Analysis of trace phytoavailable heavy metals in saline soil extract by one-step electroextraction coupled with in situ desorption microplasma optical emission spectrometry.

On-site and sensitive analysis of phytoavailable heavy metals is the key to fast evaluate the pollution incidents, while the development of convenient and efficient sample introduction approaches against matrix interference is crucial to improve the performances of field-deployable instruments. Herein, trace phytoavailable heavy metals in soil are first extracted by 0.1 M NaNO3, afterwards adsorbed onto an activated carbon tip via electroextraction (EE), and finally analyzed by dielectric barrier discharge (DBD) microplasma optical emission spectrometry (OES) via in situ desorption. The activated carbon tip is not only able to extract heavy metals from alkali metals/alkaline earth metals matrix, resisting the interference of coexisting anions and non-electroactive species in saline soil extract, but also significantly improves the detection sensitivity of subsequent DBD-OES analysis by increasing loading amounts of analytes. Taking the key heavy metals pollution as model, the detection limits of Cd, Zn, Cu and Pb reach 0.8, 2.3, 6.0 and 4.5 µg kg-1, respectively, and precisions are within 2.7-4.6%. The accuracy and practicability of the present miniaturized EE-DBD-OES device have been verified by measuring several certified reference materials and real soil samples, providing a promising tool for convenient and sensitive analysis of trace phytoavailable heavy metals in soil.

Quantum chemical calculation studies toward microscopic understanding of retention mechanism of Cs radioisotopes and other alkali metals in lichens.

We evaluate stability of cesium (Cs) and other alkali-metal cation complexes of lichen metabolites in both gas and aqueous phases to discuss why lichens can retain radioactive Cs in the thalli over several years. We focus on oxalic acid, (+)-usnic acid, atranorin, lecanoric acid, and protocetraric acid, which are common metabolite substances in various lichens including, e.g., Flavoparmelia caperata and Parmotrema tinctorum retaining Cs in Fukushima, Japan. By performing quantum chemical calculations, their gas-phase complexation energies and aqueous-solution complexation free energies with alkali-metal cations are computed for their neutral and deprotonated cases. Consequently, all the molecules are found to energetically favor cation complexations and the preference order is Li[Formula: see text]Na[Formula: see text]K[Formula: see text]Rb[Formula: see text]Cs[Formula: see text] for all conditions, indicating no specific Cs selectivity but strong binding with all alkali cations. Comparing complexation stabilities among these metabolites, lecanoric and protocetraric acids seen in medullary layer are found to keep higher affinity in their neutral case, while (+)-usnic acid and atranorin in upper cortex exhibit rather strong affinity only in deprotonated cases through forming stable six atoms' ring containing alkali cation chelated by two oxygens. These results suggest that the medullary layer can catch all alkali cations in a wide pH range around the physiological one, while the upper cortex can effectively block penetration of metal ions when the metal stress grows. Such insights highlight a physiological role of metabolites like blocking of metal-cation migrations into intracellular tissues, and explain long-term retention of alkali cations including Cs in lichens containing enough such metabolites to bind them.

Optimized Multimetal Sensitized Phosphor for Enhanced Red Up-Conversion Luminescence by Machine Learning.

In this research, machine learning including the genetic algorithm (GA) and support vector machine (SVM) algorithm is used to solve the "low up-conversion luminescence (UCL) intensity" problem in order to find the optimal phosphor with enhanced red UCL emission using multielement K/Li/Mn metal modulation. Compared with the first generation of phosphors, the best phosphors' fluorescence intensity occurs in the third generation optimized by the GA, with a stronger brightness (4.91-fold), a higher relative quantum yield (6.40-fold), and an enhanced tissue penetration depth (by 5 mm). The single and multiple dopants effect on the upconversion intensity of K+Li+Mn sensitizers is also studied: the intensity increases first and then decreases with the increase of Yb/Er/K+Li+Mn content, and the optimized K+Li+Mn concentration is 6.03%. In order to confirm the stability of the brightness optimization by the GA, a batch of phosphors was synthesized with the same element proportion, and the similarity of fluorescence intensity of two batches of phosphors was evaluated by the SVM algorithm with the classification accuracy index. Finally, the optimized phosphor was used for bioimaging and phosphor-LED.

Accumulation Pattern of Inorganic Elements in Scaly Tooth Mushroom (Sarcodon imbricatus) from Northern Poland.

