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1.
Hg concentrations in seawater are usually too low to allow direct (without pre-concentration and removal of salt matrix) measurement of its isotope ratios with multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS). Therefore, a new method for the pre-concentration of Hg from large volumes of seawater was developed. The final method allows for relatively fast (about 2.5 L h−1) and quantitative pre-concentration of Hg from seawater samples with an average Hg recovery of 98 ± 6%. Using this newly developed method we determined Hg isotope ratios in seawater. Reference seawater samples were compared to samples potentially impacted by anthropogenic activity. The results show negative mass dependent fractionation relative to the NIST 3133 Hg standard with δ202Hg values in the range from −0.50‰ to −1.50‰. In addition, positive mass independent fractionation of 200Hg was observed for samples from reference sites, while impacted sites did not show significant Δ200Hg values. Although the influence of the impacted sediments is limited to the seawater and particulate matter in very close proximity to the sediment, this observation may raise the possibility of using Δ200Hg to distinguish between samples from impacted and reference sites.  相似文献   

2.
A robust method allowing the routine determination of n(87Sr)/n(86Sr) with at least five significant decimal digits for large sets of mineral water samples is described. It is based on 2 consecutive chromatographic separations of Sr associated to multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) measurements. Separations are performed using commercial pre-packed columns filled with “Sr resin” to overcome isobaric interferences affecting the determination of strontium isotope ratios. The careful method validation scheme applied is described. It included investigations on all parameters influencing both chromatographic separations and MC-ICPMS measurements, and also the test on a synthetic sample made of an aliquot of the NIST SRM 987 certified reference material dispersed in a saline matrix to mimic complex samples. Correction for mass discrimination was done internally using the n(88Sr)/n(86Sr) ratio. For comparing mineral waters originating from different geological backgrounds or identifying counterfeits, calculations involved the well known consensus value (1/0.1194) ± 0 as reference. The typical uncertainty budget estimated for these results was 40 ‘ppm’ relative (k = 2). It increased to 150 ‘ppm’ (k = 2) for the establishment of stand alone results, taking into account a relative difference of about 126 ‘ppm’ systematically observed between measured and certified values of the NIST SRM 987. In case there was suspicion of a deviation of the n(88Sr)/n(86Sr) ratio (worst case scenario) our proposal was to use the NIST SRM 987 value 8.37861 ± 0.00325 (k = 2) as reference, and assign a typical relative uncertainty budget of 300 ‘ppm’ (k = 2). This method is thus fit for purpose and was applied to eleven French samples.  相似文献   

3.
An on-line flow injection spectrofluorimetric method for the direct determination of aluminium in water samples is described. The method is based on the reaction of aluminium with N-o-vanillidine-2-amino-p-cresol (OVAC) in acidic medium at pH 4.0 to form a water-soluble complex. The excitation and emission wavelengths were 423.0 and 553.0 nm, respectively, at which the OVAC-Al complex gave the maximum fluorescence intensity at pH 4.0 in a 50% methanol-50% water medium at 50 °C. An interference from fluoride ions was minimised by the addition of Be2+. Other ions were found not to interfere at the concentrations likely to be found in natural waters. The proposed methods were validated in terms of linearity, repeatability, detection limit, accuracy and selectivity. Under these conditions, the calibration was linear up to 1000 μg L−1 (r = 0.999). The limit of detection (3σ) for the determination of Al(III) was 0.057 μg L−1 and the precision for multiple determinations of 3 ng mL−1 Al(III) prepared in ultra-pure water was found to be 0.62% (n = 10).The Schiff base ligand could be used to determine ultra-trace aluminium from natural waters. Analysis of environmental certified reference materials showed good agreement with the certified values. The procedure was found to be equally applicable to both freshwater and saline solutions, including seawater.  相似文献   

