Determination Of Halogen Research Articles

Combined in-situ determination of halogen (F, Cl) content in igneous and detrital apatite by SEM-EDS and LA-Q-ICPMS: A potential new provenance tool

Apatite is an accessory mineral that is widely present in most igneous and metamorphic rocks, and is a common detrital component in clastic rocks. As apatite typically incorporates U at sufficient concentrations to enable thermochronometry (e.g., U-Pb, fission track, and (UTh)/He), it is commonly used in detrital provenance studies. Apatite also incorporates a wide range of trace elements at concentrations readily detectable by routine laser ablation-quadrupole-inductively coupled plasma-mass spectrometry (LA-Q-ICPMS) analysis, which can also yield diagnostic provenance information (in particular Sr-Y-REE). However, detrital thermochronometry is of limited use in the case of source terrane(s) with similar crystallisation or cooling histories, while trace elements may yield non-diagnostic provenance information when their source rocks are lithologically similar (e.g., co-genetic granitoids). Here we test a complementary provenance approach which exploits F and Cl substitution into the stoichiometric Z-site in the apatite lattice. Halogen abundance in igneous apatite typically reflects the source melt composition and its subsequent differentiation history, offering potential for provenance discrimination. We apply this method to apatite from bedrock samples of five late- to post-tectonic granitoids in the Grampian and Moine terranes of the Scottish Caledonides, which yield zircon UPb ages of ca. 425–398 Ma. Emplacement over this relatively short time window makes it difficult to discriminate between sediment sourced from these plutons using radiometric dating alone. Apatite F content was measured using an energy dispersive X-ray spectrometer coupled to a scanning electron microscope (SEM-EDS), while Cl and trace element (Sr-Y-REE) abundances were determined by LA-Q-ICPMS. We show that the sampled granitoids can be divided into three groups based on their apatite trace element contents and into three separate groupings based on their F and Cl abundances; all five plutons can thus be discriminated from each other using their integrated trace elements and F-Cl systematics. The granitoid groups identified by their apatite F and Cl contents correlate with those depicted by their modal mineralogy as defined in Quartz-Alkali Feldspar-Plagioclase (QAP) space, with granitoids richer in K-Feldspar (and thus more evolved) yielding apatites with higher F contents. As a pilot study, we also analysed apatite from modern river sediment in the Spey River catchment of the Grampian terrane, for which UPb age data were also acquired. The Spey detrital apatites yield UPb ages that are indistinguishable at the 2σ-level, but their trace element abundances allow three bedrock types to be distinguished: I-type granitoids, S-type granitoids and medium- to high-grade metamorphic rocks. The detrital apatite F and Cl data do not permit such straightforward discrimination, as apatites from S-type granitoid and metamorphic rocks have comparably low Cl contents. However, the detrital apatites with I-type granitoid affinity display significant dispersion in halogen contents (yielding the lowest F abundances with correspondingly the highest Cl contents), which identifies the presence of several more “mafic” I-type granitoid bodies in the Spey catchment. Apatite F and Cl abundances thus have potential for detailed characterisation of the individual components of granitoid suites, including delineating I-type granitoids or the presence of less evolved magmatic bodies among detrital apatites.

TXRF intensity dependence on position of dried residue on sample carrier and TXRF determination of halogen in liquid samples

Total reflection X‐ray fluorescence (TXRF) spectroscopy is an effective technique for simultaneous multi‐elemental trace analysis of a small volume of a sample placed on a flat substrate. An internal standard method is usually applied for quantitative TXRF analysis of liquid samples such as drinking water and environmental samples. However, it was difficult to determine Cl and Br because they were lost as volatile hydrogen halide compounds by adding an acid internal standard solution. Thus, we attempted to apply the traditional calibration curve method for the determination of halogens without internal standard. If internal standard method is not applied, the TXRF intensity drastically changes depending on the relative position of the dried residue to the detector. Therefore, we investigated the relationship between TXRF intensity and the position of dried residue relative to the detector. As a result, it was confirmed that TXRF intensity critically depended on the position of the dried residue on the sample carrier. The position of the droplet of the sample solution was carefully controlled by using an air blower in order to place the dried residue at the most effective position on the sample carrier. We could successfully make a calibration curve for Cl with a good relationship without internal standard. Finally, Cl in the NaCl solutions (0 –5 ppm, 10 µl) was successfully determined by the calibration curve method using a table‐top TXRF instrument. The limit of detection of Cl was 63 ppb (ng/ml). Copyright © 2016 John Wiley & Sons, Ltd.