Several studies have documented contamination levels and daily intake of metallic elements from foodstuffs including rice, maize, pulses, vegetables, fruits, fish, meat, egg, milk etc., however, limited literature is available on metal contamination levels in wild growing mushrooms and possible human exposure via consumption of it. Sarcodon imbricatus is an edible mushroom, commonly consumed in many parts of the world. Very few studies have been conducted on inorganic elemental composition in fruiting bodies (edible part) of this fungus. In this study, elements such as silver (Ag), aluminum (Al), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co,) chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), phosphorous (P), lead (Pb), rubidium (Rb), strontium (Sr) and zinc (Zn) were measured in caps and stems of fruiting bodies of S. imbricatus collected from the Wdzydze forests in Central and the Augustowska Primeval forest in Eastern Poland. Results revealed that a wide variation in concentrations of various metals in caps and stems samples collected from the two forests. Toxic metallic elements such as Cd and Hg showed preferential accumulation in caps than stems samples from both the forests. However, the concentrations of Cd, Hg and Pb in the mushroom samples were below the established weekly intake tolerance limits.

Could biological tissue preservation methods change chemical elements proportion measured by energy dispersive X-ray spectroscopy?

Energy dispersive X-ray spectroscopy (EDS) is a powerful technical tool used in the biomedical field to investigate the proportion of chemical elements of interest in research, such as heavy metal bioaccumulation and the enzymatic cofactors and nanoparticle therapy in various pathologies. However, the correct evaluation of the proportion of the elements is subject to some factors, including the method of sample preservation. In this study, we seek to investigate the effect of biological tissue preservation methods on the proportion of chemical elements obtained by the EDS methodology. For such, we used EDS to measure the proportion of chemical elements with biomedical interest in preserved livers, using three common methods for preserving biological tissues: (a) freezing, (b) paraformaldehyde fixative solution, and (c) Karnovsky solution. We found an increased level of sodium and reduced contents of potassium and copper in samples fixed in fixative solutions, when compared to frozen samples (p < 0.05). Our data indicate that preservation methods can change the proportion of chemical elements in biological samples, when measured by EDS. Frozen preservation should be preferred to retain the actual chemical content of samples and allow a correct assessment of the proportion of their elements.

Variations in the Metallic Ion Concentration in the Silk Gland and Cocoon of Silkworm Antheraea assamensis helfer.

The natural spinning process in silkworms involves the conformation transition of the liquid silk protein present in the silk gland to make fiber. This conformation transition is influenced by different factors, and some studies suggested that changes in the metallic ion concentrations is one of them (Zhou et al. 2005). This study investigated the changes in the metallic ion compositions in the silk glands (before and during spinning) and cocoons of non-mulberry silkworm Antheraea assamensis helfer. Intact silk glands were dissected from mature 5th instar A. assamensis larvae. The glands were rinsed with deionized water and divided into five divisions: posterior silk gland (PSG), middle silk gland (MSG), anterior silk gland (ASG), posterior middle (PM) and anterior middle (AM) division of silk gland. Cocoon pieces and the gland parts were dried and digested in acid mixture to quantify the metallic contents in an atomic absorption spectrophotometer (Shimadzu, AA7000). We determined seven metals (Na, K, Mg, Ca, Cu, Zn, Fe) present in the different parts of the secretory pathway as well as in the fibers of A.assamensis. Our results suggested that the concentrations of Mg, Ca, Na, and K were more abundant in the gland than the Cu and Zn. Fe concentration was found comparatively less in amount in the gland. Amount of Ca found to be higher in the cocoons. The differences in the metallic ion concentrations in the gland parts before and during spinning suggested the possibility of their role in the formation of silk thread from luminal silk.

Determination of inorganic cations in biological fluids using a hybrid capillary electrophoresis device coupled with contactless conductivity detection.

We describe the assembly of a hybrid electrophoresis device that contains fused silica capillaries interconnected to a microfabricated interface in a cross format for the determination of inorganic cations in biological samples. The sample transport in the proposed hybrid device was performed under gated injection mode and the separations were monitored with a capacitively coupled contactless conductivity detector. The capillary extremities were inserted into polypropylene tubes to create solution reservoirs. Sensing electrodes were produced using stainless-steel hypodermic needles previously cut with 2.0 mm length. The running composition and injection time were optimized and the best results were found using 50 mmol/L lactic acid, 20 mmol/L histidine and 3 mmol/L 18-crown-6 ether, and an electrokinetic injection time of 15 s. The separation of six inorganic cations was achieved with baseline resolution, and efficiencies were between 9.1 × 103 and 5.4 × 104 plates/m. The proposed hybrid device was explored for determining the concentration levels of inorganic cations in urine, saliva, and tear samples, employing Li+ as an internal standard. The achieved results were in good agreement with the data reported in the literature. The reliability of the proposed method ranged from 93 to 98%, thus suggesting satisfactory accuracy for bioanalytical applications.

