Effective elimination of organic matter interference in boron isotopic analysis by thermal ionization mass spectrometry of coral/foraminifera: micro-sublimation technology combined with ion exchange

In order to better estimate the effectiveness of micro-sublimation technology on the elimination of organic matter interference during boron isotopic analysis, a series of improved experiments was carried out using simple apparatus. Recovery rates after micro-sublimation were measured for boric acid solutions with different B contents or different B/organic matter ratios. The improved micro-sublimation procedure combined with ion-exchange technology was then used to test natural samples (coral and foraminifera) for the separation of boron. Our results show that the time taken for 100% recovery of different amounts of B differed and that the proportions of B/organic matter within the natural organic matter have little effect on the relationship between the recovery rates of B and the micro-sublimation times. The experiments further confirm that the organic matter does indeed have an effect on boron isotope analyses by positive thermal ionization mass spectrometry and that the use of micro-sublimation can effectively remove interferences from the organic matter during boron isotopic analysis.     

The determination of microgram and sub-microgram amounts of boron : II. The separation of boron by distillation and the evaporation of distillates

Methyl alcohol distillates containing μg amounts of boron may be evaporated without loss of boron by first adding water, sodium hydroxide and glycerol. The resulting residues can be used directly in the curcumin absorptiometric methods previously described. The distillation techniques developed over the last decade by the United Kingdom Atomic Energy authority are briefly described, as these can be used for the separation of boron from practically all types of sample, including organic matter after it has been ashed with lime. In all cases aqueous solutions of the samples are made slightly acid (pH 1.5–5) and evaporated nearly to dryness Residues are then treated with methyl alcohol in one of three ways according to their properties. It is essential to use all-silica distillation apparatus and platinum dishes for collecting distillates. Notes are given of other precautions necessary to minimize contamination from reagents and other sources. The methods are rapid and suitable for routine analysis on up to 10 g of sample. Under favourable conditions, the limit of detection is of the order of 0.01 p.p.m. of boron. A precision of better than 5% can be obtained with amounts exceeding about 0.2 p.p m.     

Rapid mass-spectrometric determination of boron isotopic distribution in boron carbide

Boron isotopic ratios are measured in boron carbide by thermionic ionization mass spectrometry with no prior chemical separation. A powder blend of boron carbide and sodium hydroxide is prepared, a small portion is transferred to a tantalum filament, the filament is heated to produce sodium borate, and the filament is transferred to the mass spectrometer where the(11)B/(10)B ratio is measured, using the Na(2)BO(2)(+) ion. Variables investigated for their effect on preferential volatilization of (10)B include the sodium hydroxide-boron carbide ratio and the temperature and duration of filament heating. A series of boron carbide pellets containing natural boron, of the type proposed for the control rods of the Fast Flux Test Facility reactor, were analysed with an apparently unbiased result of 4.0560 for the (11)B/(10)B ratio (standard deviation 0.0087). The pellets contained over 3% metal impurities typically found in this material. Time of analysis is 45 min per sample, with one analyst.     

Metal ions binding onto a lignocellulosic substrate extracted from wheat bran: a NICA-Donnan approach

In this study ion binding to solid organic matter was investigated. We used the NICA-Donnan model to describe the interaction between Cu(II), Pb(II), and Cd(II) ions and a lignocellulosic substrate extracted from wheat bran. Such a material represents a very cheap and flexible substrate, which can be used as a natural filter to remove toxic metal ions from industrial effluents or applied in the decontamination and rehabilitation of abandoned industrial sites. Moreover, such a material also represents a very simple model of natural organic matter derived from lignin and cellulose, for which there is now a lack of thermodynamic data as far as their interaction with toxic metal ions is concerned. Experimental results were obtained in various conditions of pH and ionic strength. In our modeling, we used the acidity constants and the concentration of sites that were determined in a previous work. The parameters deduced from the NICA-Donnan model were also compared to thermodynamic data available for other cases of natural organic matter, mainly humic substances.     

