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In the earlier parts of this series of reviews , the most relevant flowing stream techniques (namely, segmented flow analysis, continuous flow analysis, flow injection (FI) analysis, sequential injection (SI) analysis, multicommuted flow injection analysis and multisyringe flow injection analysis) applied to the determination of several core inorganic parameters for water quality assessment, such as nutrients and anionic species including nitrogen, sulfur and halogen compounds, were described.In the present paper, flow techniques are presented as powerful analytical tools for the environmental monitoring of metal ions (alkaline and alkaline-earth metals, and elemental and harmful transition metals) as well as to perform both multielemental and speciation analysis in water samples. The potentials of flow techniques for automated sample treatment involving on-line analyte separation and/or pre-concentration are also discussed in the body of the text, and demonstrated for each individual ion with a variety of strategies successfully applied to trace analysis. In this context, the coupling of flow methodologies with atomic spectrometric techniques such as flame atomic absorption spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma mass spectrometry (ICPMS) or hydride-generation (HG)/cold-vapor (CV) approaches, launching the so-called hyphenated techniques, is specially worth mentioning. [Copyright &y& Elsevier]

The contents of 36 elements were determined in Pleurozium schreberi moss collected along 12 linear transects at 56 sampling points running radially up to a distance of 14 km from the secondary smelter ground at Příbram in the Czech Republic. Moss monitoring techniques enabled an assessment of the distribution of relative and, for many elements, the absolute atmospheric deposition rates that have been found for many elements in the details of land cadastres and allotments over an area of 700 km2. In addition to the hot spots for accumulation of smelter elements centred on the smelter ground, other unexpected hot spots caused by the operation of previously underplayed pollution sources are revealed in fine-scale contour maps. The decrease in element content in moss with distance from the centres of the main hot spots were described remarkably well by regression equations. The results of PCA indicated that the distribution of these elements in moss in the area is substantially controlled by 4 factors. The smelter was found to be the crucial current emitter of Ag, As, Cd, Cu, (Hg), In, Pb, Sb and Zn. Gravel production from stone material from abandoned uranium pits has been a major source of Al, As, Be, Ce, Cr, Fe, Ga, La, Li, Nd, Pr, Sc, Th, U, V and Y pollution, and a piston-ring works has been contaminating the area heavily with Mo. The fourth factor controlling the distribution of Cs, Rb and Tl in moss may be the combined operation of non-industrial anthropogenic and geogenic factors. The content of some elements in the moss correlated with selected geomorphological characteristics. The estimated enormous deposition loads of many potentially hazardous elements from the smelter and the stone mill from the former uranium pit in the town should be taken into account as a hazard to the inhabitants. The plan to continue utilising the 20 remaining heaps from the abandoned uranium pits for gravel production should be abandoned because it would lead to major further contamination of the area. Fine-scale moss monitoring techniques have proved to be a powerful tool for determining the deposition rates of many elements around diverse point sources of pollution in the landscape. [ABSTRACT FROM AUTHOR]

A flow-injection system for multielemental analysis with a mercury(II) preconcentration step using a resin Chelite-S® (Serva Feinbiochemica Heidelberg, Part No. 41709) packed minicolumn by inductively coupled plasma atomic emission spectroscopy is described. A mercury reductive elution procedure with a mixture of SnCl[sub 2]/HCl was used, which allows use of 6mol/L HC1 solution instead of concentrated hydrochoric acid. The main parameters related to ICP operation, such as radio frequency power (950-1750W), auxiliary argon flow (0.0-1.5 L/min) and spray chamber nebulizer pressure (15-35 psi), were studied. Optimization of the FIA system was reached by defining the best eluent carrier stream (1.4-2.8 mL/min), Hg° carrier stream (10-40 mLmin[sup -1]), loading time (0.5-4.0 min), sample flow rate (1.25-10.0 mL/min), temperature of reactor gas-liquid separator (GLS) (25-75°C) and eluent volume (50-350 µL). Throughput is around 30 samples per hour for analytical solutions within the range 50-2500 ng Hg(II)/L. Results from certified material showed good precision (RSD < 3%, n = 12) and no statistical difference was observed for real samples analyzed by AAS and by the proposed system. [ABSTRACT FROM AUTHOR]