Major signal suppression from metal ion clusters in SFC/ESI-MS - Cause and effects.

The widening application area of SFC-MS with polar analytes and water-containing samples facilitates the use of quick and simple sample preparation techniques such as "dilute and shoot" and protein precipitation. This has also introduced new polar interfering components such as alkali metal ions naturally abundant in e.g. blood plasma and urine, which have shown to be retained using screening conditions in SFC/ESI-TOF-MS and causing areas of major ion suppression. Analytes co-eluting with these clusters will have a decreased signal intensity, which might have a major effect on both quantification and identification. When investigating the composition of the alkali metal clusters using accurate mass and isotopic pattern, it could be concluded that they were previously not described in the literature. Using NaCl and KCl standards and different chromatographic conditions, varying e.g. column and modifier, the clusters proved to be formed from the alkali metal ions in combination with the alcohol modifier and make-up solvent. Their compositions were [(XOCH3)n + X]+, [(XOH)n + X]+, [(X2CO3)n + X]+ and [(XOOCOCH3)n + X]+ for X = Na+ or K+ in ESI+. In ESI-, the clusters depended more on modifier, with [(XCl)n + Cl]- and [(XOCH3)n + OCH3]- mainly formed in pure methanol and [(XOOCH)n + OOCH]- when 20 mM NH4Fa was added. To prevent the formation of the clusters by avoiding methanol as modifier might be difficult, as this is a widely used modifier providing good solubility when analyzing polar compounds in SFC. A sample preparation with e.g. LLE would remove the alkali ions, however also introducing a time consuming and discriminating step into the method. Since the alkali metal ions were retained and affected by chromatographic adjustments as e.g. mobile phase modifications, a way to avoid them could therefore be chromatographic tuning, when analyzing samples containing them.

Characterization of Final Action Official MethodSM 2011.19 and First Action Official Method 2015.06 Performance at Analyte Levels Corresponding to CODEX STAN 72 (1981) Minimum Levels.

A limited single-laboratory validation (SLV) was conducted in the authors' laboratory to investigate the performance of AOAC Official MethodsSM 2011.19 Determination of Chromium (Cr), Selenium (Se), and Molybdenum (Mo) in Infant Formula and Adult Nutritional Products by Inductively Coupled Plasma/Mass Spectrometry and 2015.06 Determination of Minerals and Trace Elements in Infant Formula and Adult/Pediatric Nutritional Formula by Inductively Coupled Plasma/Mass Spectrometry at analyte levels below the practical LOQs (PLOQs) already published for these Final Action Official Methods. This work was needed to verify that the actual LOQs were below the minimum requirements for minerals in infant formula as given in CODEX STAN 72 (1981). Linearity studies at low levels were conducted as well as the analysis of blanks over multiple days to establish the LOQs (as opposed to PLOQs) for these nutrients. Several placebo matrixes from the AOAC Stakeholder Panel on Infant Formula and Adult Nutritionals (SPIFAN) program were tested over multiple days at two different sample sizes to quantitate the effect of doubling the sample size given in the original publications. The SLV results indicate that both methods can meet the Codex minimum requirements as-is, without modification of the methods, albeit with a relaxation of the stringent precision criteria originally established for these methods by SPIFAN. Precision can be improved by doubling the sample size, but this step is not necessary to use the method for its intended purpose. A concurrent collaborative study of Method 2015.06 showed that the RSDR obtained across eight laboratories for several infant formula placebos containing mineral concentrations between the PLOQ and LOQ were indeed worse than SPIFAN expectations, but reasonable Horwitz ratios (HorRat) were nonetheless obtained for these analytes.

Alkali metals levels in the human brain tissue: Anatomical region differences and age-related changes.