Natural dissolved organic matter affects electrospray ionization during analysis of emerging contaminants by mass spectrometry

Dissolved organic matter (DOM), present in many forms in water, can interfere with analysis of organic contaminants by atmospheric pressure ionization–mass spectrometry. A quantitative analysis of this interference, or matrix effect, on organic contaminant target analyte measurements was carried out using un-fractionated and fractionated dissolved natural organic matter from the Suwannee River, GA (SROM), a standard reference material, that was directly infused into the tandem mass spectrometer during multiple reaction monitoring (MRM) of a suite of endocrine disrupting compounds–pharmaceuticals and personal care products (EDC/PPCPs). Most target analytes suffered signal suppression in the presence of both fractionated and un-fractionated SROM, however greater interferences were measured with fractionated relative to bulk SROM. This finding is consistent with the view of organic matter as a supramolecular association of low molecular mass components having separate charged and structural features revealed only after dissociation.     

Determination of boron isotopic variations in aquatic systems with negative thermal ionization mass spectrometry as a tracer for anthropogenic influences

A technique for precise boron isotope ratio measurements with a high detection power has been developed by negative thermal ionization mass spectrometry (NTIMS). Relative standard deviations in the range of 0.03-0.3% have been obtained for the determination of the (11)B/(10)B isotope ratio using nanogram amounts of boron. Ba(OH)(2) has been applied as ionization promoter for the formation of negative thermal ions. By adding MgCl(2) better reproducibilities of the measurement have been achieved. A possible interference of BO(-)(2) ions at mass number 42 by CNO(-) could be excluded by the sample preparation technique used. Contrary to other NTI techniques no dependence of the measured isotope ratio on the boron amount used has been observed. Anthropogenic and natural saline influences in ground water have been successfully identified by boron isotope ratio determinations with this NTIMS method, due to the different isotopic composition of boron in natural and anthropogenic substances. In sewage, the boron isotope ratio is substantially influenced by washing powder, which contains low (11)B/(10)B ratios (expressed in delta(11)B values normalized to the standard reference material NIST SRM 951). In contaminated ground water, low delta(11)B values are normally correlated with high boron and high chloride concentrations. On the other hand, delta(11)B shifts to higher values in less contaminated samples. For ground water with saline influences, only the delta(11)B determination, and not the boron or chloride content, allowed the correct identification of this natural source of contamination.     

Precise determination of boron in titanium by inductively coupled plasma mass spectrometry

A method was developed for the determination of boron in titanium by inductively coupled plasma mass spectrometry (ICP-MS). A commercially available PTFE sample introduction system, leading to the desired low detection limits for boron, was used. The method is suitable for the determination of boron concentrations down to about 1 μg g^?1 in the solid material. The influence of the internal standard on the precision was studied and beryllium was selected as the internal standard. For the titanium analysed (BCR reference material 090), the ICP-MS result agreed with those obtained using other techniques. Several bars of titanium reference material were supplied and a study of the homogeneity of boron in this material was made. Using analysis of variance on the results obtained for the different bars, the homogeneity of boron in the reference material could be estimated to be better than 2.1%.     

Determination of boron in high-purity tantalum materials by on-line matrix separation/inductively coupled plasma mass spectrometry

A method for the determination of ultratrace amounts of boron in high-purity tantalum materials [tantalum metal, tantalum(v) oxide, tantalum pentachloride and tantalum pentaethoxide] is described. On-line anion-exchange matrix separation combined with inductively coupled plasma mass spectrometry (ICP-MS) was employed for the determination of boron at the ng g(-1) level. Tantalum materials were dissolved using HF and/or HNO3 prior to analysis. The loss of boron in the sample preparation procedure was examined as the recovery of boron by adding a definite amount of boron to each tantalum material sample before decomposition, and it was almost negligible. In an anion-exchange method using 0.1 M HF carrier solution, tantalum and boron in the sample solution were first adsorbed on a strongly basic anion-exchange resin. Next, boron was eluted from the resin with 5 M HCl, whereas tantalum was retained strongly adsorbed. The eluted boron was introduced directly into the ICP-MS system for quantitative analysis at m/z 10 and 11. Because of the long elution time of boron, the transient signal was integrated in the time range 70-300 s on the chromatogram. Although the elution of boron in the time range was ca. 40% of total boron in the sample solution injected, the determination limits (10sigma) obtained by the present method were 30, 25, 15 and 13 ng g(-1) for tantalum metal, tantalum(v) oxide, tantalum pentachloride and tantalum pentaethoxide, respectively. The method was applied to the determination of boron in commercially available high-purity tantalum materials and it was found that the concentrations of boron were in the ng g(-1)-microg g(-1) range.     