This study determined the content in 39 trace and ultratrace elements, among them 16 rare earth elements, in 153 wines from the Canary Islands (Spain). Analyses were performed by ICP-MS. Rare earth elements were strongly correlated among one another, red wines mean contents in these elements being lower than those of white and rosé wines, and they are not suitable to classify wines according to the island of origin. Contrarily, good recognition and prediction abilities were achieved with the other 23 elements in both linear discriminant analysis (96.7 and 95.4%, respectively) and back-propagation artificial neural network (100 and 99.3%, respectively) to classify wines according to the island of origin. The most discriminant elements were established. [ABSTRACT FROM AUTHOR]

Four catfish fillet homogenate treatments before multielemental metal analysis by simultaneous inductively coupled plasma/atomic emission spectroscopy were compared in triplicate. These treatments were: nitric acid wet-ashing by Parr bomb digestion; nitric acid wet-ashing by microwave digestion; tetramethylammonium hydroxide/nitric acid wet digestion; and dryashing. The tetramethylammonium hydroxide/nitric acid method was imprecise (coefficients of variation 20%). The dry-ashing method was fast and sensitive but had low recoveries of 50% for spiked Pb and Al and was not as precise as the Parr bomb or microwave treatments. The Parr bomb method was the most precise method but was less sensitive than the microwave method which had nearly the same precision. The microwave method was then adapted to homogenates of small whole fish 3cm in length. The whole fish homogenate required more vigorous digestion conditions, and addition of more acid after the evaporative step because of the presence of less oxidizable and acidsoluble components than fillet. The whole fish homogenate was also more heterogeneous than catfish fillet. A quality assurance protocol to demonstrate homogenate uniformity is essential. The use of a non-specialized microwave oven system allowed precise results for fillet and whole fish homogenates. [ABSTRACT FROM AUTHOR]

Portable X-ray fluorescence spectrometry (pXRF) is a well-known and accepted method for earth-materials analysis. It is also promising for analysis of plant tissues. However, some factors must be assessed in order to obtain a protocol for plants mainly for in-field measurements of intact and fresh leaves. This work defines an experimental approach for two distinct plant leaves (Spinach and Post Oak) considering water content (94% and 52% w / w , respectively) and anatomy. Using a commercial pXRF system equipped with a Rh X-ray tube, some conditions for in-situ and ex-situ analysis were assessed to obtain the concentrations of macro (P, K, Ca, Mg, and S) and micronutrients (Fe, Zn, Cu, and Mn). For in-situ applications, the penetration of X-rays through Pinus wood was evaluated. In this case, the goal was to propose a simple way to scan fresh and intact plant leaves in the field, using the wood as a background stage. Thus, the minimum wood thickness to avoid any influence of soil surface was investigated. Afterward, the following factors were assessed: i) the effect of water content; ii) the number of overlapped and pressed leaves on pXRF results; iii) the effect of adaxial or abaxial leaf surface. For ex-situ applications, the thickness of oven-dried and ground (< 0.6 mm) plant material packed into pXRF sample cup was tested. After pXRF analysis, the sum of all elements in the wood corresponded to only 0.91% having no significant influence on elemental composition of the leaves. In a qualitative manner, intact and fresh leaves can be placed on a 1-cm thick Pinus wood stage for analysis. Comparing fresh and dry leaves, water did have an effect on reported elemental concentrations, mainly for spinach leaves. For Post Oak leaves there was also an effect caused by water content but less than spinach, suggesting that for leaves with low water content (e.g., <50%) the effect of water content may be small. For both studied plant leaves there was no effect of adaxial or abaxial surface. For ex-situ analysis of oven-dried and ground plant material, the thickness in the sample cup must be strongly considered. This work suggests at least 1 cm thickness is required for accurate readings; thickness >1 cm is desirable. pXRF analysis of fresh and intact plant leaves in the field is possible in a qualitative manner. [Display omitted] • Procedure for in-field and qualitative assessment of plant leaves via pXRF was proposed. • Stable pXRF readings were reached with at least 1 cm thickness of plant material. • Scanning either adaxial or abaxial surface yielded similar results. • High water content of plant leaves considerably influence the pXRF results. [ABSTRACT FROM AUTHOR]

An X-ray fluorescence (XRF) system that uses radioisotopes in an orthogonal configuration between the source, sample, and detector is described. The advantage of such a system is that for large (bulk) samples or in vivo measurements, the background caused by Compton scattering in the sample is minimized. High reproducibility for nonuniform samples is obtained by reducing the sample size and thus the effects of nonuniformity in the spatial response of such a system. Germane to any accurate analytical method is the use of proper mathematical algorithms for data evaluation. The problem is acute, in particular, when photopeaks with low counting statistics are to be analyzed. In the case of a single photopeak on flat background, optimal energy window size, which maximizes the signal-to-noise ratio, for trapezoidal intergration is described. The sensitivity and minimum detection limit at different energies together with background considerations are discussed. [ABSTRACT FROM AUTHOR]