Ion Chromatography for Rapid and Sensitive Determination of Total Chlorine in Water

In this article, we report a new method that involves adsorption, oxygen bomb combustion, and ion chromatography for the preconcentration and determination of adsorbable organic halogen. This method can be divided into four steps, including: macroporous resin adsorption enrichment, optimization, oxygen bomb combustion, and ion chromatography determination. The project studies the macroporous resin adsorb organic halide pollutants and subsequent burn by an oxygen bomb combustion analyzer. The organic halogen in the aerobic environment combusts into hydrogen chloride. The water absorbing hydrogen chloride was then determined by ion chromatography. The influences of some adsorption and combustion parameters, such as the adsorption time, adsorption solution volume, solution pH, hexachlorobenzene acid concentration, combustion oxygen pressure, among others, on their respective adsorption efficiency were investigated. In the optimal condition, the adsorption time was 3.5 h; solution volume was 20 mL; pH was 4; combustion absorption time was 15 min; and the chloride calibration working range was from 1 ppm to 20 ppm (R 2 = 0.9998). Finally, the proposed method was successfully applied to the determination of organic halogen in water samples. The recoveries of chlorine (at spiked concentrations of 10 ppm and 20 ppm into water) in real samples ranged from 92.2% to 101.0%. Intra-day precision (N = 3) in terms of peak area, expressed as relative standard deviation, was found to be within the range of 0.68%–1.97%.

Determination of bromide, bromate and other anions with ion chromatography and an inductively coupled plasma mass spectrometer as element-specific detector

An implementation of the Dionex IonPac AS12A analytical column with an element-specific ICP-MS detection is described for the simultaneous determination of halogen and oxyhalogen anions, sulfate, phosphate, selenite, selenate and arsenate. The chromatographic separation was achieved in less than 4 min with an aqueous 11 m M (NH 4) 2CO 3 (pH 11.2, adjusted with aqueous ammonia) as eluent. Special emphasis was given to optimize the ICP-MS detection conditions for the reliable detection (RSD<5%) of bromate and bromide at a bromine concentration level of 1.0 μg l −1 with 50 μl sample injection volume. In order to achieve the highest detector response for bromine species an ultrasonic nebulizer equipped with a membrane desolvator had to be employed. The detection limits ( S/ N=3, sample injection volume 50 μl) obtained with the IC–ICP-MS after the optimization were 0.67 μg l −1 for BrO 3 −, 0.47 μg l −1 for Br −, 69 μg l −1 for ClO 2 −, 4 μg l −1 for Cl −, 47 μg l −1 for ClO 3 −, 13 μg l −1 for SO 4 2−, 36 μg l −1 for PO 4 3−, 0.4 μg l −1 for SeO 3 2−, 0.3 μg l −1 for SeO 4 2−, and 0.4 μg l −1 for AsO 4 3−.

Determination and location of halogen in mangrove root tissues by PIXE method

The localization of chlorine and bromine in mangrove ( Bruguiera gymnorrhiza L.) root tissue was determined using the particle induced X-ray emission (PIXE) method. A proton beam of 2.0 MeV collimated to 0.2 × 2 mm bombarded the surface of a root section. A qualitative determination of chlorine and bromine showed a different content among tissues. Assuming the chloride anion to be the counter anion for the sodium cation in root tissue, a considerable amount of sodium chloride was accumulated in pith tissue. The pith may play a significant role in osmoregulation. Contents of strontium, analogue to calcium, were higher in exodermis and aerenchyma. These tissues need more calcium than other tissues to make up cell wall turgidity.

Some Recent Approaches to Micro- and Ultramicro-Elemental Organic Analysis

Automatic instrumentation has been developed for the microdetermination of various elements in organic samples ranging from 2 to 3mg. The author has devised a microanalyzer for carbon, hydrogen and nitrogen which embodies a pump system for collecting the combustion gas; this device operates on the principle of thermal conductometry for determining the three elements. The pump system is also useful for the microdetermination of organic oxygen in collecting equivalent carbon monoxide, which is then determined by infrared photometry. Organic halogen and sulfur compounds are mineralized in the conventional oxygen flask combustion and the resulting halide and sulfate ions are titrated potentiometrically with standard silver nitrate or barium chloride by means of an ion-selective glass electrode for getting the end point. Equivalence points are characterized by extremely sharp points of inflection; i.e. short lengths on the steeply rising sections of the titration curve. Ultramicrodetermination of elements in 0.5mg organic sample or lessare vital in the field of biochemistry. Dry combustion in a sealed tube has been proposed to minimize the blank value and to eliminate loss of reaction products. Accurate determination of nitrogen and later of carbon, hydrogen and nitrogen simultaneously has become possible. This approach has been further extended to the determination of halogen and sulfur.