Aromaticity of planar boron clusters confirmed

Low-energy boron clusters are characterized by two-dimensional geometry. Aromaticity of these planar boron clusters was established in terms of topological resonance energy (TRE). All planar boron clusters were found to be highly aromatic with large positive TREs even if they have 4n pi-electrons. Aromaticity must therefore be the origin of unusual planar or quasi-planar geometry. Thus, the aromaticity concept is as useful in boron chemistry as it is in general organic chemistry. It is evident that the Hückel 4n + 2 rule of aromaticity should not be applied to such polycyclic pi-systems. Some of the boron clusters are in the triplet electronic state to attain higher aromaticity. Multivalency and electron deficiency of boron atoms are responsible for lowering the energies of low-lying pi molecular orbitals and then for enhancing aromaticity. For polycyclic pi-systems, paratropicity does not always indicate antiaromaticity.     

K 0-prompt gamma ray activation analysis for estimation of boron and cadmium in aqueous solutions

K ₀-PGAA (prompt gamma activation analysis) has been used to estimate boron and cadmium contents in industrial and environmental materials from some different local areas as well as, samples from different locations in Burullus and Qarun Lakes. A high efficiency Compton background suppression gamma-ray spectrometry by anti-coincidence counting with a NaI(Tl) shield around a central HPGe detector for in beam PGAA using a ²⁵²Cf neutron source has been calibrated and described in this paper. The facility is principally designed for measurement of the prompt gamma-ray spectra obtained due to thermal neutron capture using 1951.14 keV gamma line of ³⁵Cl as the internal mono-standard comparator. A calibration curves were developed in which a set of boron and cadmium standards were tested and the count rate to boron and cadmium mass curves were determined. This set of boron and cadmium measurements was compared with a method for determining composition using K ₀-PGAA. Conventional prompt neutrons capture Gamma-ray results were in a good agreement with the data obtained by K ₀-PGAA method. Detection limits and self-shielding study are presented.     

Analysis of boron in biological reference materials using prompt gamma activation analysis

Summary A prompt gamma activation analysis facility has been constructed on the ST1 horizontal beam port at the HANARO research reactor, KAERI in 2003. The detector system consists of a high-purity Ge detector surrounded by BGO/NaI(Tl) scintillators as an annulus type to reject the Compton scattered photons. Detection sensitivity for boron was obtained from the prompt gamma-ray spectra of boric acid, B(OH)₃, containing 0.1-65 μg boron. The net peak for the calculation of the boron concentration was obtained by eliminating the sodium 472 keV peak, involved in the boron 478 keV peak. The biological samples used are NIST SRMs such as Peach Leaves, Apple Leaves, Tomato Leaves, Spinach Leaves, Total Diet, Typical Diet, Oyster Tissue and Corn Bran, etc. The measured values for high boron concentration showed up to a 3% of the relative, but in a low concentration below 5 ppm, present values were higher than the certified ones.     

Rapid accurate isotopic measurements on boron in boric acid and boron carbide

A procedure is described whereby rapid and accurate isotopic measurements can be performed on boron in boric acid and boron carbide after fusion of these compounds with calcium carbonate. It allows the determination of the isotopic composition of boron in boric acid and boron carbide and the direct assay of boron or the (10)B isotope in boron carbide by isotope-dilution mass spectrometry.     

