Pneumatoamperometric determination of chlorine in water

Free chlorine in water can be determined by acidifying the water sample, purging it with nitrogen and determining the chlorine present in the nitrogen stream with a gold porous electrode. The current response of gold porous electrode is related to the concentration of free chlorine by using a calibration curve. This pneumatoamperometric method gives results fully comparable to the standard o-toluidine photometric method used for water supplies. It is uninfluenced by the presence of other dissolved oxidants and requires only one milliliter of sample.     

Pneumatoamperometric determination of sulfur dioxide in air on ppb level

A simple device for the determination of sulfur dioxide at ppb concentrations in air is described. The device is composed of an enrichment unit operating continuously on the basis of gas extraction into polydisperse aerosol of a liquid transferring sulfur dioxide from liter amount of air into microliter amount of liquid. The analyte is determined pneumatoamperically from the concentrate on a gold-plated porous Teflon electrode. The detection limit is 0.3 ppb (v), i.e. 0.87 microgram/m3 of sulfur dioxide, the linear range covers several orders of magnitude. The analytical response is obtained few tenths of seconds after the gas contaminated with sulfur dioxide has entered the enrichment unit.     

Use of neutron activation analysis in determination of total organic chlorine and bromine

Neutron activation analysis is practically the only high-sensitivy element-selective detection method for chlorine, bromine and iodine. This method is just ideal for organic halogen determination after separation of organically bound species from inorganic. In recent years we have analysed organic chlorine and bromine from thousands of different kind of samples with different separation methods. For water samples we have used activated-carbon adsorption and for solid samples mostly propanone or combined alkaline/propanone extraction before activated-carbon adsorption. Inorganic chlorides were removed from the carbon by nitrate wash. The detection limits for total organic chlorine and bromine are 5 and 0.5 g/l for water (sample size 100 ml) and 0.3 and 0.1 g/g dry weight (sample size 1 g) for sediment.     

A flow injection-ETAAS system for the on-line determination of total and dissolved silica in waters

In this work total (Si-tot) and ‘soluble’ or reactive (Si-sol) concentrations of silicon in natural and tap waters were sequentially determined by electrothermal atomic absorption spectrometry (ETAAS). First, samples were on-line diluted based on the merging-zone principle in order to allow the determination of Si-tot within the 300–1000 μgSi l⁻¹ range. After the dilution process, a sub-sample was collected in the capillary of a sampling arm assembly (SAA). Thereafter, samples were subject to a precipitation/dissolution process in order to allow the determination of Si-sol within the 280–850 μgSi l⁻¹. Si-sol was precipitated with ammonium chloride and collected on the walls of a knotted coil. The precipitate was dissolved with ammonium molybdate in an acidic medium (HNO₃) and a sub-sample was then collected in the SAA. In both cases, 10 μl volumes of the sub-sample were injected into the atomizer with the previous introduction of 20 ng of Eu as chemical modifier (10 μl) by the spectrometer autosampler. The recovery values obtained with natural waters spiked samples were over 46% and the agreement between observed and certified samples values was good. The proportion of Si-sol in comparison with the Si-tot was high (85–95%) in most natural waters. The precision of the method was 2.4–3.5 and 4.5–6.2% (n=10) for the determination of Si-tot and Si-sol, respectively.     

Automatic method for the determination of ortho-phosphate and total dissolved phosphorus in the marine environment

Summary An automatic method for the determination of ortho-phosphate in seawater is described. It is based on the original molybdenum blue method and is very sensitive because of the very small dilution of samples by reagents. An all-glass reaction manifold is proposed, the use of plastic material should be avoided as far as possible. The described method may also be used in a slightly modified version for the determination of total dissolved phosphorus, when samples are first digested with peroxidisulfate. Orthophosphate and total dissolved phosphorus can be determined exactly in the concentration range from 0.01–5 g at P/l with a sampling frequency of 30 h^–1.

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Automatische Methode zur Bestimmung von ortho-Phosphat und gelöstem Gesamt-Phosphor in Meerwasser

Zusammenfassung Für die Bestimmung von ortho-Phosphat in Seewasser wird eine automatische Methode beschrieben, die auf der üblichen Molybdänblaumethode basiert und sehr empfindlich ist, weil die Proben mit einer sehr geringen Menge Reagenz verdünnt werden. Für die Reaktionseinheit wird ein Allglassystem vorgeschlagen, der Einsatz von Plastikmaterial sollte weitgehend vermieden werden. Die beschriebene Methode ist in leicht modifizierter Form auch für die Bestimmung von gelöstem Gesamt-Phosphor geeignet, wenn die Proben zuvor mit Peroxodisulfat aufgeschlossen werden. Die Methode liefert bei einer Probenfrequenz von 30 h^–1 für ortho-Phosphat und gelösten Gesamt-Phosphor genaue Ergebnisse im Bereich von 0,01–5 g at P/1.

