. Although only AgNPs were targeted in this study, the method presented, with the corresponding adaptations, could be applied to NPs of any other composition that include an element with different naturally available isotopes.

An Approach Based on an Increased Bandpass for Enabling the Use of Internal Standards in Single Particle ICP-MS: Application to AuNPs Characterization.

This paper proposes a novel approach to implement an internal standard (IS) correction in single particle inductively coupled plasma mass spectrometry (SP ICP-MS), as exemplified for the characterization of Au nanoparticles (NPs) in complex matrices. This approach is based on the use of the mass spectrometer (quadrupole) in bandpass mode, enhancing the sensitivity for the monitoring of AuNPs while also allowing for the detection of PtNPs in the same measurement run, such that they can serve as an internal standard. The performance of the method developed was proved for three different matrices: pure water, a 5 g L-1 NaCl water solution, and another water solution containing 2.5% (m/v) tetramethylammonium hydroxide (TMAH)/0.1% Triton X-100. It was observed that matrix-effects impacted both the sensitivity of the NPs and their transport efficiencies. To circumvent this problem, two methods were used to determine the TE: the particle size method for sizing and the dynamic mass flow method for the determination of the particle number concentration (PNC). This fact, together with the use of the IS, enabled us to attain accurate results in all cases, both for sizing and for the PNC determination. Additionally, the use of the bandpass mode provides additional flexibility for this characterization, as it is possible to easily tune the sensitivity achieved for each NP type to ensure that their distributions are sufficiently resolved.

A novel approach for adapting the standard addition method to single particle-ICP-MS for the accurate determination of NP size and number concentration in complex matrices.

This paper presents a novel approach, based on the standard addition method, for overcoming the matrix effects that often hamper the accurate characterization of nanoparticles (NPs) in complex samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). In this approach, calibration of the particle size is performed by two different methods: (i) by spiking a suspension of NPs standards of known size containing the analyte, or (ii) by spiking the sample with ionic standards; either way, the measured sensitivity is used in combination with the transport efficiency (TE) for sizing the NPs. Moreover, such transport efficiency can be readily obtained from the data obtained via both calibration methods mentioned above, so that the particle number concentration can also be determined. The addition of both ionic and NP standards can be performed on-line, by using a T-piece with two inlet lines of different dimensions. The smaller of the two is used for the standards, thus ensuring a constant and minimal sample dilution. As a result of the spiking of the samples, mixed histograms including the signal of the sample and that of the standards are obtained. However, the use of signal deconvolution approaches permits to extract the information, even in cases of signal populations overlapping. For proofing the concept, characterization of a 50 nm AuNPs suspension prepared in three different media (i.e., deionized water, 5% ethanol, and 2.5% tetramethyl ammonium hydroxide-TMAH) was carried out. Accurate results were obtained in all cases, in spite of the matrix effects detected in some media. Overall, the approach proposed offers flexibility, so it can be adapted to different situations, but it might be specially indicated for samples for which the matrix is not fully known and/or dilution is not possible/recommended.

Extraction induced by microemulsion breaking as a novel tool for the simultaneous determination of Cd, Mn, Pb and Sb in gasoline samples by ICP-MS and discrete sample introduction.