4.
A water circulation system with the almost same element composition and socket type was adopted in coral Acropora culture under different seawater pH value conditions and the data of the relationship between boron isotopic compositions of coral and seawater pH value by thermoelectric ionization mass spectrometer were obtained. According to the correlations between αcarb-3 of coral and the pH value of cultured seawater, αcarb-3 was not a constant but related to pH value, indicating that B(OH)3 also incorporated carbonate. Therefore, the theoretical formula could not be used to calculate the seawater pH value from the δ11Bcarb value of the measured marine biological carbonate. The empirical equations obtained experimentally would be an alternative method to calculate the seawater pH value. In addition, the mixed precipitation of CaCO3 and Mg(OH)2 was found in aquaculture tanks with high pH value, and the δ11B of the solid was significantly higher than that of cultured seawater. The result indicated that the presence of Mg(OH)2 had a significant effect on the boron isotope fractionation, which deserved our attention.  相似文献   

5.
Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2 L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n = 6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved δ65Cu was 0.40–0.68‰.  相似文献   

6.
Inorganic calcium carbonate precipitation from natural seawater and saline water at various pH values was carried out experimentally. The results show the clear positive relationships between boron concentration and δ11B of inorganic calcium carbonate with the pH of natural seawater and saline water. However, the variations of boron isotopic fractionation between inorganic calcite and seawater/saline water with pH are inconsistent with the hypothesis that B(OH)4- is the dominant spe-cies incorporated into the biogenic calcite structure. The isotopic fractionation factors α between synthetic calcium carbonate precipitate and parent solutions increase systematically as pH increases, from 0.9884 at pH 7.60 to 1.0072 at pH 8.60 for seawater and from 0.9826 at pH 7.60 to 1.0178 at pH 8.75 for saline water. An unusual boron isotopic fractionation factor of larger than 1 in synthetic calcium carbonate precipitated from seawater/saline water at higher pH is observed, which implies that a substantial amount of the isotopically heavier B(OH)3 species must be incorporated preferentially into synthetic inorganic carbonate. The results propose that the incorporation of B(OH)3 is attributed to the formation of Mg(OH)2 at higher pH of calcifying microenvironment during the synthetic calcium carbonate precipitation. The preliminary experiment of Mg(OH)2 precipitated from artificial seawater shows that heavier 11B is enriched in Mg(OH)2 precipitation, which suggests that isotopically heavier B(OH)3 species incorporated preferentially into Mg(OH)2 precipitation. This result cannot be applied to explain the boron isotopic fractionation of marine bio-carbonate because of the possibility that the unusual environment in this study appears in formation of marine bio-carbonate is infinitesimal. We, however, must pay more attention to this phenomenon observed in this study, which accidentally appears in especially natural environment.  相似文献   

7.
A new technique for stable lead (Pb) isotope extraction from seawater is established using Toyopearl AF-Chelate 650 M® resin (Tosoh Bioscience LLC). This new method is advantageous because it is semi-automated and relatively fast; in addition it introduces a relatively low blank by minimizing the volume of chemicals used in the extraction. Subsequent analyses by HR ICP-MS have a good relative external precision (2σ) of 3.5‰ for 206Pb/207Pb, while analyses by MC-ICP-MS have a better relative external precision of 0.6‰. However, Pb sample concentrations limit MC-ICP-MS analyses to 206Pb, 207Pb, and 208Pb. The method was validated by processing the common Pb isotope reference material NIST SRM-981 and several GEOTRACES intercalibration samples, followed by analyses by HR ICP-MS, all of which showed good agreement with previously reported values.  相似文献   

8.
A simple copolymer, poly(NIPAM-co-N_AN), consisting of N-isopropylacrylamide (NIPAM) and 9-aminomethylanthracene (N_AN) units behaves as a temperature-driven on/off fluorescence indicator of pH window (2-12): showing an ‘on-off’ fluorescence intensity profile against the pH window at 15 °C, while showing an ‘off-on-off’ profile at 34 °C.  相似文献   