Based on green analytical chemistry principles it is important to evolve procedures that convert solid samples into solutions without using excessive reagent quantities, energy, temperature, and avoiding waste generation. To reach this aim, a simple infrared assisted digestion (IRAD) method for animal feed analysis was proposed. Infrared radiation (IR) with 2 mL of HNO 3 and 2 mL of H 2 O 2 were assessed, presenting low dissolved organic carbon (DOC) and residual acidity (RA) in the final digest, being fully compatible with microwave induced plasma atomic emission spectrometry (MIP OES). Calcium, Cd, Cu, Fe, K, Mg, Na, P, Sr and Zn were determined in reference materials and in animal feeds. Limits of quantification were between 2.52 and 284 mg kg−1 for Ca and P respectively. Recovery values ranged 80–120%, with relative standard deviations (RSD%) under 8%. The friendliness offered by the IRAD MIP OES method was evaluated by two green indexes. Concentrations in feedstuffs were compared with National Research Council (NRC) recommendations. [Display omitted] • An IRAD MIP OES procedure was developed as efficient green digestion method. • The whole sample treatment procedure could be completed in 30 min for 18 samples. • Ca, Cd, Cu, Fe, K, Mg, Na, P, Sr and Zn were analyzed in animal feed by MIP OES. • The greenness of the development procedure was assessed using two indexes. • The analytical proposed method could be employed for swine feed quality control. [ABSTRACT FROM AUTHOR]

Beehive products possess nutritional value and health-promoting properties and are recommended as so-called "superfoods". However, because of their natural origin, they may contain relevant elemental contaminants. Therefore, to assess the quality of bee products, we examined concentrations of a broad range of 24 selected elements in propolis, bee pollen, and royal jelly. The quantitative analyses were performed with inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The results of our research indicate that bee products contain essential macronutrients (i.e., K, P, and S) and micronutrients (i.e., Zn and Fe) in concentrations depending on the products' type. However, the presence of toxic heavy metals makes it necessary to test the quality of bee products before using them as dietary supplements. Bearing in mind that bee products are highly heterogenous and, depending on the environmental factors, differ in their elemental content, it is necessary to develop standards regulating the acceptable levels of inorganic pollutants. Furthermore, since bees and their products are considered to be an effective biomonitoring tool, our results may reflect the environment's condition in west-central Poland, affecting the health and well-being of both humans and bees. [ABSTRACT FROM AUTHOR]

Seventy-three samples of alcoholic beverages and juices that were purchased on the Polish market and home-made were analyzed for their elemental profiles. The levels of 23 metals were determined by ICP-MS (Ag, Ba, Bi, Cd, Co, Cr, Li, Mn, Ni, Pb, Sr and Tl), ICP-OES (Al, B, Ca, Cu, Fe, K, Mg, Na, Ti and Zn) and CVAAS (Hg) techniques in twenty-five samples of ciders widely available on the Polish market; six samples of home-made ciders; two samples of juices used in the production of these ciders; and forty samples of low-percentage, flavored alcoholic beverages based on beer. The gathered analytical data confirmed that the final elemental fingerprint of a product is affected by the elemental fingerprint of the ingredients used (apple variety) as well as the technology and equipment used by the producer, and in the case of commercial ciders, also the impact of type of the packaging used was proven. These factors are specific to each producer and the influence of the mentioned above parameters was revealed as a result of the performed analysis. Additionally, the inclusion of the home-made ciders in the data set helped us to understand the potential origin of some elements, from the raw materials to the final products. The applied statistical tests revealed (Kruskal–Wallis and ANOVA) the existence of statistically significant differences in the concentration of the following metals: Ag, Al, B, Bi, Co, Cr, Cu, Fe, K, Li, Mg, Na, Ni, Ti and Zn in terms of the type of cider origin (commercial and home-made). In turn, for different packaging (can or bottle) within one brand of commercial cider, the existence of statistically significant differences for Cu, Mn and Na was proved. The concentrations of all determined elements in the commercial cider from the Polish market and home-made cider samples can be considered as nontoxic, because the measured levels of elements indicated in the regulations were lower than the allowable limits. Moreover, the obtained results can be treated as preliminary for the potential authentication of products in order to distinguish the home-made (fake) from the authentic products, especially for premium-class alcoholic beverages. [ABSTRACT FROM AUTHOR]