Determination of nanoequivalent amounts of organic halogens by sample combustion—flow-injection conductimetry with on-line preconcentration

A simple and sensitive sample combustion—flow-injection technique for measuring nanoequivalent amounts of organic halogens (except fluorine) is presented. The determination of volatile organic halogen (VOX) in water and total organic halogen (TOX) in air, in solid substances and in aqueous solutions is discussed in detail. The sample is subjected to high-temperature combustion in a stream of oxygen. Decomposition products containing halogen are preconcentrated from the gas stream by absorption in a capillary denuder tube coated with a 0.1–0.4 mM aqueous solution of a hydrazine monohydrohalide salt; meanwhile carbon-, sulphur- and nitrogen-containing combustion products are removed by the carrier gas. The hydrohalic acid formed in the liquid film is then eluted with a stream of the absorbent circulated through an electrolytic conductivity microdetector. The change in specific conductance due to the presence of the hydrohalic acid in the effluent stream is linearly related to the amount of halogen in the sample (e.g., up to 100 neq of chlorine). The limit if detection for VOX is 0.01 μeq l−1 and for TOX in air 0.2 μeq m−3. A simple determination takes 5 min. The precision was better than 5% (P=95%) for 3–100 neq of chlorine. The method is also suitable for the determination of total halogen (TX) in aqueous solutions and solid substances. Further, it allows the determination of the partial amounts of halogen species included in the VOX, TOX or TX content of the sample.

Photochemical Decomposition for Determination of Organic Sulfur and Organic Halogen in Aqueous Solution by Ion Chromatography

Photochemical Decomposition for Determination of Organic Sulfur and Organic Halogen in Aqueous Solution by Ion Chromatography

Comparison of two methods for the determination of total organic halogen (TOX) in receiving waters

Two methods for the determination of total organic halogen (TOX), orginating from bleaching of pulp, in receiving waters have been compared. One of the methods (AC/MC) is based on adsorption of the halogenated matter onto an activated carbon sorbent. The halogen is determined by a microcoulometric technique after combustion of the carbon. The other method (XAD/PT) uses an XAD resin as sorbent and the determination of the halogen is carried out by potentiometric titration after a schöniger combustion of the resin eluate.Both methods showed good performance for samples consisting of spent bleach liquors diluted with distilled, fresh and brackish water. The repeatability was very good with a relative standard deviation less than a few per cent. The detection limit of the AC/MC method is about 0.1 μmol/1 and for the XAD/PT method about ten times higher. The AC/MC method gave in most cases 10–20% higher TOX concentrations compared to the XAD/PT method.

Determination of Organic Halogen and Sulphur Compounds in Domestic Refuse Samples by Ion Chromatography

Abstract The aim of this investigation is-the estimation of the impact on the environment caused by organic halogen and sulphur compounds contained in domestic refuse samples. Samples were collected in the whole Federal Republic of Germany under statistical aspects. After sorting, grinding and Wickbold-combustion the compounds chloride, fluoride and sulphate were determined.

A new method for simultaneous determination of nitrogen, hydrogen and halogen in organic compounds

A new method for the determination of nitrogen, hydrogen and halogen in organic compounds is described. It is based on flash combustion in a fast stream (100 ml/min) of an automatically generated gas mixture (CO2+20% O2). A sample placed in an aluminium capsule and mixed with about 20 mg of V2O5 is combusted in the presence of CO3O4 coated on porous silica. Rapid gravimetric methods for final determination of hydrogen and halogens and a volumetric method for nitrogen are used. The combustion process has been examined by a rapid photography technique, mass spectrometry and gas chromatography. From an extensive statistical analysis (about 300 analyses) of various compounds containing C, H, O, N, Br, Cl, I and S, the following precision is obtained:sN=0.03–0.15%;sH=0.09–0.14%;s=0.07–0.20% absolute. The automation of the final determination of nitrogen and hydrogen has been examined.

