Development and field evaluation of a new diffusive sampler for Hydrogen Sulphide in the ambient air

A diffusive sampler for the determination of hydrogen sulphide (H₂S) based on collection on a paper filter coated with silver nitrate followed by optical densitometric determination of the metal sulphide was developed. Laboratory tests were conducted in controlled atmosphere to evaluate linearity, uptake rate, face velocity effects, sample stability, influence of relative humidity and of interferents, precision and accuracy. The measured uptake rate for H₂S was determined in experiments involving sampling at different concentration levels in comparison to a wet standard colorimetric technique. The precision of the measurements for co-located passive samplers was lower than 15%. The accuracy of the data collected is within 20% of the actual value measured by the wet method. The sampler is capable of reliable measurements of H₂S at common levels of a polluted atmosphere in urban settings yielding average concentration levels over one month and beyond. Diffusive sampling can be adopted to analyse in detail the temporal and spatial trends of H₂S concentration in ambient air and in specific historic buildings or in museums. Figure At the end of sampling cap #2 is removed and optical density is measured     

Development of highly sensitive cadmium iondashselective electrodes by titration method and its application to cadmium ion determination in industrial waste water

Characteristics of cadmium iondashselective electrode made cadmium sulphide (CdS)-silver sulphide (Ag(2)S) mixture were studied. CdS-Ag(2)S mixtures were obtained by gas/solid-phase reaction between silver-cadmium mixed powder and hydrogen sulphide gas (dry method) and by ionic reaction between cadmium-silver mixed ions and sulphide ion (wet method). As a result, it was found that the CdS-Ag(2)S mixture had to be made in the condition of excess existence of sulfur and had better regulate the excess sulfur quantity minimum, for the CdS-Ag(2)S pressed membrane gave a good Nernstian response against the cadmium ion concentration change. As the best way, CdS-Ag(2)S mixture was obtained by adding sulphide ion solution to 5 mol% cadmium ion and 95 mol% silver ion mixed solution while measuring silver sulphide (Ag(2)S) electrode potential as an indicator electrode. According to the reaction was stopped when the potential variation from the initial potential in the sulphide ion solution reached at 87-116 mV which the sulphide ion concentration became 10(-3) - 10(-4) of the initial concentration, the cadmium ion membrane pressed diameter of 8 mm and thickness of 2 mm showed a Nernstian response from 10(-8) to 10(-1) M of cadmium ion concentration. Furthermore, aiming to its application for industrial waste water, masking buffer for interfering metal ions such as lead ion (Pb(2+)) and copper ion (Cu(2+)), which were possibly coexisted and to adjust total ionic strength and pH of sample was developed. The present Cd(2+) iondashselective electrode was applied to the determination of Cd(2+) in the industrial waste water. The good regression line with correlation factor of 0.984 was obtained compared with the conventional atomic absorption spectroscopy.     

Hydrogen sulphide removal from the effluents of a phosphoric acid production unit by absorption into chlorinated seawater under alkaline conditions

Atmospheric pollution during the manufacturing of Wet process Phosphoric Acid (WPA) is a critical environmental issue. The aim of this study was to examine the absorption of hydrogen sulphide (H₂S) emitted by this process into a chlorinated seawater solution under alkaline conditions. Parameters such as pH, sodium hypochlorite (NaOCl) concentration, gas flow rate, operating time and volumetric ratio of the liquid as well as gas phases (Q/Q) were investigated for their effects on H₂S absorption efficiency. It was found that sodium hypochlorite is an effective and economical H₂S oxidant. Moreover, according to the obtained results, a dose of 1 g Cl₂/l and a pH of 11 are recommended. The preferred gas flow rate in this study was equal to 15 l/min. Under these conditions, more than 98% of the hydrogen sulfide was removed, even at relatively high H₂S concentrations in industrial gas released from the plants of the Tunisian Chemical Group (GCT).     