Multi-elemental (Ca, Mg, Na, K, Al, As, Ba, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Tl, V, and Zn) and stable isotope (i.e., δ2H, δ18O, and δ13CDIC) analyses were performed on 13 (8 Slovenian and 5 imported) bottled mineral and spring waters from the Slovenian market. In addition, 87Sr/86Sr isotope ratios were determined for the first time. In all analyzed bottled waters, the majority of elements were present although in low concentrations, and according to EU legislation, all were suitable for human consumption. Also, concentrations of major elements (Ca, Mg, Na, and K) were in general agreement with the values reported on the bottle labels, and any differences were the consequence of the natural variability of the water source used for bottling. The exception was one spring water, for which the source location changed, which was confirmed by the δ2H, δ18O, and δ13CDIC data. Two mineral waters had distinctive elemental compositions due to the particular geology of their recharge areas. The δ13CDIC was also investigated to decipher the carbonate contribution in the bottled waters. The results suggest that dissolution of carbonates and non-equilibrium carbonate dissolution by carbonic acid produced from soil zone CO2 are the predominant geochemical processes influencing the δ13CDIC values of bottled water. [ABSTRACT FROM AUTHOR]

Agrometallomics, as an independent interdiscipline, is first defined and described in this review. Metallic elements widely exist in agricultural plants, animals and edible fungi, seed, fertilizer, pesticide, feedstuff, as well as the agricultural environment and ecology, and even functional and pathogenic microorganisms. So, the agrometallome plays a vital role in molecular and organismic mechanisms like environmetallomics, metabolomics, proteomics, lipidomics, glycomics, immunomics, genomics, etc. To further reveal the inner and mutual mechanism of the agrometallome, comprehensive and systematic methodologies for the analysis of beneficial and toxic metals are indispensable to investigate elemental existence, concentration, distribution, speciation, and forms in agricultural lives and media. Based on agrometallomics, this review summarizes and discusses the advanced technical progress and future perspectives of metallic analytical approaches, which are categorized into ultrasensitive and high-throughput analysis, elemental speciation and state analysis, and spatial- and microanalysis. Furthermore, the progress of agrometallomic innovativeness greatly depends on the innovative development of modern metallic analysis approaches including, but not limited to, high sensitivity, elemental coverage, and anti-interference; high-resolution isotopic analysis; solid sampling and nondestructive analysis; metal chemical species and metal forms, associated molecular clusters, and macromolecular complexes analysis; and metal-related particles or metal within the microsize and even single cell or subcellular analysis.

Whisky (whiskey) consists of many trace elements coming from the raw materials used in its fermentation, distillation and maturation processes. These ingredients assure the exceptional organoleptic characteristics of the beverage. Their analysis is important to better control the stages of fermentation, distillation, taste repeatability and for product quality assurance as well as from the brand protection point of view. This article presents the usefulness of modern analytical techniques based on elemental analysis. ICP mass spectrometry and CV atomic absorption spectroscopy were applied to distinguish whisky produced in Scotland from whisky coming from Ireland and the United States. The collected semi-quantitative data were used for multivariate analysis performed using the Statistica 10.0 software. The results showed that Irish whiskey is characterized by quite a high amount of Ba and Ti compared with other samples, which made it possible to distinguish this sample from the others. No strict correlation was found between the type of whisky and the amount of trace elements, however, the projection of objects on the first two components revealed that single malt samples created one cluster. [ABSTRACT FROM AUTHOR]

In this work, a method of recalculation of results of X-ray fluorescence (XRF) technique to Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) method was elaborated for biosorption studies. Equations that calibrate XRF to ICP-OES were determined, as a biosorbent strawberry, blackcurrant and raspberry seeds after supercritical CO2 extraction were used. ICP-OES showed a better precision and lower detection limits than XRF. The latter technique is cheaper, requires minimal sample preparation and gives faster results. Linear regression of the data gave almost 1:1 correlations without additional correction (for Cu r2 = 0.9998, Mn r2 = 0.807, Zn r2 = 0.979). Calibration and quantification of intensities of XRF was obtained using ICP-OES measurements after samples digestion with HNO3 in a microwave system. High positive correlations were estimated for Cu, Mn, Zn. It was demonstrated that XRF technique can be used together with other well established techniques (ICP-OES) to produce quantitative data from biosorption studies. Elaboration of cheap and quick analytical methodology is an important aspect in development of new processes and products based on biosorption process. [ABSTRACT FROM AUTHOR]