Poly(neutral red): Electrosynthesis,Characterization, and Application as a Redox Mediator

The synthesis by electropolymerization, the characterization, and applications of poly(neutral red) (PNR), including as a redox mediator, are reviewed. PNR's high electrical conductivity and its redox characteristics have led to special applications of the polymer, and it has been used for the development of electrochemical and optical sensors. Moreover, the attractive properties of PNR allow it to be applied in the development of electrochemical biosensors. Future perspectives are indicated.     

Biomethylation and biotransformation of arsenic in a freshwater food chain: Green alga (chlorella vulgaris)→shrimp (neocaridina denticulata)→killifish (oryzias iatipes)

Tolerance, bioaccumulation, biotransformation and excretion of arsenic compounds by the fresh–water shrimp (Neocaridina denticulata) and the killifish (Oryzias latipes) (collected from the natural environment) were investigated. Tolerances (LC₅₀) of the shrimp against disodium arsenate [abbreviated as As(V)], methylarsonic acid (MAA), dimethylarsinic acid (DMAA), and arsenobetaine (AB) were 1.5, 10, 40, and 150μg As ml^?1, respectively. N. denticulata accumulated arsenic from an aqueous phase containing 1 μg As ml^?1 of As(V), 10 μg As ml^?1 of MAA, 30 μg As ml^?1 of DMAA or 150 μg As ml^?1 of AB, and biotransformed and excreted part of these species. Both methylation and demethylation of the arsenicals were observed in vivo. When living N. denticulata accumulating arsenic was transferred into an arsenic–free medium, a part of the accumulated arsenic was excreted. The concentration of methylated arsenicals relative to total arsenic was higher in the excrement than in the organism. Total arsenic accumulation in each species via food in the food chain Green algae (Chlorella vulgaris) → shrimp (N. denticulata) → killifish (O. latipes) decreased by one order of magnitude or more, and the concentration of methylated arsenic relative to total arsenic accumulated increased successively with elevation in the trophic level. Only trace amounts of monomethylarsenic species were detected in the shrimp and fish tested. Dimethylarsenic species in alga and shrimp, and trimethylarsenic species in killifish, were the predominant methylated arsenic species, respectively.     

Arsenic metabolism in a freshwater food chain: Blue–green alga (Nostoc sp.)→ shrimp (Neocaridina denticulata)→ carp (Cyprinus carpio)

Bioaccumulation and biomethylation of inorganic arsenic were investigated in a three-step fresh-water food chain consisting of an autotroph (blue- green alga: Nostoc sp.), a herbivore (shrimp: Neocaridina denticulata) and a carnivore (carp: Cyprinus carpio). The autotroph, herbivore and carnivore survived in arsenic-containing water below 1000, 2 and 60 mg As(V) dm^?3, respectively. Bioaccumulation of arsenate by Nostoc sp. was decreased with an increase in the nitrogen concentration of the medium. Arsenic(V) was accumulated from the water phase and part-methylated by the carp, as well as by the algae and shrimp. Arsenic was mostly accumulated in the gut of the carp. The predominant arsenical in the guts was the monomethylarsenic species. Arsenic accumulation via food in the above three-step food chain decreased by one order of magnitude and the relative concentration of methylated arsenic to the total arsenic accumulated increased successively with an elevation in the trophic level. When arsenicals were transferred via the food chain, no monomethylarsenic, or only a trace amount, was detected in the three organisms. Dimethylarsenic in the alga, both dimethyl- and trimethyl-arsenic in shrimp, and trimethyl-arsenic in carp, were the predominant methylated arsenic species, respectively.     

Exposure assessment of heavy metals in water and sediments from a Western Mediterranean basin (Rio Guadalhorce,Region of Andalusia,Southern Spain)