9.
A visual strip has been developed for sensing iron in different aqueous samples like natural water and fruit juices. The sensor has been synthesized by UV-radiation induced graft polymerization of acrylamide monomer in microporous poly(propylene) base. For physical immobilization of iron selective reagent, the in situ polymerization of acrylamide has been carried out in the presence of 1,10-phenanthroline. The loaded strip on interaction with Fe(II) in aqueous solution turned into orange red color and the intensity of the color was found to be directly proportional to the amount of Fe(II) in the aqueous sample. The minimal sensor response with naked eye was found for 50 ng mL−1 of Fe in 15 min of interaction. However, as low as 20 ng mL−1 Fe could be quantified using a spectrophotometer. The detection limit calculated using the 3s/S criteria, where ‘s’ is the standard deviation of the absorbance of blank reagent loaded strip and ‘S’ is the slope of the linear calibration plot, was 1.0 ng mL−1. The strip was applied to measure Fe in a variety of samples such as ground water and fruit juices.  相似文献   

10.
The formation of spherical micelles in aqueous solutions of poly(N-methyl-2-vinyl pyridinium iodide)-block-poly(ethylene oxide), P2MVP-b-PEO and poly(acrylic acid)-block-poly(vinyl alcohol), PAA-b-PVOH has been investigated with light scattering-titrations, dynamic and static light scattering, and 1H 2D Nuclear Overhauser Effect Spectroscopy. Complex coacervate core micelles, also called PIC micelles, block ionomer complexes, and interpolyelectrolyte complexes, are formed in thermodynamic equilibrium under charge neutral conditions (pH 8, 1 mM NaNO3, = 25 °C) through electrostatic interaction between the core-forming P2MVP and PAA blocks. 2D 1H NOESY NMR experiments show no cross-correlations between PEO and PVOH blocks, indicating their segregation in the micellar corona. Self-consistent field calculations support the conclusion that these C3Ms are likely to resemble a ‘patched micelle’; that is, micelles featuring a ‘spheres-on-sphere’ morphology.  相似文献   

11.
An aluminum hydroxide coprecipitation method for the determination of cadmium, copper and lead by flame atomic absorption spectrometry in aqueous solutions, seawater and mineral water samples has been investigated. The coprecipitation conditions, such as the effect of the pH, the amount of carrier element, the effect of possible matrix ions and the time were examined in detail for the studied elements. It was found that cadmium, copper and lead are co-precipitated quantitatively (≥95%) with aluminum hydroxide at pH 7 with low R.S.D. values of around 2 to 3%. Detection limits (38) were 6 ng ml−1 for Cd, 3 ng ml−1 for Cu and 16 ng ml−1 for Pb. The method proposed was validated by the analysis of HPS 312205 seawater standard reference material and spiked mineral water samples.  相似文献   

12.
An autonomous multi-parameter flow-through CO2 system has been developed to simultaneously measure surface seawater pH, carbon dioxide fugacity (fCO2), and total dissolved inorganic carbon (DIC). All three measurements are based on spectrophotometric determinations of solution pH at multiple wavelengths using sulfonephthalein indicators. The pH optical cell is machined from a PEEK polymer rod bearing a bore-hole with an optical pathlength of ∼15 cm. The fCO2 optical cell consists of Teflon AF 2400 (DuPont) capillary tubing sealed within the bore-hole of a PEEK rod. This Teflon AF tubing is filled with a standard indicator solution with a fixed total alkalinity, and forms a liquid core waveguide (LCW). The LCW functions as both a long pathlength (∼15 cm) optical cell and a membrane that equilibrates the internal standard solution with external seawater. fCO2 is then determined by measuring the pH of the internal solution. DIC is measured by determining the pH of standard internal solutions in equilibrium with seawater that has been acidified to convert all forms of DIC to CO2. The system runs repetitive measurement cycles with a sampling frequency of ∼7 samples (21 measurements) per hour. The system was used for underway measurements of sea surface pH, fCO2, and DIC during the CLIVAR/CO2 A16S cruise in the South Atlantic Ocean in 2005. The field precisions were evaluated to be 0.0008 units for pH, 0.9 μatm for fCO2, and 2.4 μmol kg−1 for DIC. These field precisions are close to those obtained in the laboratory. Direct comparison of our measurements and measurements obtained using established standard methods revealed that the system achieved field agreements of 0.0012 ± 0.0042 units for pH, 1.0 ± 2.5 μatm for fCO2, and 2.2 ± 6.0 μmol kg−1 for DIC. This system integrates spectrophotometric measurements of multiple CO2 parameters into a single package suitable for observations of both seawater and freshwater.  相似文献   