The link between trace elements imbalances (both "toxic" and "essential") in the human brain and neurodegenerative disease has been subject of extensive research. More recently, some studies have highlighted the potential role of the homeostasis deregulation of alkali metals in specific brain regions as key factor in the pathogenesis of neurodegenerative diseases such as multiple sclerosis and Alzheimer's disease. Using flame atomic emission spectrometry and inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion of the samples, alkali metals (Na, K, Li, Rb and Cs) were determined in 14 different areas of the human brain (frontal cortex, superior and middle temporal gyri, caudate nucleus, putamen, globus pallidus, cingulated gyrus, hippocampus, inferior parietal lobule, visual cortex of the occipital lobe, midbrain, pons, medulla and cerebellum) of adult individuals (n=42; 71±12, range: 50-101 years old) with no known history and evidence of neurodegenerative, neurological or psychiatric disorder. Potassium was found as the most abundant alkali metal, followed by Na, Rb, Cs and Li. Lithium, K and Cs distribution showed to be quite heterogeneous. On the contrary, Rb and Na appeared quite homogeneously distributed within the human brain tissue. The lowest levels of Na, K, Rb and Li were found in the brainstem (midbrain, medulla and pons) and cerebellum, while the lowest levels of Cs were found in the frontal cortex. The highest levels of K (mean±sd; range 15.5±2.5; 8.9-21.8mg/g) Rb (17.2±6.1; 3.9-32.4µg/g and Cs (83.4±48.6; 17.3-220.5ng/g) were found in putamen. The highest levels of Na and Li were found in the frontal cortex (11.6±2.4; 6.6-17.1mg/g) and caudate nucleus (7.6±4.6 2.2-21.3ng/g), respectively. Although K, Cs and Li levels appear to remain largely unchanged with age, some age-related changes were observed for Na and Rb levels in particular brain regions (namely in the hippocampus).

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

The microwave induced plasma with optical emission spectrometry (MIP-OES) in 23 elements determination in geological samples.

The article presents the optimisation, validation and application of the microwave induced plasma optical emission spectrometry (MIP-OES) dedicated for a routine determination of Ag, Al, B, Ba, Bi, Ca, Cd, Cr, Cu, Fe, Ga, In, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sr, Tl, Zn, in the geological samples. The three procedures of sample preparation has been proposed: sample digestion with the use of hydrofluoric acid for determination of total concentration of elements, extraction by aqua regia for determination of the quasi-total element concentration and extraction by hydrochloric acid solution to determine contents of the elements in acid leachable fraction. The detection limits were on the level 0.001-0.121 mg L(-1) (from 0.010-0.10 to 1.2-12 mg kg(-1) depend on the samples preparation procedure); the precision: 0.20-1.37%; accuracy 85-115% (for recovery for certified standards materials analysis and parallel analysis by independent analytical techniques: X-ray fluorescence (XRF) and flame absorption spectrometry (FAAS)). The conformity of the results obtained by MIP-OES analytical procedures with the results obtained by XRF and FAAS analysis allows to propose the procedures for studies of elemental composition of the fraction of the geological samples. Additionally, the MIP-OES technique is much less expensive than ICP techniques and much less time-consuming than AAS techniques.

Variability of microchip capillary electrophoresis with conductivity detection.

Microfluidic CE with conductivity detection platforms could have an impact on the future development of smaller, faster and portable devices. However, for the purpose of reliable identification and quantification, there is a need to understand the degree of irreproducibility associated with the analytical technique. In this study, a protocol was developed to remove baseline drift problems sometimes observed in such devices. The protocol, which consisted of pre-conditioning steps prior to analysis, was used to further assess measurement variability from 24 individual microchips fabricated from six separate batches of glass substrate. Results show acceptable RSD percentage for retention time measurements but large variability in their corresponding peak areas (with some microchips having variability of ∼50%). Sources of variability were not related to substrate batch but possibly to a number of factors such as applied voltage fluctuations or variations in microchannel quality, for example surface roughness that will subsequently affect microchannel dimensions.

Structural elucidation studies of 15-membered azalide macrocycles using H/D exchange and ESI-MS(n.).

A comprehensive study of fragmentation pathways of 15-membered azalide macrocycles using electrospray ionisation with multistage mass spectrometry (ESI-MS(n)) is presented in this work. Hydrogen/deuterium (H/D) exchange experiments and high-resolution mass spectrometry were used to investigate the proposed fragmentation pathways. In addition, the fragmentation patterns of sodium adduct ions [M+Na](+) of the macrocycles were also investigated as the presence of an alkali metal interacting with the aglycone ring influences the product-ion spectra.

Age-related effects of major and trace element concentrations in rat liver and their mutual relationships.