Determination of trace quantities of boron with two new colorimetric reagents

Two new color reactions with boron are reported. Sensitive methods have been developed for their use. A new method for the decomposition of fruit tree leaves and alfalfa, and the subsequent separation of the boron is described.The reagents are 5-benzamido-6'-chloro-1, 1 '-bis (anthraquinonyl) amine(I) and 5-p-toluidino-1,1'-bis (anthraquinonyl) amine(II). Concentrated (96%) sulfuric acid is used as the solvent. The formation of the boron complex of the reagents was found to be dependent on the following variables: time of heating, temperature, sulfuric acid content and the presence of diverse ions.Solutions of the two complexes follow Beer's law over the boron range indicated: Compound I, 0 to 0.5 γ at wavelength of 635 mμ and Compound II, 0 to 0.4 γ at wavelength 720 mμ. The sensitivities are 1 : 300,000,000 and 1 : 200,000,000, respectively. The standard deviation was calculated for the determination of boron with each compound. Results showed 0.002 absorbance unit, i.e., 0.001 γ of boron for Compound I and 0.005 absorbance unit, i.e., 0.002 γ of boron for Compound II.The method of decomposing the leaves and alfalfa samples is based upon destroying all the organic matter with a mixture of 96% sulfuric acid and 30% hydrogen peroxide within, the distilling flask. Boron is then distilled off as the volatile trimethyl ester. The standard deviation of the method is 0.58%.     

Preparation and structural characterization of three types of homo- and heterotrinuclear boron complexes: salen[[B-O-B][O2BOH]], salen[[B-O-B][O2BPh]], and salen[[B-O-B][O2P(O)Ph]

Three types of homo- and heterotrinuclear boron complexes have been obtained in moderate to good yields from reactions of salen-type ligands with boric acid and combinations of boric acid with phenylboronic and phenylphosphonic acid. The products are air-stable and have relatively high melting points (>290 degrees C) but are poorly soluble or insoluble in common organic solvents. They have been characterized as far as possible by elemental analysis, mass spectrometry, IR, (1)H, (11)B, and (31)P NMR spectroscopy, and X-ray crystallography. Furthermore, theoretical calculations have been performed for representative examples to permit a complete comparison of the different structure types. A detailed analysis of the molecular structures showed that the complexes are constructed around a central B(3)O(3) or B(2)PO(3) ring. The salen ligands are attached to two boron atoms of these rings, which have therefore tetrahedral coordination geometries. The complexes contain seven- and eight-membered heterocycles of the B(2)C(n)ON(2) (n = 2, 3) type with chair or twisted-chair and boat-chair or chair-chair conformations, respectively. In the homotrinuclear complexes one of the three boron atoms is three-coordinate and can therefore still act as Lewis acid, thus making these products interesting for catalytic applications, e.g. in asymmetric synthesis. Depending on the substitutents attached to the boron atoms, these complexes show a relationship with either trimetaboric acid, boroxine, or the tetraborate dianion found in Borax.     

Removal of boron(III) by N-methylglucamine-type cellulose derivatives with higher adsorption rate

To obtain adsorbents for boron(III) derived from a natural polymer, two forms (powder and fiber) of N-methylglucamine-type cellulose derivatives were newly synthesized. After the graft polymerization of two forms of cellulose with vinyl monomer having epoxy groups, the N-methylglucamine-type cellulose derivatives were obtained by the reaction of the grafted cellulose with N-methylglucamine. The adsorption capacities of the cellulose derivatives for boron(III) were the same levels as that of a commercially available N-methylglucamine-type polystyrene resin. However, the cellulose derivatives adsorbed boron(III) more quickly than the polystyrene resin. The adsorption and desorption of boron(III) with a column method using the cellulose fiber were achieved at a higher flow rate than that using the polystyrene resin. In addition, the boron(III), adsorbed on the cellulose fiber column, was quantitatively recovered with dilute hydrochloric acid in 20- and 200-fold increased concentrations. Consequently, it was found that the cellulose derivatives were superior to the polystyrene resin as adsorbents for boron(III) for treatment of a large quantity of wastewater.     