13.
Alkali-fusion in conjunction with a fluoride selective electrode were used to quantify ‘total fluorine’, being organic fluorine + inorganic fluoride, for the seed of 13 species of Gastrolobium from south-west Western Australia. Intact seed covering spatial and temporal distributions, as well as G. bilobum, G. calycinum and G. parviflorum seed dissected into cotyledons and testa + aril, were analysed. Analysis found significant intra-and inter-species variation, both temporally and spatially, with intact seed concentrations ranging from 1.6 ± 0.3 mg kg−1 in G. spinosum from Mundaring to 1063.9 ± 77.8 mg kg−1 for G. cuneatum from Torbay. Approximately 87% of the ‘total fluorine’ was found to be in the seed cotyledons. Additional analysis detected little inorganic fluoride, indicating the majority of fluorine in the seed is organically bound. Parent compound(s) of the fluorine, seed toxicity and the implications of the results for seed chemical defense are discussed.  相似文献   

14.
In this study we show how low temperature glow discharge plasma can be used to prepare bi-layered chromatography adsorbents with non-adsorptive exteriors. The commercial strong anion exchange expanded bed chromatography matrix, Q HyperZ, was treated with plasmas in one of two general ways. Using a purpose-designed rotating reactor, plasmas were employed to either: (i) remove anion exchange ligands at or close to the exterior surface of Q HyperZ, and replace them with polar oxygen containing functions (‘plasma etching and oxidation’); or (ii) bury the same surface exposed ligands beneath thin polymer coatings (‘plasma polymerization coating’) using appropriate monomers (vinyl acetate, vinyl pyrrolidone, safrole) and argon as the carrier gas. X-ray photoelectron spectroscopy analysis (first ∼10 nm depth) of Q HyperZ before and after the various plasma treatments confirmed that substantial changes to the elemental composition of Q HyperZ's exterior had been inflicted in all cases. The atomic percent changes in carbon, nitrogen, oxygen, yttrium and zirconium observed after being exposed to air plasma etching were entirely consistent with: the removal of pendant Q (trimethylammonium) functions; increased exposure of the underlying yttrium-stabilised zirconia shell; and introduction of hydroxyl and carbonyl functions. Following plasma polymerization treatments (with all three monomers tested), the increased atomic percent levels of carbon and parallel drops in nitrogen, yttrium and zirconium provided clear evidence that thin polymer coats had been created at the exteriors of Q HyperZ adsorbent particles. No changes in adsorbent size and surface morphology, nor any evidence of plasma-induced damage could be discerned from scanning electron micrographs, light micrographs and measurements of particle size distributions following 3 h exposure to air (220 V; 35.8 W L−1) or ‘vinyl acetate/argon’ (170 V; 16.5 W L−1) plasmas. Losses in bulk chloride exchange capacity before and after exposure to plasmas enabled effective modification depths within hydrated Q HyperZ adsorbent particles to be calculated as 0.2–1.2 μm, depending on the conditions applied. The depth of plasma induced alteration was strongly influenced by the power input and size of the treated batch, i.e. dropping the power or increasing the batch size resulted in reduced plasma penetration and therefore shallower modification. The selectivity of ‘surface vs. core’ modification imparted to Q HyperZ by the various plasma treatments was evaluated in static and dynamic binding studies employing appropriate probes, i.e. plasmid DNA, sonicated calf thymus DNA and bovine serum albumin. In static binding studies performed with adsorbents that had been exposed to plasmas at the 5 g scale (25 g L−1 of plasma reactor), the highest ‘surface/core’ modification selectivity was observed for Q HyperZ that had been subjected to 3 h of air plasma etching at 220 V (35.8 W L−1). This treatment removed ∼53% of ‘surface’ DNA binding at the expense of a 9.3% loss in ‘core’ protein binding. Even more impressive results were obtained in dynamic expanded bed adsorption studies conducted with Q HyperZ adsorbents that had been treated with air (220 V, 3 h) and ‘vinyl acetate/argon’ (170 V, 3 h) plasmas at 10.5 g scale (52.5 g L−1 of plasma reactor). Following both plasma treatments: the 10% breakthrough capacities of the modified Q HyperZ adsorbents towards ‘surface’ binding DNA probes dropped very significantly (30–85%); the DNA induced inter-particle cross-linking and contraction of expanded beds observed during application of sonicated DNA on native Q HyperZ was completely eradicated; but the ‘core’ protein binding performance remained unchanged cf. that of the native Q HyperZ starting material.  相似文献   