Concentrations of heavy metals (Cd, Cr, Cu, Ni and Pb) were measured in sediment and water from a representative Western Mediterranean basin in South Spain: Guadalhorce River. In the later twentieth century, cities such as Málaga (capital of the Costa del Sol), have suffered the impact of the mass summer tourism. The ancient industrial activities, abandoned mine sites and the actual urbanisation and coastal development, recreation and tourism, wastewater treatment facilities, have been sources of pollution. This river has been heavily modified, with three dams for volume regulation purposes owing to the climatic cycles, with some years very dry and others with torrential rains. In this study, different indices to assessment of sediment contamination, statistical tools (Kruskall–Wallis test, Conglomerate analysis), sequential extraction methods and environmental quality guidelines have been employed to assess the possible contamination of this basin. Other physical–chemical parameters as chloride concentration, pH and conductivity were also measured. The results indicated that Ni and Cu were the most troublesome metals because they were more easily mobilisable than Cr and Pb; Ni exceeds the SQGs guidelines, and Cu presents considerable contamination. These metals were derived from lithogenic and anthropogenic sources, respectively, according to the enrichment factors (EF) values. Ni was the most dangerous because Ni concentrations exceeded the threshold effect concentration (TEC) below which harmful effects are unlikely to be observed, in 96.6% of the samples analysed and even the probable effect concentration (PEC) above which harmful effects are likely to be observed, in 56.6%. The cause of this pollution was postulated to be by abandoned Ni mines, which indicates that the pollution from mining persists during several decades. Multivariate analyses used in this study provide important tools for better understanding of the pollution source identification.     

Iridium(I) pyridyl azolate complexes with saturated red metal-to-ligand charge transfer phosphorescence; fundamental and potential applications in organic light-emitting diodes

Preparation of a new series of neutral metal complexes [(cod)Ir(fppz)] (1), [(cod)Ir(bppz)] (2), [(cod)Ir(fptz)] (3) and [(cod)Ir(bptz)] (4), bearing one cod ligand and a pyridyl azolate chelate are reported. A single-crystal X-ray diffraction study of 3 reveals the expected distorted square-planar geometry. The lowest absorption band consists of IrI atom increased triplet dpi-->pi* transitions (3MLCT), the assignment of which is firmly supported by the theoretical approaches. Complexes 1-4 exhibit weak phosphorescence in degassed solution at room temperature, whereas much more intense, solid-state phosphorescence appears in the range 622-649 nm. The pure MLCT emission was used as a prototypical model to address its remarkable spectral differences from the IrIII isoquinoline pyrrolide complex (5), which has mainly 3pipi phosphorescence. Complex 3 was used as a dopant to fabricate red-emitting phosphorescent organic light-emitting diodes (OLEDs). For the 7 % doped device, a maximum brightness of 3010 cd m-2 was achieved at an applied voltage of 15 V and with CIE coordinates of (0.56, 0.33), demonstrating for the first time the potential of neutral IrI complexes in OLED applications.     

Electron spin resonance (ESR/EPR) of free radicals observed in human red hair: a new,simple empirical method of determination of pheomelanin/eumelanin ratio in hair

The definition of the concentration of pheomelanin in the skin is an issue of great interest because in the case of being influenced by UV radiation, it manifests itself as a prooxidant, causing various skin disorders including melanoma that might help to explain the relatively high incidence of skin cancer among individuals with red hair. The ESR spectra of red hair samples were investigated. It was found that at low microwave power, they are characterized by two types of spectra. Red hair ESR signals result from a superposition of two spectral shapes, a singlet spectrum as a result of the existence of eumelanin and a triplet spectrum as a result of the existence of pheomelanin. At high microwave power, only triplet spectra shape was detected, caused by saturation of the eumelanin singlet. Using different concentration ratios of black to red hair, we measured ESR spectra and plotted the ratio values in each sample against a measured ‘g‐factor’ (experimental). We found that there is a linear relationship between these two parameters. So, it is evident that using these results, the concentration ratio of pheomelanin to eumelanin in a sample of hair can be easily determined by an almost noninvasive method. This can be considered a potential advantage for many practical activities compared with other invasive methods. The concentration dependence curve of pheomelanin (µg/mg) on g_exp‐factor in an ESR spectrum of hair has been designed, which allows the determination of the amount of pheomelanin in hair of any color. Copyright © 2014 John Wiley & Sons, Ltd.     

Ambient mass spectrometry using desorption electrospray ionization (DESI): instrumentation, mechanisms and applications in forensics, chemistry, and biology

Analytical characteristics of DESI are summarized. Examples of applications to small and large molecules, to in situ analysis, and to high-throughput analyses are presented. Evidence is provided for both a heterogeneous charge-transfer mechanism and a droplet pick-up mechanism of ionization. The speed, lack of the need for sample preparation, selectivity, and sensitivity of DESI are all demonstrated and discussed. Instrumentation is also discussed. Forensic applications as well as emerging areas of application including tissue imaging are given emphasis.     