Development of a quantification method for the analysis of malodorous sulphur compounds in gaseous industrial effluents by solid-phase microextraction and gas chromatography-pulsed flame photometric detection

A quantification method for malodorous sulphur compounds in gaseous industrial effluents using solid-phase microextraction sampling followed by gas chromatography-pulsed flame photometric detection has been developed. A comparative study showed that polydimethylsiloxane-Carboxen fibre led to sufficient sensitivity to achieve the microg m(-3) human perception levels of the five analytes studied (hydrogen sulphide, methanethiol, ethanethiol, dimethyl sulphide, dimethyl disulphide). However, this coating is known to suffer from competitive adsorption, which may lead to inaccurate quantification. Therefore, external calibration can only be used under a limited range of concentrations, which were determined from Fick's diffusion law. This approach was tested on a real gaseous sample and compared with the standard addition method. Good correlations were found for ethanethiol, dimethyl sulphide and dimethyl disulphide. However, for more volatile sulphur compounds (i.e., hydrogen sulphide and methanethiol), the easy-to-use external calibration could not be applied and standard additions had to be performed for accurate quantification.     

Production of activated carbons from biodegradable waste materials as an alternative way of their utilisation

New carbonaceous adsorbents were prepared by means of direct, physical and chemical activation of corn cobs and cherry stones as well as coffee and tobacco industry waste materials. The effect of activation method on the textural parameters, acid-base character of the surface and sorption properties toward toxic gases of the materials obtained was tested. Depending on the precursor as well as method of preparation, the final products were micro/mesoporous activated carbons of surface area reaching to 1426 m²/g, showing largely different acid-base properties of the surface. The results obtained in our study have proved that a suitable choice of the activation procedure for industrial and agricultural biodegradable waste materials permits production of cheap carbonaceous adsorbents with very high sorption capacity towards nitrogen dioxide and hydrogen sulphide reaching to 83 mg NO₂/g_ads and 215 mg H₂S/g_ads, respectively.     

Determination of sulphur species in solidified cryolite melts

Solidified cryolite melts containing a known amount of Na₂SO₄ (0?C713 mg kg^?1 SO ₄ ^2? ), Na₂S, FeS, and CdS (0?C400 mg kg^?1 S^2?) together with industrial electrolyte samples were tested for the content of sulphate and sulphide ions by ion chromatography. Added and analytically determined contents of sulphate and sulphide were compared and processed by means of linear regression analysis. It was found that the method of ion chromatography yields satisfying results (uncertainty below 1.1 %) and that it is especially suitable for the determination of low content of soluble sulphate or sulphide in solidified cryolite electrolytes. The method can be used for the estimation of insoluble sulphide content in cryolite melts as well. Results of industrial samples analysis showed that the content of sulphate and sulphide in the samples is influenced by their treatment before the analysis.     

A flow analysis system with an amperometric detector for the determination of hydrogen sulphide in waters

 A flow analysis system with an amperometric H₂S detector and a gas extraction unit as well as an integrated coulometric calibration unit is described, which allows an on-line determination of hydrogen sulphide in aquatic samples. By variation of different parameters (e.g. flow rate, gas injection volume, pH of solution) a wide dynamic working range of concentrations from 1 μmol/l H₂S to 750 μmol/l is accessible. The sampling rate is about 36 samples h⁻¹ using an average flow rate of 1.78 ml/min and a gas injection volume of 28 μl. The measuring system is designed as a portable device. In combination with the polyethylene-tube of a PTFE-underwater pump field-measurements on board are possible. Received: 16 February 1995/Revised: 5 April 1995/Accepted: 11 April 1995 Acknowledgements. This work was supported by the Bundesminister für Forschung und Technologie under the project “DYSMON II” (03F0123D) and by the Fonds der Chemischen Industrie zur F?rderung von Chemie und Biologischer Chemie. Correspondence to: P. Jeroschewski     

Gleichzeitige Bestimmung von Sulfit und Sulfid in sulfathaltigen Gemischen

Zusammenfassung Sulfit- und Sulfidschwefel werden in einer Entwicklungsapparatur nacheinander als SO₂ und H₂S ausgetrieben und nach bekannten Methoden acidimetrisch bzw. jodometrisch titriert. Zur Zersetzung der Sulfite dient 20%ige Perchlorsäure, die bei Gegenwart von HgCl₂ kein H₂S frei macht. Zur Zersetzung der Sulfide werden anschließend SnCl₂ und HCl zugefügt.