Determination of organic halogen in hexane solution

Determination of organic halogen in hexane solution

Quantitative determination of halogen elements in organic compounds by atomic absorption spectrophotometry

In the previous paper, authors reported on the quantitative determination of halogen-containing drugs by atomic absorption spectrophotometry using air acetylene flame with good accuracy. In this study, it has been found that determination of sublimable halogen containing compounds such as 1-chlorophenazine, hexachlorobenzene and ο-bromobenzoic acid may be carried out successfully by employing a more proper reductive decomposition method.The recommended procedures are as follows: Nonsublimable compounds, such as, p-chloroaniline and p-bromoacetanilide, were fused with metallic sodium of 1020 times as much as the weight, and after an excess metallic sodium being decomposed with water, the residues were filtered off and the filtrate was used for the measurement. Then, a proper amount of the sample solution (14 ml) was made acidic with nitric acid, followed by the addition of 5ml of 100μg/ml silver nitrate solution, and the resultant solution was warmed on a water-bath for 1 min. It was kept standing for 30min at a roomtemperature, the precipitates were filtered off and the filtrate was diluted to 100ml with water, then an excess amounts of silver were determined by atomic absorption spectrophotometer. However, this procedure is not applicable to the sublimable compounds such as 1-chlorophenazine, and the following manipulation was performed according to the method of Yano, et al. That is, in a 50ml capacity of flask, a compound was dissolved in 2 ml of alcohol (n-butanol, iso-amyl alcohol, etc.) with a reflux condenser and warmed. After an addition of metallic sodium, the resultant solution was boiled for 30 min and then it was kept standing for 10 min at a room-temperature. After an addition of water, insoluble materials were filtered off and the filtrate was used for the measurement. Standard solutions of Cl, Br, and I for working curves were prepared according to the similar procedures. In order to ascertain the repeatability, the compounds of various halogen contents were analyzed and the standard deviation was calculated to be 0.210.53.In conclusion, this method has been found to be applicable to the quantitative determination of halogen elements in organic compounds.

Hot-flask determination of chlorine

The hot-flask combustion-diffusive absorption method for the decimilligram determination of halogen has been improved by the addition of 1 μl of orthophosphoric acid to the sample before the combustion. Alkali- and other ash-containing as well as inorganic compounds can now be easily analyzed. It was applied to the determination of chlorine with automatic differential electrolytic potentiometric titration.

Determination of halogen in copolymers by dye‐partition technique and calculation of r1 therefrom

Determination of halogen in copolymers by dye‐partition technique and calculation of r₁ therefrom

Determination of halogen in copolymers by dye‐partition technique and calculation of r1 therefrom

AbstractHalogen‐bearing polymers have been prepared by copolymerization of monomers (M1) such as styrene, methyl methacrylate, methyl acrylate, and vinyl acetate with traces of chlorine‐bearing monomers (M2) such as allyl chloride and tetrachloroethylene at varying M1:M2 ratios in the 100:1 composition range. The halogen atoms in the copolymers were transformed to quaternary pyridinium halide groups by quaternization with pyridine. The copolymer compositions and the monomer reactivity ratio r1 were determined by the estimation of the quaternary halide groups in the copolymers by the dye‐partition technique, with aqueous disulfine blue VN150 in 0.01M hydrochloric acid as the dye reagent.

Hot-flask combustion methods for decimilligram determination of halogen and other elements in organic compounds

Two new, very simple and fast combustion methods for decimilligram determination of halogens and other elements in organic compounds were described. They can be considered as combinations of Schöniger's flask combustion method and Ingram's flash combustion method. Diffusion was used for the absorption of the combustion products in one of the methods.

Simultaneous determination of carbon hydrogen, halogen, or sulfur content by the deflagration combustion method

1. Methods have been developed to carry out the simultaneous and separate determination of carbon, hydrogen, halogen or sulfur by deflagration combustion. 2. The presence of elements in the molecule which form nonvolatile oxides during combustion does not prevent the C and H being determined. 3. The method gives good reproducible results with an error in determination which does not exceed ±0.3%.

On the use of nitrite in the determination of halogen in organic compounds

A few properties of nitrite are cited which are useful for the determination of halogens and perhaps also of sulfur in organic compounds. Procedures using this reagent for the determination of chlorine and bromine in ordinary organic compounds and compounds containing mercury, using flask combustion, and a procedure for microdetermination of chlorine and bromine using combustion and subsequent hydrogenation are described.

Simultaneous determination of carbon, hydrogen, sulfur, and halogens

1. A method is developed for the simultaneous and separate determination of carbon, hydrogen, sulfur, and halogen. 2. The presence of elements forming nonvolatile oxides in the combustion does not interfere in the determination. These elements can be determined simultaneously as ash from the increase in weight of a quartz tube.