This study reports a simple and efficient method for the simultaneous determination of Cd, Mn, Pb, and Sb at trace levels in gasoline samples by discrete sample introduction in inductively coupled plasma mass spectrometry (ICP-MS), employing the extraction induced by microemulsion breaking as a sample preparation method. In this work, a microemulsion was formed by mixing 0.7 mL of the gasoline sample with 0.28 mL of ethanol and 0.02 mL of 7 mol L-1 HNO3 solution. Afterwards, 0.1 mL of ultrapure water was added to induce microemulsion breaking. This lead to the formation of two different phases: (i) a top organic phase and (ii) a bottom aqueous phase that contained acid, ethanol and the extracted analytes. After that, 20 µL of the bottom phase (extract) was collected, and the analyte concentrations were determined by discrete sample introduction in ICP-MS. Calibration curves with 20 µg L-1 of Rh as an internal standard were set up to each analyte in the range from 1 up to 10 µg L-1, wherein the standard solutions were prepared in the matrix-matched extract (70:25:5, ethanol: deionized water: 7 mol L-1 HNO3 solution). The optimization of the EIMB conditions was carried out by analyzing the effects of the parameters that could affect the extraction efficiency, such as the relation between the nature of the alcohol and the proportion of the volumes of the microemulsion constituents (sample, HNO3 and alcohol), acid concentration, and the water volume used for the microemulsion breaking. The following limits of detection relative to the amount of sample were obtained: 0.03 (Cd), 0.49 (Mn), 0.07 (Pb) and 0.02 (Sb), all of them in µg L-1. The accuracy of the method was evaluated by the analysis of spiked samples, because no certified gasoline reference material is available. The average recoveries achieved for every analyte ranged from 96% to 114%. The developed methodology was successfully applied to the determination of these metals in five commercial gasoline samples.

On the effect of using collision/reaction cell (CRC) technology in single-particle ICP-mass spectrometry (SP-ICP-MS).

In this work, the effects of using collision/reaction cell (CRC) technology in quadrupole-based ICP-MS (ICP-QMS) instrumentation operated in single-particle (SP) mode have been assessed. The influence of (i) various CRC gases, (ii) gas flow rates, (iii) nanoparticle (NP) sizes and (iv) NP types was evaluated using Ag, Au and Pt NPs with both a traditional ICP-QMS instrument and a tandem ICP-mass spectrometer. It has been shown that using CRC technology brings about a significant increase in the NP signal peak width (from 0.5 up to 6 ms). This effect is more prominent for a heavier gas (e.g., NH3) than for a lighter one (e.g., H2 or He). At a higher gas flow rate and/or for larger particle sizes >100 nm), the NP signal duration was prolonged to a larger extent. This effect of using CRC technology has been further demonstrated by characterizing custom-made 50 and 200 nm Fe3O4 NPs (originally strongly affected by the occurrence of spectral overlap) using different CRC approaches (H2 on-mass and NH3 mass-shift). The use of NH3 (monitoring of Fe as the Fe(NH3)2+ reaction product ion at m/z = 90 amu) induces a significant peak broadening compared to that observed when using H2 (6.10 ±â€¯1.60 vs. 0.94 ±â€¯0.49 ms). This extension of transit time can most likely be attributed to the collisions/interactions of the ion cloud generated by a single NP event with the CRC gas and it even precludes 50 nm Fe3O4 NPs to be detected when using the NH3 mass-shift approach. Based on these results, the influence of a longer peak width on the accuracy of SP-ICP-MS measurement data (NP size, particle number density and mass concentration) must be taken into account when using CRC technology as a means to overcome spectral overlap. To mitigate the potential detrimental effect of using CRC technology in the characterization of NPs via SP-ICP-MS(/MS), the use of light gases and low gas flow rates is recommended.

Determination of chlorine via the CaCl molecule by high-resolution continuum source graphite furnace molecular absorption spectrometry and direct solid sample analysis.

This work investigates the possibilities of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of Cl in solid samples via the CaCl molecule and measurement of its molecular absorption. The method proposed is based on addition of 400µg Ca as molecule-forming reagent and of 20µgPd as chemical modifier, which helps to stabilize the analyte and enhances sensitivity. The molecular spectrum for CaCl offers different lines with different limits of detection and linear ranges, which permitted to analyze solid samples with different Cl contents. The lowest limit of detection (0.75ng Cl, corresponding to 0.75µgg-1 for a typical sample mass of 1mg) could be achieved by combination of three of the most sensitive lines in the vicinity of 620.862nm, while the amplest linear range (up to 860ng Cl) was achieved by selection of the less sensitive line at 377.501nm. The method developed enabled the direct determination of Cl in solid samples using simple external calibration with aqueous standards. Good precision (5-9% RSD) and accuracy was attained in a series of certified samples of very different nature (i.e. coal, iron oxide, polyethylene, human hair, pine needles, rice flour and milk) and with very different Cl contents, ranging from about 50µgg-1 to 1% (w/w) Cl. The method appears as particularly useful for Cl determination in samples with elevated Ca contents, for which biased results with other diatomic molecules, such as AlCl or SrCl, may be obtained.