The carbon versus mass diagram to visualize and exploit FTICR‐MS data of natural organic matter

A two‐dimensional diagram is proposed, in which the carbon number of each formula is plotted against its nominal mass, to visualize large sets of molecular formula data that can be derived from data generated by ultrahigh‐resolution Fourier transform ion cyclotron resonance‐MS. In such a carbon versus mass (CvM) diagram, each formula (C_cH_hO_o) is unambiguously described by c, its (nominal) mass and the parameter i = c + o. Calculations of chemically allowable formulas illustrate that organic molecules occupy only certain spaces in such a diagram. The extension of these spaces increases with molecular mass in x‐direction (hydrogenation) and y‐direction (oxygenation). The data sets of molecules determined in natural organic matter(NOM) occupy only a certain range of the allowable space. The intensity of the mass spectrometric signals can be included as the third dimension into a CvM diagram. Separate CvM diagrams can be plotted for NOM molecules that include different heteroatoms. The benefits of the CvM diagram are illustrated by application onto data sets of fulvic acids from riverine and marine origin, of secondary organic aerosol, including organosulfates and organonitrates, as well as of ozonation of fulvic acids. The CvM diagram is a useful tool to visualize the elemental regularities in NOM isolates as well as the differences between isolates. It may also be applicable to large sets of molecular formula data generated in other disciplines such as petroleum biogeochemistry or metabolomics. Copyright © 2010 John Wiley & Sons, Ltd.     

酚基吡啶硼配合物发光材料

主要介绍双酚基吡啶硼配合物的合成、分子结构、分子堆积结构及其在有机电致发光器件中的应用.研究结果表明一些双酚基吡啶硼配合物可以作为发光材料制备性能优良的电致发光器件.     

Combinations of hydroxyl-terminated polybutadiene and boron

Mixing and curing experiments with suspensions of boron in hydroxyl-terminated polybutadiene (HTPB) have been performed. In kneading experiments on a plastograph very high viscous masses with bad curing properties were obtained. The experiments indicated that HTPB is attached with its OH groups to acidic impurities on the surface of the boron powder. By adding a basic substance, such as octadecyl amine, mixing and curing were undertaken with much less difficulty.     

土壤中有效硼含量测定方法优化与对比

为确保第三次全国土壤普查数据真实可靠,需对相关标准检测方法进行反复验证以优选出适合在全国范围内推广的方法。目前NY/T 1121.8-2006甲亚胺-H比色法测定土壤有效硼灵敏度较低,显色温度及光照等因素容易对测定结果造成干扰。鉴于此,本文对沸水浴浸提-甲亚胺-H比色法测定土壤有效硼过程中的浸提时间、浸提方式以及显色条件等关键因素进行了分析,并探究方法测定优化条件。结果表明提取时间选择12 min、加盖浸提以及23 ℃避光显色处理,可以较好地减少有效硼测定过程中的误差,获得更为准确的结果。同时对电感耦合等离子体光谱法（ICP-OES）测定土壤有效硼进行了验证,比色法、ICP-OES法的检出限分别为0.012 mg/kg、0.009 mg/kg,均满足分析测定的要求。方法准确度和精密度验证结果表明二者均可用于土壤有效硼的测定,并且实际样品测定结果无显著性差异。其中,比色法适用于测定高含量（>0.5 mg/kg）样品,ICP-OES法适用于中、低含量样品的测定。结合第三次全国土壤普查内业检测定点工作中的经验,本文建议将ICP-OES法作为第三次全国土壤普查有效硼测定的首选方法,以期为“三普”内业检测提供参考和借鉴。     

Extractive spectrophotometric and fluorimetric determination of boron with 2,2,4-trimethyl-1,3-pentanediaol and carminic acid

Boric acid at μg/ml or ng/ml level can be extracted from 1-6M hydrochloric acid into 2,2,4-trimethyl-1,3-pentanediol solution in chloroform and thus separated from many ions which interfere in the usual spectrophotometric methods. The boron is determined directly in the organic phase without back-extraction into water, by adding a solution of carminic acid in a mixture of sulphuric and glacial acetic acids (1+2 v/v) and measuring the absorbance at 549 nm. The molar absorptivity is 2.58 × 10⁴ l.mole⁻¹.cm⁻¹ and Beer's law is valid for the 0.05–0.4 μg/ml boron range. In the fluorimetric method, 509 or 547 nm can be used as the excitation wavelength and 567 nm for emission measurement, giving a linear response in the 8–120 ng/ml boron range. Both methods have been applied to determination of boron in plants and natural waters with good precision and accuracy.