Regular ArticleBoron Determination—A Review of Analytical Methods
Abstract
This paper reviews published methods of sample preparation, determinand purification, and the determination of boron concentration and isotopic composition in a sample. The most common methods for the determination of B concentration are spectrophotometric and plasma-source spectrometric methods. Although most spectrophotometric methods are based on colorimetric reactions of B with azomethine-H, curcumin, or carmine, other colorimetric and fluorometric methods have also been used to some extent. These methods, in general, suffer from numerous interferences and have low sensitivity and precision. Application of nuclear reaction and atomic emission/absorption spectrometric (AES/AAS) methods has remained limited because these methods have poor sensitivity and suffer from serious memory effects and interferences. Among a large number of published nuclear reaction methods only prompt-γ spectrometry has been of practical use. The prompt-γ method can determine B concentration in intact samples, which makes this method especially useful for some medical applications, including boron neutron capture therapy. However, this is a time-consuming method and not suitable for detection of low levels of B. Inductively coupled plasma optical emission spectrometry (ICP-OES) created a new dimension in B determination because of its simplicity, sensitivity, and multielement capability. However, it suffers interferences and is not adequately sensitive for some nutritional and medical applications involving animal tissues that are naturally low in B. All methods involving the measurement of B isotopic composition require a mass spectrometer. Thermal ionization mass spectrometry (TIMS) and secondary ion mass spectrometry (SIMS) have been used to measure isotopic composition of B; however, these methods are time consuming and require extensive sample preparation and purification. Development of inductively coupled plasma mass spectrometry (ICP-MS) not only overcame most of the drawbacks of earlier methods, but also its capabiltiy of measuring B isotopes made possible (1) B concentration determination by isotope dilution, (2) verification of B concentration by isotope fingerprinting in routine analysis, and (3) determination of total B concentration and B isotope ratio for biological tracer studies in the same run. Therefore, plasma source MS appears to be the method of choice among present-day technologies.
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Boron compounds play a crucial role in various industries, and accurate quantification of boron is essential for quality control and environmental monitoring. This study presents a simple, rapid, and reliable method for determining boron in aqueous solutions using suppressed ion chromatography coupled to electrospray ionisation-triple quadrupole mass spectrometry (IC-ESI-QqQ-MS). Boric acid (B(OH)3) was retained as the tetrahydroxyborate ion (B(OH)4−) on a CarboPac PA300-4 μm anion-exchange column using isocratic elution with 40 mM KOH. During the neutralization process at the suppressor, B(OH)4− was converted to B(OH)3, which subsequently generated the metaborate ion [BO2]− (m/z 43) within the electrospray ionisation source. By employing a pseudo-selected reaction monitoring (SRM) transition from m/z 43 to m/z 43, the method achieved a limit of detection (LOD) of 2.45 μg/L of boron, the lowest reported in the literature to-date for an IC-based method. The analytical performance of the method demonstrated no carry-over issues, no matrix interferences, and excellent intra- and inter-run repeatability of 2.03% and 3.41%, respectively. The method was applied to the evaluation of boron uptake and retention by Tasmanian Oak timber blocks, treated by dip-diffusion in a boric acid solution of 2.5% Boric Acid Equivalent (BAE, m/m) under controlled laboratory conditions. Quantitative determination of the retained and unretained boron allowed a mass balance evaluation and confirmed the accuracy and reliability of the method, with recoveries ranging from 99.3% to 100.2%.
Smartphone digital image colorimetry combined with dispersive solid-phase microextraction for the determination of boron in food samples
2023, Food ChemistrySimple, inexpensive and accurate analytical methods are in high demand. Dispersive solid-phase microextraction (DSPME) was used in combination with smartphone digital image colorimetry (SDIC) to determine boron in nuts as an approach replacing existing costly alternatives. A colorimetric box was designed to capture images of standards and sample solutions. ImageJ software was used to link pixel intensity to the analyte concentration. Under optimum extraction and detection conditions, linear calibration graphs were obtained with coefficients of determination (R2) above 0.9955. Percentage relative standard deviations (%RSD) were below 6.8 %. The limits of detection (LOD) ranged between 0.07 and 0.11 μg mL−1 (1.8 to 2.8 μg g−1), which were sufficient for detection of boron in nut samples (i.e., almond, ivory, peanut and walnut), with percentage relative recoveries (%RR) between 92.0 and 106.0 %.