Determination of ultra-trace amounts of prosthesis-related metals in whole blood using volumetric absorptive micro-sampling and tandem ICP - Mass spectrometry.

This paper reports on an evaluation of the suitability of a novel sample collection approach, volumetric absorptive micro-sampling (VAMS), in the context of the determination of ultra-trace concentrations of prosthesis-related metals (Al, Ti, V, Co, Cr, Ni, Sr and Zr) in whole blood. In a first phase, a simple dilute-and-shoot approach (100-fold dilution) followed by tandem ICP - mass spectrometry (ICP-MS/MS) analysis was developed for the accurate and sensitive determination of the target elements. The ICP-MS/MS method relies on the use of mass shift reactions proceeding when pressurizing the collision/reaction cell (CRC) with CH3F/He for dealing with spectral overlap. Limits of detection (LoDs) between 0.3 and 30 ng L-1 were attained in a multi-element approach. The accuracy of the method was demonstrated via successful analysis of the reference materials Seronorm Whole Blood Levels 1 and 3, and real venous blood samples, spiked with the target elements at different concentration levels (5-50 µg L-1). Although the implementation of VAMS devices introduced contamination problems for Al, Cr and Ni, VAMS followed by ICP-MS/MS analysis shows potential for future real-life routine applications when assessing levels of Ti, V, Co, Sr and/or Zr.

Inductively coupled plasma - Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra)trace elements ­ A tutorial review.

This paper is intended as a tutorial review on the use of inductively coupled plasma - tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H2, O2 and NH3, also the use of promising alternative gases, such as CH3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis.

Lead screening in DBS by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry: application to newborns and pregnant women.

BACKGROUND: DBS have become a clinical specimen especially adequate for establishing home-based collection protocols. In this work, high-resolution continuum source graphite furnace atomic absorption spectrometry is evaluated for the direct monitoring of Pb in DBS, both as a quantitative tool and a screening method. METHODOLOGY: The development of the screening model is based on the establishment of the unreliability region around the threshold limits, 100 or 50 µg l(-1). More than 500 samples were analyzed to validate the model. CONCLUSION: The screening method demonstrated high sensitivity (the rate of true positives detected was always higher than 95%), an excellent LOD (1 µg l(-1)) and high throughput (10 min per sample).

Interference-free determination of ultra-trace concentrations of arsenic and selenium using methyl fluoride as a reaction gas in ICP-MS/MS.

Interference-free conditions, allowing straightforward As and Se determination, can be obtained by using CH3F (a mixture of 10% CH3F and 90% He) as a reaction gas in tandem ICP-mass spectrometry (ICP-MS/MS). Both target elements react via CH3F addition and subsequent HF elimination, rendering AsCH2 (+) and SeCH2 (+) the respective favored reaction product ions. Instrumental limits of detection were 0.2 ng L(-1) for As and below 10 ng L(-1) for Se, using either (77)Se, (78)Se, or (80)Se. Neither addition of carbon to the solutions, nor admixing of additional He into the octopole reaction cell resulted in a further improvement of the LoDs, despite the increase in analyte signal intensity. By using synthetic matrices, containing elements giving rise to ions interfering at either the original mass-to-charge ratios or those of the reaction products, absence of spectral overlap could be demonstrated. This conclusion was corroborated by successful As and Se determination in a collection of reference materials from plant, animal, or environmental origin, displaying a considerable range of As and Se contents. These accurate results were obtained via external calibration using Te as an internal standard. The high efficiency reaction between As and CH3F and the possibility to use the major isotope of Se provides enhanced detection power versus other techniques, such as sector-field ICP-mass spectrometry, while the possibility to monitor at least three Se isotopes interference-free also enables isotopic analysis.