     

Automatic methods for the determination of total dissolved and particulate carbohydrates in the marine environment

Summary The methods recommended for the determination of total dissolved and particulate carbohydrates in the marine environment are based on the l-tryptophan/sulfuric acid reaction. Automatic measurements are performed with a Technicon AutoAnalyzer II. Glucose is used for the calibration procedure. Interfering nitrate and nitrite are also measured with a Technicon AutoAnalyzer II; the values are subtracted from the total reading of the carbohydrate analyzer after calibration. Particulate carbohydrates are measured after sulfuric acid digestion of the residue on glassfiber filters. Both methods permit total carbohydrates to be determined exactly in the concentration range from 0.1–30 mol/l.

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Automatische Methoden zur Bestimmung von gelöstem und partikulärem Gesamt-Kohlenhydrat in Meerwasser

Zusammenfassung Die für die Bestimmung gelösten und partikulären Gesamt-Kohlenhydrats in Seewasser empfohlenen Methoden basieren beide auf der l-TryptophanSchwefelsäure-Reaktion. Die Messungen erfolgen automatisch im Technicon AutoAnalyzer II. Zur Eichung wird Glucose benutzt. Störendes Nitrat und Nitrit werden ebenfalls mit einem Technicon AutoAnalyzer II gemessen; die entsprechenden Werte werden nach Eichung vom Gesamtsignal des Zuckeranalysators abgezogen. Partikuläre Kohlenhydrate werden nach Aufschluß des Rückstandes auf Glasfaserfiltern mit Schwefelsäure gemessen. Beide Methoden liefern genaue Ergebnisse im Bereich von 0.1–30 mol/l.

     

A problem in the spectrophotometric determination of dissolved total phosphorus in brackish anoxic waters

When dissolved total phosphorus in anoxic brackish waters was determined spectrophotometrically by the heteropoly molybdenum blue method after oxidation with potassium peroxodisulfate, negative dissolved organic phosphorus contents were obtained from the differences between the total phosphorus and inorganic phosphorus contents. A major cause of this inconsistency is coprecipitation of phosphate with the colloidal hydrated iron(III) oxide produced fro miron in these waters, or the formation of iron(III) phosphate during the oxidation process. The problem can be avoided by oxidation with nitric and perchloric acids.     

The use of tungsten trioxide in the coulometric determination of total chlorine in organic and inorganic materials

Samples are placed on tungsten trioxide in a platinum boat for combustion or pyrolysis. Moistened oxygen is used as the combustion and carrier gas. The hydrochloric acid formed is titrated with electrolytically generated silver ions. Coals, spent catalysts, aqueous solutions and other organic and inorganic substances with chlorine contents in the range of 1 mg kg^-1 up to several percent can be analysed reproducibly.     

Liquid chromatographic determination of the total available free and intrachain lysine in various foods

A method for the quantitative determination of the total available lysine in various foods is developed. The method is based on the reaction of the amino groups on the lysine molecule with fluorodinitrobenzene and is capable of furnishing simultaneous determination of the available intrachain lysine (known as N-epsilon-[2,4-dinitrophenyl]-L-lysine) or the available free and/or N-terminal lysine (known as N,N'-di-[2,4-dinitrophenyl]-L-lysine). Optimum conditions for separation and quantitation are studied. The results show the proposed method to be both accurate and precise and suitable for food samples containing hydrolyzed proteins.     

Determination of total chlorine in waste oil

Summary A simple method has been developed to determine the concentration of organic chlorine in waste oil. The determination is based on the conversion of organic chlorine to inorganic chloride by reaction with sodium biphenyl followed by extraction with nitric acid and a mixture of nitric acid and water. The concentration of chloride is determined by direct potentiometry with an ion-selective electrode. The limit of determination amounts to 3·10^–5 mol·l^–1 chloride ions with a standard deviation of 3.5%. Different samples of waste oil have been analyzed and the results have been compared to those obtained by combustion in a H₂/O₂ flame followed by potentiometric titration with silver nitrate.     