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Summary A method has been developed for the simultaneous determination of sulphite and sulphide in sulphates. The sulphites are decomposed by 20% perchloric acid in presence of mercuric chloride which prevents evolution of hydrogen sulphide. Sulphur dioxide is absorbed in alkaline hydrogen peroxide, an excess is back-titrated by acid. The sulphides are then decomposed by stannous chloride and hydrochloric acid. The hydrogen sulphide is absorbed in cadmium acetate solution and titrated with iodine.

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Wir danken der Deutschen Forschungsgemeinschaft und dem Verband der Chemischen Industrie (Fonds der Chemie) für die Förderung der Arbeit durch Sachbeihilfen sowie Frau E.-M. Rinne und Frl. H. Schirra für ihre verständnisvolle und sorgfältige Mitarbeit.     

Calibration transfer between electronic nose systems for rapid In situ measurement of pulp and paper industry emissions

Electronic nose systems when deployed in network mesh can effectively provide a low budget and onsite solution for the industrial obnoxious gaseous measurement. For accurate and identical prediction capability by all the electronic nose systems, a reliable calibration transfer model needs to be implemented in order to overcome the inherent sensor array variability. In this work, robust regression (RR) is used for calibration transfer between two electronic nose systems using a Box–Behnken (BB) design. Out of the two electronic nose systems, one was trained using industrial gas samples by four artificial neural network models, for the measurement of obnoxious odours emitted from pulp and paper industries. The emissions constitute mainly of hydrogen sulphide (H₂S), methyl mercaptan (MM), dimethyl sulphide (DMS) and dimethyl disulphide (DMDS) in different proportions. A Box–Behnken design consisting of 27 experiment sets based on synthetic gas combinations of H₂S, MM, DMS and DMDS, were conducted for calibration transfer between two identical electronic nose systems. Identical sensors on both the systems were mapped and the prediction models developed using ANN were then transferred to the second system using BB–RR methodology. The results showed successful transmission of prediction models developed for one system to other system, with the mean absolute error between the actual and predicted concentration of analytes in mg L⁻¹ after calibration transfer (on second system) being 0.076, 0.1801, 0.0329, 0.427 for DMS, DMDS, MM, H₂S respectively.     

Determination of selenium, zinc and cadmium in antidandruff shampoos by atomic spectrometry after microwave assisted sample digestion

Microwave assisted pre-treatments for atomic spectrometric determination (inductive coupled plasma-optical emission spectrometry, ICP-OES or flame atomic absorption spectrometry, FAAS) of metallic elements, usually present in antidandruff shampoos, are proposed. They are based on the digestion of the sample with HNO₃ into a closed reactor, which is irradiated at 800 W for a few minutes. Selenium was determined by ICP-OES. The limit of detection was 0.11 mg l⁻¹; the relative standard deviation (R.S.D.) for the selenium content in the samples was in the 0.6–3.6% range. The results obtained were in agreement with the label contents and the recovery of the proposed method was in the 100–106% range. Zinc and cadmium were determined by FAAS. The limit of detection for zinc determination was 0.078 mg l⁻¹; the R.S.D. for zinc contents was in the 0.8–8.6% range. A limit of detection of 0.09 mg l⁻¹ was obtained for cadmium determination; the R.S.D. for cadmium contents was in the 0.7–2.7% range. The determinations were performed after two different sample mineralization pre-treatments — dry ashing (in an electric furnace) and wet mineralization (in a microwave oven). Both methodologies provided comparable results for zinc and cadmium determination in shampoos. The proposed microwave assisted digestion procedures allow a precise and accurate determination of selenium, zinc and cadmium in commercial antidandruff shampoos, and the sample pre-treatment is less time-consuming than the classic methods.     