Potential of methyl fluoride as a universal reaction gas to overcome spectral interference in the determination of ultratrace concentrations of metals in biofluids using inductively coupled plasma-tandem mass spectrometry.

Methyl fluoride (a mixture of 10% CH3F and 90% of He) was evaluated as a reaction gas in inductively coupled plasma-tandem mass spectrometry (ICPMS/MS) in the context of the determination of ultratrace concentrations of medically relevant metals (Al, Co, Cr, Mn, Ni, Ti, and V) in blood serum and urine. Via product ion scanning, whereby only ions of the mass-to-charge ratio of the target nuclide were admitted into the octopole reaction cell, the various reaction product ions formed for each of the target elements were identified at different CH3F gas flow rates. Limits of detection (LODs) and of quantification (LOQs) and linearity of the calibration curve were documented under (i) optimized ICPMS/MS conditions for single-element monitoring and (ii) compromise conditions, allowing for multielement determination. Even under compromise settings, instrumental LODs were below 10 ng/L for all target elements, while the use of CH3F provided interference-free conditions for their determination in the biofluids of interest. Quantitative data obtained for Seronorm blood serum and urine reference materials were in excellent agreement with the corresponding reference values and/or results obtained using double-focusing sector-field ICPMS (for those elements for which no certified values were available or that were affected during reconstitution), proving the potential of this reaction gas for multielement ultratrace analysis via ICPMS/MS.

Accurate determination of ultra-trace levels of Ti in blood serum using ICP-MS/MS.

Ti is frequently used in implants and prostheses and it has been shown before that the presence of these in the human body can lead to elevated Ti concentrations in body fluids such as serum and urine. As identification of the exact mechanisms responsible for this increase in Ti concentrations, and the risks associated with it, are not fully understood, it is important to have sound analytical methods that enable straightforward quantification of Ti levels in body fluids (for both implanted and non-implanted individuals). Until now, only double-focusing sector field ICP-mass spectrometry (SF-ICP-MS) offered limits of detection that are good enough to deal with the very low basal levels of Ti in human serum. This work reports on the development of a novel method for the accurate and precise determination of trace levels of Ti in human serum samples, based on the use of ICP-MS/MS. O2 and NH3/He have been compared as reaction gases. While the use of O2 did not enable to overcome all spectral interferences, it has been shown that conversion of Ti(+) ions into Ti(NH3)6(+) cluster ions by using NH3/He as a reaction gas in an ICP-QQQ-MS system, operated in MS/MS mode, provided interference-free conditions and sufficiently low limits of detection, down to 3 ng L(-1) (instrumental detection limit obtained for the most abundant Ti isotope). The accuracy of the method proposed was evaluated by analysis of a Seronorm Trace Elements Serum L-1 reference material and by comparing the results obtained with those achieved by means of SF-ICP-MS. As a proof-of-concept, the newly developed method was successfully applied to the determination of Ti in serum samples obtained from individuals with and without Ti-based implants. All results were found to be in good agreement with those obtained by means of SF-ICP-MS. The typical basal Ti level in human serum was found to be <1 µg L(-1), while values in the range of 2-6 µg L(-1) were observed for implanted patients.

Cross-sectional relationship between chronic stress and mineral concentrations in hair of elementary school girls.

Chronic stress exposure is associated with diverse negative health outcomes. It has been hypothesised that stress may also negatively affect the body's mineral status. This study investigates the association between chronic stress and long-term mineral concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), phosphorus (P) and zinc (Zn) in scalp hair among elementary school girls. Complete information on child-reported stress estimates (Coddington Life Events Scale (CLES)), hair cortisone and hair mineral concentrations, and predefined confounders in the stress-mineral relationship (i.e. age, body mass index, physical activity, diet, hair colour and parental education) was provided cross-sectionally for 140 girls (5-10 years old). The relationship between childhood stress measures (predictor) and hair minerals (outcome) was studied using linear regression analysis, adjusted for the abovementioned confounders. Hair cortisone concentrations were inversely associated with hair mineral concentrations of Ca, Mg, Zn and the Ca/P ratio. Children at risk by life events (CLES) presented an elevated Ca/Mg ratio. These findings were persistent after adjustment for confounders. This study demonstrated an independent association between chronic stress measures and hair mineral levels in young girls, indicating the importance of physiological stress-mineral pathways independently from individual or behavioural factors. Findings need to be confirmed in a more heterogeneous population and on longitudinal basis. The precise mechanisms by which stress alters hair mineral levels should be further elucidated.