The concentrations of 22 major and trace elements in livers from rats aging from 5 to 113 weeks old were determined. The rats investigated were the same rats previously reported with respect to 29 elements in bones (femur) and 26 elements in kidneys. The samples were decomposed with high-purity nitric acid and hydrogen peroxide. Seven elements (Na, Mg, P, K, Ca, Fe and Zn) were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES), and 15 elements (Mn, Co, Cu, As, Se, Rb, Sr, Mo, Cd, Sn, Sb, Cs, Ba, Pb and Bi) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Analysis of variance (ANOVA) for age variations indicated that the concentrations of many elements, such as Mg, P, K, Mn, Fe, Cu, Zn, Sr, Mo and Cd, were almost constant across the ages of the rats with the exception of 5 weeks old (p > 0.05). Arsenic, Pb and Bi showed significant increasing trends, while Na and Co showed decreasing trends (p < 0.01). Selenium showed a decreasing trend except at the initial stage of 5-9 weeks old. Calcium, Rb, Sn, Sb, Cs and Ba showed significant age-related variations, but their patterns were not monotonic. The liver clearly contrasts with the kidneys, in which many elements showed significant age-related variations with increasing trends. The concentration ranges of Mg, P, K, Mn, Cu, Zn, and Mo were controlled within 15% across all ages of rats. The homeostasis of the aforementioned elements may be well established in the liver. The toxic elements, such as Cd, Pb and Bi, showed a narrow concentration range among age-matched rats.

The evolutionary ecology of dwarfism in three-spined sticklebacks.

1. Body size is a defining phenotypic trait, but the ecological causes of its evolution are poorly understood. Most studies have considered only a single putative causal agent and have failed to recognise that different environmental agents are often correlated. 2. Darwin suggested that although trait variation across populations is often associated with abiotic variation, evolution is more likely to be driven by biotic factors correlated with the abiotic variation. This hypothesis has received little explicit attention. 3. We use structural equation modelling to quantify the relative importance of abiotic (pH, metal concentrations) and biotic (competition, predation) factors in the evolution of body size in three-spined sticklebacks Gasterosteus aculeatus on the island of North Uist, Scotland. We combine phenotypic data from multiple isolated populations, detailed characterisation of their environment and a common garden experiment that establishes the genetic basis of size differences. 4. Three-spined sticklebacks on North Uist show almost unprecedented intraspecific evolution of body size that has taken place rapidly (<16,000 years). The smallest fish mature at only 7% of the mass of ancestral, anadromous fish. Dwarfism is associated with reduced abundance of a smaller competitor species, the nine-spined stickleback Pungitius pungitius, and with low pH indicative of poor resource conditions. Dwarfism also tends to occur where an important predator, the brown trout Salmo trutta, is also small. The abundance of P. pungitius and the size of S. trutta are themselves related to underlying abiotic environmental variation. 5. Despite the close association between abiotic and biotic factors across populations, our results support Darwin's hypothesis that biotic factors, associated with variation in the abiotic environment, are more important in explaining evolution than is abiotic variation per se. This study demonstrates the importance of considering the relationships between environmental variables before conclusions can be drawn about the causes of (body size) evolution on islands.

Separation of alkali metals using isotachophoresis with cryptand 222 as a leading electrolyte additive.

This work shows how the inclusion of cryptand 222 as a leading electrolyte additive in isotachophoresis affects the electrophoretic mobilities of alkali metal cations. Using isotachophoresis the separation of alkali metals can be difficult due to the similar electrophoretic mobilities of three of the ions: caesium, rubidium and potassium. However, the presence of cryptand 222 in the leading electrolyte retards the mobilities of the caesium, rubidium and potassium to a different extent allowing separations to be made. A novel electrolyte system was formulated which consisted of a leading electrolyte of 10 mM caesium hydroxide, 0.75 mM cryptand 222 buffered to pH 9.4 with glycylglycine and a terminating electrolyte of 10 mM tetrabutylammonium hydroxide. The use of this electrolyte system allowed good separations of mixtures of rubidium, potassium, sodium and lithium to be achieved. The method was also applied to the analysis of edible salt samples.

A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR.

The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2 < r (Å) < 3 region via the difference method has enabled all the nearest neighbour correlations to be deconvolved. The diffraction data provides the first direct experimental evidence of split Na-O nearest-neighbour correlations in these melt quench bioactive glasses, and an analogous splitting of the Li-O correlations. The observed correlations are attributed to the metal ions bonded either to bridging or to non-bridging oxygen atoms. (23)Na triple quantum MAS (3QMAS) NMR data corroborates the split Na-O correlations. The structural sites present will be intimately related to the release properties of the glass system in physiological fluids such as plasma and saliva, and hence to the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimizing material design.