Bio-based tri-functional epoxy resin (TEIA) blend cured with anhydride (MHHPA) based cross-linker: Thermal,mechanical and morphological characterization

A novel renewable resource based tri-functional epoxy resin from itaconic acid (TEIA) was blended with petroleum based epoxy resin (DGEBA) and fabricated at different ratios. Then, it was by thermally cured with methylhexahydrophthalic anhydride (MHHPA) in presence of 2-methylimidazole (2-MI) catalyst. The tensile, modulus, strength of virgin epoxy resin (41.97 MPa, 2222 MPa) increased to 47.59 MPa, 2515 MPa, respectively, with the addition of 30% of TEIA. The fracture toughness parameter, critical stress intensity factor (K_IC) revealed enhancement of toughness in the TEIA bio-based blends system. The thermomechanical properties of TEIA (tri-functional epoxy resin from itaconic acid) modified petroleum-epoxy networks were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The fracture morphology was also studied by the scanning electron microscopy and atomic force microscopy respectively.     

DNA/BSA binding interactions and VHPO mimicking potential of vanadium(IV) complexes: Synthesis,structural characterization and DFT studies

Vanadium(IV) Schiff base complexes (VOL¹‐VOL³) were synthesized and characterized by elemental analysis, various spectral methods and single crystal XRD studies. Structural analysis of VOL² reveals that the central vanadium ion in the complex is six coordinate with distorted octahedral geometry. Density functional theory (DFT) and time dependent (TD‐DFT) studies were used to understand the electronic transitions observed in the complexes in UV–Vis spectra. The electrochemical behavior of the complexes was investigated in acetonitrile medium exhibit quasi‐reversible one electron transfer. The DNA and BSA protein binding interaction of vanadium complexes has been explored by UV–Vis and fluorescence spectral methods and viscosity measurements reveal that the complexes interact with CT‐DNA through intercalation mode and follows the order VOL¹ < VOL³ < VOL². The complexes exhibit binding interactions with BSA protein. The complexes act as chemical nuclease and cleave DNA in the presence of H₂O₂. The 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) assay was used to evaluate the radical scavenging activity demonstrate the antioxidant property of the complexes. The antimicrobial activity was screened for several microorganisms, Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli. The mimicking of vanadium haloperoxidase was investigated by the bromination of the organic substrate phenol red by vanadium complexes in the presence of bromide and H₂O₂.     

Imposex in Sea Snails,Caused by Organotin (Tributyltin and Triphenyltin) Pollution in Japan: a Survey

A country-wide survey and laboratory experiments on imposex (a superimposition of male sex organs on female sea snails) in Japanese sea snails were carried out: 38 species were observed to be affected by imposex. For the rock shell, Thais clavigera , the percentage occurrence of imposex was 100% at almost all sites surveyed. The degree of imposex seemed to be positively correlated with the concentrations of tributyltin (TBT) and triphenyltin (TPT) in the species. The results of laboratory experiments showed that imposex in T. clavigera was initiated and promoted by both TBT and TPT. Many oviduct-blocked individuals, which were thought to be sterile, were observed in T. clavigera at sites near marinas and harbours. The effects of organotin pollution on the population of T. clavigera were observed at the sites near marinas. From the results of the additional country-wide survey on imposex in T. clavigera during 1993–1995, serious organotin pollution and imposex symptoms in the species are still continuing in Japan. © 1997 by John Wiley & Sons, Ltd.     

Synthesis, characterization, spectroscopic, and electrochemiluminescence properties of a solvatochromic azacrown-containing cyanoruthenate(II): potential applications in separation and indirect photometric detection of cations and amino acids in HPLC