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.

Hair minerals and metabolic health in Belgian elementary school girls.

Literature has repeatedly shown a relationship between hair minerals and metabolic health, although studies in children are currently lacking. This study aims to investigate hair levels of calcium (Ca), copper (Cu), magnesium (Mg), iron (Fe), phosphorus (P), and zinc (Zn) and their association with (1) overweight/obesity and (2) metabolic health in Flemish elementary school girls between 5 and 10 years old. Two hundred eighteen girls participated in this study as part of the baseline ChiBS project. Children were subjected to physical examinations, blood and hair sampling. Hair minerals were quantitatively determined via inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion. Body mass index (BMI) and body fat percentage (BF%) were studied as anthropometric parameters, and a metabolic score (including systolic and diastolic blood pressure, insulin resistance and non-high-density lipoprotein (non-HDL) cholesterol as parameters) was calculated, with higher scores indicating a more unhealthy metabolic profile. Hair Ca, Ca/Mg, and Ca/P positively correlated with the anthropometric parameters. An inverse correlation was observed between Ca, Mg, and Ca/P in hair and the metabolic score. Inverse correlations were also observed for individual metabolic parameters (i.e., diastolic blood pressure, homeostasis model assessment for insulin resistance, non-HDL cholesterol). In particular, girls with a total number of three or more metabolic parameters above the age-specific 75th percentile showed significantly reduced hair Ca, Mg, and Ca/P concentrations. This study showed reduced hair mineral concentrations in young girls with a more unhealthy metabolic profile. Positive associations were observed between some minerals and BMI and BF%.

Direct trace-elemental analysis of urine samples by laser ablation-inductively coupled plasma mass spectrometry after sample deposition on clinical filter papers.

Collection of biological fluids on clinical filter papers shows important advantages from a logistic point of view, although analysis of these specimens is far from straightforward. Concerning urine analysis, and particularly when direct trace elemental analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is aimed at, several problems arise, such as lack of sensitivity or different distribution of the analytes on the filter paper, rendering obtaining reliable quantitative results quite difficult. In this paper, a novel approach for urine collection is proposed, which circumvents many of these problems. This methodology consists on the use of precut filter paper discs where large amounts of sample can be retained upon a single deposition. This provides higher amounts of the target analytes and, thus, sufficient sensitivity, and allows addition of an adequate internal standard at the clinical lab prior to analysis, therefore making it suitable for a strategy based on unsupervised sample collection and ulterior analysis at referral centers. On the basis of this sampling methodology, an analytical method was developed for the direct determination of several elements in urine (Be, Bi, Cd, Co, Cu, Ni, Sb, Sn, Tl, Pb, and V) at the low µg L(-1) level by means of LA-ICPMS. The method developed provides good results in terms of accuracy and LODs (≤1 µg L(-1) for most of the analytes tested), with a precision in the range of 15%, fit-for-purpose for clinical control analysis.

Mineral concentrations in hair of Belgian elementary school girls: reference values and relationship with food consumption frequencies.