Fluorometric investigation of boric acid-pyridoxal 5′ phosphate interaction: A turn-on-fluorescence assay for the detection of boric acid in water bodies and fetal bovine serum
2023, Microchemical JournalBoron is a trace element that is beneficial to plants as well as human and animal health. Boron supplementation is beneficial for absorbing vitamin D and magnesium, activating antioxidant enzymes and anticancer treatments. However, environmental accumulation of boron exceeding the permissible limit harms plants, animals and humans. Boric acid (BA), a form of boron, is known to interact with biomolecules such as NAD+/NADH, vitamin C, vitamin D, vitamin B1 and vitamin B6 determined through techniques like NMR, mass spectrometry, and FTIR. The fluorescence interaction of BA with the biologically active form of vitamin B6, Pyridoxal 5′ phosphate (PLP), has not been explored to date. Therefore, this study reports the interaction mechanism of BA with PLP via fluorescence spectroscopy analysis. The absorption, excitation and fluorescence lifetime measurements indicate that BA may form a complex through the mono or di-esterification of the phenolic hydroxyl group and aldehyde of PLP at different pH, forming the boronate esters. BA addition enhanced the fluorescence intensity of PLP by 12–22-fold in phosphate buffer (at acidic, neutral, and basic pH conditions). On the other hand, in citrate buffer at pH 4.0, BA enhanced PLP fluorescence by 28-fold. The binding constant for BA in phosphate buffer and citrate buffer was found to be 173 mol−1·L and 623 mol−1·L, respectively. At the same time, the detection limit for BA was found to be 445 μg/L and 212 μg/L in respective buffers. Therefore, PLP was used as a turn-on fluorescent probe to detect and quantify BA in water bodies and fetal bovine serum (FBS). The developed method successfully detected BA in environmental water bodies, achieving an average recovery rate of 99.84% (with a relative standard deviation (RSD) of 0.38%) in phosphate buffer and 81.59% (RSD, 4.56%) in citrate buffer. Furthermore, detecting BA in PLP-spiked FBS has been demonstrated in citrate buffer at pH 4.0, yielding an average recovery rate of 108.25% (RSD, 3.19%). Therefore, this study provides a basis for understanding the interaction of biomolecules like vitamins with boronates which aid in development of novel boronate based therapeutics and also helps in understanding the metabolic reactions of vitamin derivatives using fluorescence spectroscopy.
Development of an external PIGE method using nitrogen from atmospheric air as external beam current normalizer and its application to nondestructive quantification of total boron mass fraction in boron containing neutron absorbers
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The separation of boron in nuclear fuels by cloud point extraction (CPE) has been a challenge due to high acidity of digested sample solutions. High acidity hampers the coacervation of micelles. As a result, the cloud point temperature increases and thus could cause the inevitable loss of boron as volatile species. Herein we have proposed a novel CPE-assisted colorimetric method for the quantification of traces of boron (B) in uranium-based fuels. A 1:1 mixture of 2-ethyl hexane-1,3-diol (EHD) and curcumin dispersed in Triton X-114 surfactant was used in the proposed CPE process. We had investigated several compounds to act as micelle surface modifiers. Among them, only bromine water (Br2) was found not only to lower the cloud point temperature (CPT, from 80 °C to 42 ± 2 °C) but also resulted in the quantitative recovery of boron (≥95%). The CPE of boron from uranium matrix in a 2.0 mol L−1 HCl medium was suitable for direct chemical quality assurance of routine uranium-based fuels. The molar extinction coefficient of the boron-EHD-curcumin complex was found to be 4.75 × 105 L mol−1 cm−1 (λmax at 458 nm) in N,N-dimethyl formamide medium. The linear dynamic range and detection limit of the proposed analytical procedure were calculated to be 10–150 ng mL−1 and 0.8 ng mL−1 respectively. The proposed analytical methodology was validated by analysis of three in-house working reference materials of uranium. Determination of traces of boron in two uranium dioxide and two metallic uranium samples were found to demonstrate the applicability of the method. The relative standard deviation of the proposed method was found to be of 3–5%.
Development of an innovative external (in air) Particle Induced Gamma-ray Emission method for rapid non-destructive determination of isotopic composition of boron in “As received” boron based ceramic neutron absorbers
2022, Analytica Chimica ActaBoron is an important element in nuclear reactor technology due to its high neutron absorption cross section of 10B isotope. Isotopic composition of B (IC, 10B/11B atom ratio) determination in finished neutron absorbers is a necessity under chemical quality control (CQC). We report an innovative greener method for rapid and non-destructive approach of isotopic composition determination of B in “as received” boron based ceramic neutron absorbers including boron carbides and hexa-borides by external (in air) Particle Induced Gamma-ray Emission (PIGE) using 3.5 MeV proton beam. It involves irradiation of “as received” powder samples wrapped in a thin Mylar film and measurement of prompt gamma rays at 429, 718 and 2125 keV from 10B(p,αγ)7Be, 10B(p,p’γ)10B and 11B(p,p’γ)11B, respectively, using a HPGe detector system. The method was standardized with natural and enriched B4C powders. For validation, the results of isotopic composition obtained from “as received” samples were compared with that obtained from pellet samples using both external and vacuum chamber PIGE methods. IC values obtained for natural to 10B enriched samples (19.8–67 atom % of 10B) are very encouraging with 1–2% and 0.3–0.7% uncertainties from single and replicate sample experiments. The method is truly non-destructive as the samples can be returned back as such after the experiment as they are not radioactive. Compared to existing PIGE method for isotopic composition of B, the developed method keeps promise for wide applications as it is simple, sensitive and rapid and it does not require vacuum, pellet preparation with a binder, exact mass of the sample and beam current measurement.