Optosensing of hydrogen sulphide through paper impregnated with lead acetate

Summary A flow-through optosensing method for hydrogen sulphide analysis is described, which involves reflectance measurements through optical fibres on paper impregnated with lead acetate. Levels as low as 50 ppb H₂S could be measured with high reproducibility within 10 s. The response was affected by flow rate and relative humidity, both of which were controlled during the measurement process. The method provides a sensitive real-time analysis of hydrogen sulphide and could be carried out remote from the instrumentation system.

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Schwefelwasserstoffbestimmung durch Bleiacetat-imprägniertes Papier mit Hilfe eines optischen Sensors

     

Isolation and ultramicro determination of hydrogen sulphide in air or water by use of ion-exchange resin

Summary A method is described for the ultramicro determination of hydrogen sulphide in gaseous mixtures or water, based on the sorption of hydrogen sulphide on columns of Amberlite IRA 400, followed by elution with 4M sodium hydroxide and colorimetric estimation as Methylene Blue. The method permits the rapid determination of 1–20g of hydrogen sulphide present at dilutions of 0.07–20 ppm in air or down to 0.1 ppM in water. The resin retains the sulphide for about 10 days without loss.

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Zusammenfassung Ein Verfahren zur Ultramikrobestimmung von Schwefelwasserstoff in Gasgemischen oder in Wasser wurde beschrieben. Es beruht auf der Adsorption an Amberlit IRA 400 und nachfolgender Eluierung mit 4-m Natronlauge. Schließlich wird als Methylenblau kolorimetrisch gemessen. 1 bis 20g H₂S können in Verdünnungen von 0,07 bis 20 ppm in Luft bzw. bis zu 0,1 ppM in Wasser bestimmt werden. Der Austauscher hält das Sulfid für 10 Tage ohne Verlust.

     

Removal of H2S from Exhaust Gas by Use of Alkaline Activated Carbon

The purpose of this research was to select an activated carbon and alkaline solution blend that generated the best H₂S adsorption on alkaline-activated carbon. RB₂ (activated carbon) impregnated with NaOH solution was shown to have the optimum H₂S removal efficiency. The optimum NaOH concentration was 50 mg per gram of carbon. H₂S adsorption via RB₂-NaOH₅₀ was five times that of a corresponding fresh-activated carbon. The adsorption equivalent of H₂S is nearly 1 (mol-H₂S/mol-AOH), therefore, H₂S + AOH AHS + H₂O was the major reaction. The H₂S adsorption isotherm corresponded to the Freundlich isotherm.     

Heated Slurry Sampling for the Determination of Cadmium in Food by Electrothermal Atomic Absorption Spectrometry

A heating procedure is reported with slurry sampling electrothermal atomic absorption spectrometry to improve the accuracy of cadmium determination in food. In comparison to conventional slurry sampling, the heating significantly increased cadmium recovery and improved the precision. For the optimized procedure, 25–250 mg of food were treated with 2% HNO₃ and 1% H₂O₂ with heating at 120°C for 20 min, followed by the addition of 50 µL of 10% Triton X-100, and homogenization in an ultrasonic bath prior to analysis. Tungsten and rhodium were employed as a permanent modifier with optimum pyrolysis and atomization temperatures of 500°C and 1500°C. Calibration with aqueous standards resulted in good agreement between certified or information values and measured results at the 95% confidence level. A characteristic mass of 0.8 ± 0.1 pg and a detection limit of 0.7 ng g^?1 for a 2% slurry were obtained. The method was employed for the direct determination of cadmium in food certified reference materials.     