Although evidence suggests that hair elements may reflect dietary habits and/or mineral intake, this topic remains controversial. This study therefore presents age-specific reference values for hair concentrations of Ca, Cu, Fe, Na, Mg, P and Zn using the LMS method of Cole, and investigates the relationship between dietary habits (i.e. food consumption frequencies) and hair mineral concentrations in 218 Belgian elementary school girls by reduced rank regression (RRR). Hair minerals were quantitatively determined via inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion of 6-cm long vertex posterior hair samples. The Children's Eating Habits Questionnaire-Food Frequency Questionnaire was used to obtain information on food consumption frequency of 43 food items in the month preceding hair collection. The established reference ranges were in line with data for other childhood or adolescent populations. The retained RRR factors explained 40, 50, 45, 46, 44 and 48 % of the variation of Ca, Cu, Fe, Mg, P and Zn concentrations in hair, respectively. Although this study demonstrated that a large proportion of hair mineral variation may be influenced by food consumption frequencies in elementary school girls, a number of food groups known to be rich sources of minerals did not show a relation with certain hair minerals. Future research should focus on mechanisms and processes involved in mineral incorporation and accumulation in scalp hair, in order to fully understand the importance and influence of diet on hair minerals.

The use of liposomes to differentiate between the effects of nickel accumulation and altered food quality in Daphnia magna exposed to dietary nickel.

A potential drawback of traditional dietary metal toxicity studies is that it is difficult to distinguish between the direct toxicity of the metal and indirect effects caused by altered concentrations of essential nutrients in the metal-contaminated diet. In previous studies it has become clear that this can hamper the study of the real impact of dietary metal exposure and also complicates the analysis of the mechanisms of dietary metal toxicity in filter-feeding freshwater invertebrates like Daphnia magna. This problem has been partly circumvented by the production of liposomes, since these vectors are invulnerable to metal-induced food quality shifts and as such can be applied to study the mechanisms of dietary metal toxicity without the confounding effect of nutritional quality shifts. The aim of current study was to evaluate if there is relevance for dietary Ni toxicity under natural exposures, i.e., when D. magna is exposed to dietary Ni via living algae, and secondly, to quantify how nutritional quality shifts contribute to the toxic effects that are observed when algae are used as contaminated food vectors. For this aim, liposomes were prepared by the hydration of phosphatidylcholine in media containing 0 (control), 10, 50, 100 and 500 mg Ni/L. The liposome particles were then mixed with uncontaminated green algae in a 1/10 ratio (on a dry wt basis) to make up diets with constant nutrient quality and varying Ni contents (i.e., 1.2 µg Ni/g dry wt in the control and 18.7, 140.3, 165.0 and 501.6 µg Ni/g dry wt in the Ni-contaminated diet, respectively). A second food type was prepared on the basis of a 1/10 mixture (on a dry weight basis) of control liposomes and Ni-contaminated algae, representing a diet that differed in Ni content (i.e., 1.2, 26.8, 84.7, 262.3 and 742.7 µg Ni/g dry wt) and concentrations of essential nutrients (in terms of P and omega 3 poly-unsaturated fatty acids like eicosapentaenoic acid and α-linolenic acid). Both diets were then simultaneously fed to D. magna during a 21-day chronic bioassay, using reproduction, growth, survival, ingestion rate and Ni bioaccumulation as endpoints. Ni delivered by liposomes caused a significant inhibition of reproduction and growth when the metal accumulated to minimum levels of 11.9 and 20.0 µg Ni/g dry wt after 7 and 14 days, respectively. Using algae as Ni vector, similar effects of dietary Ni exposure occurred when algae had been pre-exposed to concentrations of at least 133 µg/L of bioavailable Ni (i.e., Ni2+), which is similar to the reproductive EC50 of waterborne Ni exposure for D. magna (115 µg Ni2+/L). While this may have some consequences for predicting chronic Ni toxicity in this range of Ni concentrations with the biotic ligand model--which could be further improved by including the dietary toxicity pathway in this model, the occurrence of such high concentrations in the field is very rare. Hence, there seems to be very little environmental relevance for dietary Ni toxicity to D. magna. Finally, besides the direct effects of Ni there was no evidence that nutritional quality shifts could have affected daphnids' growth, but it is very likely that the impairment of reproduction at toxic exposure levels of Ni was also partly the result of reduced fatty acid levels.