15.
Two novel cyanine dyads, in which a naphthalimide unit is attached to benzoindole ring of unsymmetric trimethine cyanine, have been synthesized via ‘Click’ reaction and characterized by 1H NMR, 13C NMR, and MS-ESI. Under the illumination of AM 1.5 (75 mW cm−2), the power conversion efficiency of cyanine I reached 4.8% (Jsc = 14.5 mA cm−2, Voc = 0.50, FF = 0.49). The results show that the two cyanine dyes are promising sensitizers for nanocrystalline dye-sensitized solar cell.  相似文献   

16.
A high-performance fluorosensor for pH measurements between 6 and 9   总被引:1,自引:0,他引:1  
Aron Hakonen  Stefan Hulth 《Talanta》2010,80(5):1964-321
This study presents a high-performance ratiometric pH optode based on the fluorophore 6,8-dihydroxypyrene-1,3-disulfonic acid (DHPDS). The two pH-sensitive terminal hydroxy groups of DHPDS facilitated dual excitation/dual emission (F1: λ1,ex = 420 nm, λ1,em = 462 nm; F2: λ2,ex = 470 nm, λ2,em = 498 nm) properties for ratiometric (RF1,F2 = F1/F2) normalization of sensor signal. The sensor demonstrated an exponentially decreasing ratiometric response with increasing pH, with a linear correlation (R2 = 0.9936) between 10log(RF1,F2) and pH within the pH interval 6-9. Precision determined as the IUPAC pooled standard deviation for the pH values 6.00, 7.01 and 9.01, was 0.0057 pH units for the fluorosensor and 0.0054 for a commercially available pH electrode used for comparison. Between the end-points of calibration at pH 7.01, the precision of the sensor was 0.0037 pH units. Effects from changes in ionic strength (Itot, 10-700 mM) were more pronounced for the electrode, with a linear (R2 = 0.9976) increase in response (δE/δpH) with increasing Itot. The DHPDS-based fluorosensor, however, retained sensitivity (δ10log(RF1,F2)/δpH = 0.8024 ± 0.0145), though with an overall increase in ratiometric signal with increasing Itot. The preserved sensitivity despite changes in ionic strength was possibly a consequence from the dual photo-acidic properties of DHPDS. Analytical characteristics of immobilized DHPDS therefore not only facilitated high-performance measurements over a wide pH range, but also opened for straightforward simultaneous measurements of pH and ionic strength.  相似文献   