A new anionic ruthenium(II) complex, (Et4N)[Ru(tpyA18C6)(CN)3] (tpyA18C6=N-[4'-(2,2':6',2'-terpyridyl)]-1,4,7,10,13-pentaoxa-16-azacyclohexadodecane), has been synthesized and characterized. The complex was found to show pronounced solvatochromic behavior and, when dissolved in solution, changed its color from purple to yellow when the solvent system was varied from pure acetonitrile to pure water. Its absorption and emission energies in various solvents showed a linear dependence of the Gutman's acceptor number. The characteristic photoluminescence and electrochemiluminescence (ECL) of the complex were also found to be progressively quenched as the proportion of water in a water/acetonitrile mixture increased. Large changes in the chemical shifts of the 1H NMR and 13C NMR signals of [Ru(tpyA18C6)(CN)3]- in different solvents were observed. The complex has also been demonstrated to serve as a mobile-phase additive in high-performance liquid chromatography for separation of metal cations and amino acids. Comparison studies with the crown-free analogue, (Et4N)[Ru(tpy)(CN)3] (tpy = 2,2':6',2'-terpyridine), showed that other than the ion-pair effect, the allosteric host-guest interaction provided by the presence of the pendant crown was essential to the separation performance of the complex. Indirect detection of nonabsorbing analytes has been achieved by monitoring the absorbance changes of the eluent at the metal-to-ligand charge-transfer (MLCT) absorption band maximum of the complex at 445 nm. The effects of pH, ionic strength, and polarity of the mobile phase as well as the complex concentration on the selectivity and resolution have also been studied.     

Identification of volatile markers for the detection of adulterants in red ginseng (Panax ginseng) juice using headspace stir‐bar sorptive extraction coupled with gas chromatography and mass spectrometry

Red ginseng (Panax ginseng) products are frequently adulterated by manufacturers with cheaper medicinal plant products including deodeok (Codonopsis lanceolata) and doraji (Platycodon grandiflorum) to increase profits. To identify possible volatile markers for the adulteration of red ginseng juices with deodeok or doraji, a headspace stir‐bar sorptive extraction method was developed. Gas chromatography with mass spectrometry and untargeted metabolomics analysis revealed that 1‐hexanol, cis‐3‐hexen‐1‐ol, and trans‐2‐hexen‐1‐ol are abundantly present in deodeok and doraji but not red ginseng. The peak area ratios in gas chromatograms of these compounds in red ginseng juices mixed with deodeok or doraji indicate that these volatile chemicals can be used as markers to detect the adulteration of red ginseng juice.     

Electrochemical Evaluation of Pollutants in the Environment: Interaction Between the Metal Ions Zn(II) and Cu(II) with the Fungicide Thiram in Billings Dam

Pesticides are organic molecules used in the control of various pests in different crops. These molecules show functional groups that can interact with metal ions, forming new species with different properties. These new compounds have been attracting attention because they can become a new environmental problem. In this work the interaction of copper and zinc metal ions with Thiram pesticide was studied using electrochemical techniques. Studies in ultrapure water showed the formation of Zn?Thiram complex with reduction potential at ?1.330 V; Cu?Thiram complex showed a cathodic peak at 0.020 V. Thiram causes a different effect on the two metal ions studied. It was observed that the ligand stabilizes more the Cu(II) than Zn(II). Both systems proved to be quasi‐reversible, controlled by the adsorption of the species on the electrode surface. The formation constants of the complexes were calculated to be 2.1×10⁵ for Zn?Thiram and 1.5×10¹⁹ for Cu?Thiram. In the samples from Billings dam, the Zn‐complex showed reduction potential at ?1.403 V; Cu‐complex exhibited a reduction peak at 0.012 V. Although there are interferers in river waters, the interaction of these metals with the pesticide showed high affinity, being possible to detect them in natural samples. The Cu(II) complex showed to be more stable in natural matrices when compared to the Zn(II) complex. The sensitivity for thiram electroanalytical determination decreases in the presence of Zn(II) and Cu(II).     

Luminescent organoplatinum(II) complexes with functionalized cyclometalated C^N^C ligands: structures, photophysical properties, and material applications