A semi-automatic alkaline peroxodisulphate method for the routine determination of total dissolved nitrogen in sea water

Nydahl's method for the determination of dissolved organic nitrogen (DON) in distilled water has been modified for the determination of total dissolved nitrogen (TDN) in sea water. Samples (9 cm³) are digested batch-wise with alkaline potassium peroxodisulphate solution. An improved buffering system permits the automatic measurement of the nitrate formed, and allows the analysis of 50–80 samples per day. DON may be determined as the difference between TDN and the sum of inorganic nitrogen species. The standard deviation of TDN determinations is 0.7 μg N dm^-3 at about 15 μg TDN dm^-3. The method is applied to a range of samples including tanker ballast water, oil platform production water, and zooplankton.     

On the determination of total dissolved tin in natural waters by direct hydride generation and non-dispersive atomic-fluorescence spectrometry

The analytical response of inorganic tin and of eleven organotin compounds of the type R(n)SnX(4-)(n) (with n = 1, 2, 3 and R = methyl, ethyl, butyl and phenyl) was compared for direct hydride generation with non-dispersive atomic fluorescence detection. Most of these compounds showed behaviour resembling that of inorganic tin, with the exception of tributyltin and the phenyltin compounds. A simple pretreatment with 10(-3)M bromine and 0.033M nitric acid at 70 degrees for 60 niin prevents any risk of underestimation and the total dissolved tin in natural waters can be determined with recoveries better than 90%, with inorganic tin as calibration standard.     

New colorimetric reagents for determination of trace amounts of oxidants and reductants

The mixed-ligand complexes H[Fe(phen)(CN)(4)] and K(2)[Fe(phen)(CN)(4)] (where phen represents 1,10-phenanthroline) have been found useful as colorimetric reagents for trace determination of reductants and oxidants. Their properties and some representative applications are described.     

Radiometric determination of ionic chlorine and oxygen in water

Two portable devices for the radiometric analysis of industrial water are described. Chlorides are precipitated by a known volume of standard silver nitrate labelled with^110mAg; the decrease of activity is proportional to the amount of ionic chlorine. Determination of dissolved oxygen is achieved by dissolution of radioactive thallium, and the activity of the effluent is directly related to the concentration of oxygen.     

Flow-injection spectrophotometric determination of residual free chlorine and chloramine

2,4-Dinitrophenylhydrazine has been suggested as a new reagent for the flow-injection spectrophotometric determination of residual chlorine based on its oxidation to 2,4-dinitrophenyldiazonium ion. The measurement of the decrease in colour intensity under reversed flow-injection (reagent injection) conditions has been used for the determination of 0.1–10 mg/l Cl present as free or combined chlorine, and for its speciation. The limit of detection was 0.05 mg/l Cl. Copper (II), iron (III) and many other ions have been found not to vitiate the results.     

The capacity and mechanisms of various oxidants on regulating the redox function of ZVI

It is well known that zero-valent iron(ZVI) could catalyze the oxidation of various oxidants to realize the rapid oxidation removal of pollutants. However, in this study, we found that the addition of different oxidants could regulate the redox function of ZVI system. In three different co-treatment systems, the effects of different oxidizers(peroxymonosulfate(PMS), persulfate(PDS), hydrogen peroxide(H_2O_2))dosages on the ratios of oxidative degradation rate and reductive degradation rate of p-nitrophenol(PNP)were studied. The effect of the H~+ released from oxidizers and the generated reactive oxygen species(ROS) in ZVI/PMS, ZVI/PDS, ZVI/H_2O_2 systems were detailed discussed. Especially, the contribution of generated ROS for reductive degradation of PNP was quantified in the ZVI/H_2O_2 system. Based on the results of TOC removal, UV–vis absorption spectra, and intermediates concentration curves, it was found that the degradation of PNP changed from reduction to oxidation with the increase of oxidant proportion.When the molar ratio of ZVI to oxidizer equal to 100, PNP was mainly degraded by reduction accompanied by slight oxidation. Combined with the results of SEM-EDS and XPS, it was confirmed that the enhanced degradation of PNP under the addition of oxidant was mainly related to the generated ROS,the additional H~+, and the corrosion products of ZVI.     

Coulometric determination of dissolved oxygen in water

The oxygen content of air-saturated distilled water has been determined at between 10 and 40 degrees by using a controlled-potential coulometric method based on an earlier published method for the iodometric determination of nitrite. The maximum error for the determinations was +/- 0.3% over the whole range, and the time of analysis about 3 min. An equation is given for the solubility in the measured range, and some thermodynamic functions are calculated.