17.
In this work, the determination of total As in seawater by hydride generation atomic fluorescence spectrometry was studied. The influence of the chemical, flow and instrumental parameters were investigated and optimized. The pre-reduction of As(V) to As(III) was performed using KI plus ascorbic acid in 3.5 mol L− 1 HCl medium. No multiplicative interference was present and external aqueous calibration could be used. The limit of detection was 36 ng L− 1, while the repeatability was 2% (n = 10), at a 500 ng L− 1 concentration level. The sample throughput was 15 h− 1 if triplicate measurements were made. The accuracy was assessed by the analysis of a seawater certified reference material and excellent agreement between the obtained and certified values was verified. The procedure was used for the analysis of seawater offshore samples collected at the Brazilian coast and results ranging from 860 to 1200 ng L− 1 were found.  相似文献   

18.
The feasibility of using sol-gel amorphous titania (TiO2) as a solid-phase sorbent for the pre-concentration of domoic acid (DA), a potent amnesic shellfish poisoning (ASP) toxin, directly from seawater was explored. The sol-gel titania material is able to adsorb DA from seawater, via the formation of ester-linkage between the carboxylic moieties of DA and the Ti-OH groups on the sorbent surface, at low pH and desorb it at high pH. The chemisorption process is not significantly interfered by the seawater matrix. The optimum pH values for the adsorption and desorption of DA were found to be pH 4 and 11, respectively. The optimal sorbent loading for the batch-type solid-phase extraction of DA was 0.67 mg-TiO2 ng-DA−1 and adsorption equilibrium was achieved in 2 h at room temperature. The desorbed DA in 500 μL of 0.1 M alkaline borate buffer can be directly derviatized by 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) in aqueous media for fluorimetric HPLC quantification. Analyte recovery, repeatability and detection limit of this titania SPE-fluorimetric HPLC determination are 89%, 6.2% and 120 pg-DA mL−1 (n = 7, P < 0.05), respectively, for a sample volume of 30 mL. This titania SPE technique should also be applicable to the pre-concentration of other polar carboxylate- and phosphonate-containing biomolecules and pharmaceuticals in complex and interfering environmental sample matrices.  相似文献   

19.
Real structure and some physicomechanical characteristics of the samples of natural beta-rhombohedral boron B as well as of its 10B and 11B monoisotopes have been studied. It was shown that the influence of 10B and 11B isotopes on physicomechanical properties of boron had a different character. In particular, the samples enriched with 11B had high values of microhardness, shear modulus (SM) and elastic limit if compared to those of boron, while the samples enriched with 10B monoisotopes were characterized with high values of thermal expansion coefficient (TEC) and thermal conductivity; lattice parameters a and c increased by the sequence: 11B, B, 10B. It was established that TEC, thermal conductivity, microhardness, SM and shear elastic limit increased in all samples at annealing for 5 h at 1500 °C regardless of isotope content.  相似文献   

20.
A novel thin-film composite (TFC) seawater reverse osmosis membrane was developed by the interfacial polymerization of 5-chloroformyloxyisophthaloyl chloride (CFIC) and metaphenylenediamine (MPD) on the polysulphone supporting membrane. The performance of the TFC membrane was optimized by studying the preparation parameters, which included the reaction time, pH of the aqueous-MPD solution, monomer CFIC concentration, additive isopropyl alcohol content in aqueous solution, curing temperature and time. The reverse osmosis performance of the resulting membrane was evaluated through permeation experiment with synthetic seawater, and the structure of the novel membrane was characterized by using SEM, AFM and XPS. Furthermore, the separation properties of the TFC membrane were tested by examining the reverse osmosis performances of various conditions, the boron rejection performance and the long-term stability. The results show that the desired TFC seawater reverse osmosis membrane has a typical salt rejection of 99.4% and a flux of about 35 L/m2 h for a feed aqueous solution containing 3.5 wt.% NaCl at 5.5 MPa, and an attractive boron rejection of more than 92% at natural pH of 7–8; that the novel seawater reverse osmosis membrane appears to comprise a thicker, smoother and less cross-linking film structure. Additionally, the TFC membrane exhibits good long-term stability.  相似文献   

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