A series of [(R'-C^N^C-R')Pt(L)] complexes with doubly deprotonated cyclometalated R'-C^N^C-R' ligands (R'-C^N^C-R'=2,6-diphenylpyridine derivatives) functionalized with carbazole, fluorene, or thiophene unit(s) have been synthesized and their photophysical properties studied. The X-ray crystal structures reveal extensive intermolecular π···π and C-H···π interactions between the cyclometalated C^N^C ligands. Compared to previously reported cyclometalated platinum(II) complexes [(C^N^C)Pt(L)], which are non-emissive in solution at room temperature, the carbazole-, fluorene- and thiophene-functionalized [(R'-C^N^C-R')Pt(L)] (L=DMSO 1-9, C≡N-Ar, 1a-9a) complexes are emissive in solution at room temperature with λ(max) at 564-619 nm and Φ=0.02-0.26. The emissions of the [(R'-C^N^C-R')Pt(L)] complexes are attributed to electronic excited states with mixed (3)MLCT and (3)IL character. The carbazole/fluorene/thiophene unit(s) allow the tuning of the electronic properties of the [(R'-C^N^C-R')Pt] moiety, with the emission maxima in a range of 564-619 nm. These are the first examples of organoplatinum(II) complexes bearing doubly deprotonated cyclometalated C^N^C ligands that are emissive in solution at room temperature. In non-degassed DMSO, the emission intensities of 6a-9a are enhanced upon exposure to ambient light. This phenomenon is caused by reacting photogenerated (1)O(2) with a DMSO molecule to form dimethyl sulfone, leading to the removal of dissolved oxygen in solution. Self-assembled nanowires and nanorods are obtained from precipitation of 3a in THF/H(2)O and 8a in DMSO/Et(2)O, respectively. The [(R'-C^N^C-R')Pt(L)] complexes are soluble in common organic solvents with a high thermal stability (>300 °C), rendering them as phosphorescent dopants for organic light-emitting diode (OLEDs) applications. Red OLEDs with CIE coordinates of (0.65±0.01, 0.35±0.01) were fabricated from 7a or 8a. A maximum external efficiency (η(Ext)) of 12.6% was obtained for the device using 8a as emitter.     

New coumarin derivative with potential antioxidant activity: Synthesis,DNA binding and in silico studies (Docking,MD, ADMET)

A new coumarin derivative, 7-((8-(4-benzylpiperidin-1-yl)octyl)oxy)-4-methyl-2H-chromen-2-one (C3), was synthesized by two-step alkylation reaction of 7-hydroxy-4-methyl coumarin. The structure and purity of the compound were characterized by its ¹H and ¹³C NMR, FT-IR and LC-MS spectral data. The DNA binding interaction of C3 was evaluated using UV–vis spectrophotometric and viscosimetric methods. These experiments showed that C3 was bound in intercalative mode. The antioxidant activity of C3 was evaluated by the DPPH method, the antioxidant activity results displayed that C3 had DPPH radical scavenging effect. The possible mechanism of antioxidant and anticancer activity of C3 was investigated via molecular docking by using two enzymes CYP450 and EGFR as receptors. The C3 also tended a good antioxidant ability based on the result of the molecular docking analysis, with good binding affinity values (-7.82 kcal/mol) and binding site interactions. Molecular Dynamics (MD) simulation was implemented to elucidate the interactions with the protein–ligand complex in 20 ns. The ADMET analyzes which paved the way for us to predict C3 as a drug candidate were also performed. All experimental and theoretical results showed that the compound C3 was a potential drug candidate as an antioxidant and anticancer agent.     

Near-infrared (NIR) to red and green up-conversion emission from silica sol-gel thin films made with La(0.45)Yb(0.50)Er(0.05)F(3) nanoparticles, hetero-looping-enhanced energy transfer (Hetero-LEET): a new up-conversion process

Bright green and red luminescence has been generated with a 980 nm diode laser from silica sol-gel thin films made with La0.45Yb0.50Er0.05F3 nanoparticles through a newly described hetero-looping-enhanced energy-transfer (hetero-LEET) up-conversion process, which exhibits a power dependence similar to that of a photon avalanche (PA). The hetero-LEET mechanism is potentially more efficient than PA, ground-state absorption/excited-state absorption (GSA/ESA), and energy-transfer (ETU) mechanisms because it combines resonant ground-state absorption with a looping or feedback process.     

Electronic structure and chain-length effects in diplatinum polyynediyl complexes trans,trans-[(X)(R3P)2Pt(C triple bond C)(n)Pt(PR3)2(X)]: a computational investigation