Determination of dissolved hexavalent chromium in industrial wastewater effluents by ion chromatography and post-column derivatization with diphenylcarbazide

A proposed EPA method for the determination of dissolved hexavalent chromium in drinking water, groundwater and industrial wastewater effluents was developed using existing ion chromatographic techniques. Two solid waste matrices were briefly investigated. Aqueous samples were passed through a 0.45-micron filter and the filtrate was either (1) left unadjusted, (2) adjusted to pH 8 or (3) adjusted to pH 10 prior to analysis by ion chromatography. The method detection limits were 0.3-0.4 micrograms/l. When analyzed within 24 h, the two pH levels and the unadjusted sample yielded ca. 100% recovery of spikes. No oxidation of trivalent chromium to hexavalent chromium was observed at pH 7, 8 or 10 when aqueous samples were spiked with 50 mg/l Cr(III).     

Flow Injection Analysis of Hydrogen Peroxide,Sulfite, Formaldehyde and Hydroxymethanesulfonic Acid in Precipitation Samples

Abstract

Hydroxymethanesulfonic acid (HMSA), the reaction product of sulfite and formaldehyde plays an important part in the aqueous phase conversion of sulfite to sulfate. HMSA is fairly stable under acidic conditions and in presence of hydrogen peroxide. Sulfite is unstable under these conditions.

A flow injection set-up was developed, which allows the determination of H₂O₂, sulfite, formaldehyde and hydroxymethanesulfonic acid.

H₂O₂ analysis by amperometric detection offers the possibility of a simple, robust field instrument. The detection limit is 5μg/l and the method is linear up to 5mg/l.

Based on the 4,4-dithiodipyridine/sulfite reaction selective and sensitive spectrophotometric detections were developed for sulfite, formaldehyde and hydroxymethanesulfonic acid. The detection limit of these compounds is 50μg/l and the method is linear up to 5mg/l.

A large fraction of S(IV) is present as HMSA in fog, dew and precipitation samples in The Netherlands.     

Tandem on-line dialysis with a double and single dialyser in flow injection dialysis — Simultaneous determination of calcium and high chloride in industrial effluents

The on-line double membrane dialyser described previously was coupled in series to a single dialyser in the manifold of a flow injection system to include the determination of samples with a high chloride content simultaneously with calcium in industrial effluents from a single sample injection. 50 μl of industrial effluent samples are injected into a carrier stream and are simultaneously dialysed in the double on-line dialyser for chloride and calcium. The dialysed chloride sample zones are further directed to a second dialyser that is incorporated in series with the first dialyser. This enables laboratories to determine samples with a very high chloride content up to 60 g/l simultaneously with calcium by using an automated tandem on-line dialysis technique. The fast and reliable fully automated two-component flow injection procedure operated at a sampling frequency of 90 samples per hour and the results obtained for chloride and calcium in industrial effluents compared well with those obtained by standard methods.     

Sea-water neutralization of effluents from the industrial processing of phosphorite. A case study in the practical use of basic knowledge in analytical and marine chemistry

It is shown that the complex reactions involved in the neutralization and dilution of industrial effluents containing SiF₄ and H₂SiF₆ with brackish water can be fully elucidated with the HALTAFALL computer program. The accuracy of the calculations was verified analytically by simple potentiometric titrations     

Measurements of H2S in the Atmosphere

Swamps and tidal flats are believed to he important natural sources of atmospheric H₂S, though it is very difficult to detect the low concentrations of this trace gas above the surface of these regions. In view of this problem an air sampling device has been developed for the sampling of atmospheric H₂S with chemically impregnated filters. The sulfide generated on the filter is analyzed in a washing solution employing a very sensitive fluorescence method. The quality of the method is demonstrated by comparative calibrations. The fluorescence method is calibrated in the liquid phase with standard solutions of sulfide. Furthermore the sampling and analyzing method is calibrated together by using H₂S calibration gases. The detection limit of the method is shown to he 10ng/m³ STP. Data of test-measurements in ambient air and some results of field-measurements in the lower troposphere are presented.