Structure and bonding in the title complexes are studied using model compounds trans,trans-[(C6H5)(H3P)2Pt(C triple bond C)(n)Pt(PH3)2(C6H5)] (PtCxPt; x = 2n = 4-26) at the B3LYP/LACVP* level of density functional theory. Conformations in which the platinum square planes are parallel are very slightly more stable than those in which they are perpendicular (DeltaE = 0.12 kcal mol(-1) for PtC8Pt). As the carbon-chain length increases, progressively longer C triple bond C triple bonds and shorter triple bond C-C triple bond single bonds are found. Whereas the triple bonds in HCxH become longer (and the single bonds shorter) as the interior of the chain is approached, the PtC triple bond C triple bonds in PtCxPt are longer than the neighboring triple bond. Also, the Pt-C bonds are shorter at longer chain lengths, but not the H-C bonds. Accordingly, natural bond orbital charge distributions show that the platinum atoms become more positively charged, and the carbon chain more negatively charged, as the chain is lengthened. Furthermore, the negative charge is localized at the two terminal C triple bond C atoms, elongating this triple bond. Charge decomposition analyses show no significant d-pi* backbonding. The HOMOs of PtCxPt can be viewed as antibonding combinations of the highest occupied pi orbital of the sp-carbon chain and filled in-plane platinum d orbitals. The platinum character is roughly proportional to the Pt/Cx/Pt composition (e.g., x = 4, 31 %; x = 20, 6 %). The HOMO and LUMO energies monotonically decrease with chain length, the latter somewhat more rapidly so that the HOMO-LUMO gap also decreases. In contrast, the HOMO energies of HCxH increase with chain length; the origin of this dichotomy is analyzed. The electronic spectra of PtC4Pt to PtC10Pt are simulated. These consist of two pi-pi* bands that redshift with increasing chain length and are closely paralleled by real systems. A finite HOMO-LUMO gap is predicted for PtCinfinityPt. The structures of PtCxPt are not strictly linear (average bond angles 179.7 degrees -178.8 degrees ), and the carbon chains give low-frequency fundamental vibrations (x = 4, 146 cm(-1); x = 26, 4 cm(-1)). When the bond angles in PtC12Pt are constrained to 174 degrees in a bow conformation, similar to a crystal structure, the energy increase is only 2 kcal mol(-1). The above conclusions should extrapolate to (C triple bond C)(n) systems with other metal endgroups.     

Structural,spectroscopic aspects,and electronic properties of (TiO2)n clusters: A study based on the use of natural algorithms in association with quantum chemical methods

In this article, we propose a stochastic search‐based method, namely genetic algorithm (GA) and simulated annealing (SA) in conjunction with density functional theory (DFT) to evaluate global and local minimum structures of (TiO₂)_n clusters with n = 1–12. Once the structures are established, we evaluate the infrared spectroscopic modes, cluster formation energy, vertical excitation energy, vertical ionization potential, vertical electron affinity, highest occupied molecular orbital (HOMO)‐lowest unoccupied molecular orbital (LUMO) gaps, and so forth. We show that an initial determination of structure using stochastic techniques (GA/SA), also popularly known as natural algorithms as their working principle mimics certain natural processes, and following it up with density functional calculations lead to high‐quality structures for these systems. We have shown that the clusters tend to form three‐dimensional networks. We compare our results with the available experimental and theoretical results. The results obtained from SA/GA‐DFT technique agree well with available theoretical and experimental data of literature. © 2013 Wiley Periodicals, Inc.     

Trace,Alkaline and Alkaline-Earth Elements in Sea Water Samples from Terra Nova Bay - Ross Sea (ANTARCTICA): A Three-Year Period of Observation

Abstract

This report concerns the correlation of the analytical results relevant to some elements obtained in filtered sea water samples collected in Terra Nova Bay and the Ross Sea (Antarctica) during three Italian expeditions. The following ranges of variability of the medians of total concentrations (ng/l) - which include time effect among expeditions and bias effect among participant groups - were found for trace elements (single values refer to elements which were only determined once by one laboratory): Sb (260), As (1.2 10³), Cd (5–50), Cr (120), Co (4), Cu (110–230), Fe (435–445), Pb (6–52), Mn (15–88), Hg (3), Ni (185–580), Se (30) and Zn (242–265). Speciation studies pointed out that 10–40% of Cd, 15–60% of Cu and 20–50% of Pb were present in the samples as an ASV-labile fraction.

As for alkaline and alkaline-earth elements, the following concentration ranges in surface sea waters, expressed in mM, were found: Li ([1.4–3.0] 10^?2), Na (394–480), K(5.1–9.9), Ca (6.4–14.7), Mg (46.2–59.0) and Sr ([7.6–10] 10^?2).

Inter- and intra-laboratory data comparison, incorrect results, local variations of concentration, including pollution effects and pack melting effect, are discussed in detail.