How to identify the sources of oil pollution
(57) Abstract:Usage: to establish the perpetrators of unauthorized discharges of oil and petroleum products into water bodies. Essence: take samples of oil from the surface of the water and of the probable sources of pollution. Remove from them the water-soluble components, remains dissolved. As the solvent used chloroform. Using thin-layer chromatography share of oil samples for major oil fraction hydrocarbons, resins, asphaltenes and simultaneously removed from them volatile components. Measure the optical density of the eluates hydrocarbon fractions compare oil samples in the ultraviolet and infrared regions of the spectrum, and the intensity of their luminescence. Identification is carried out by the coincidence or difference of the concentrations of hydrocarbons, resins and asphaltenes in the samples, as well as relations of the optical characteristics of hydrocarbon fractions E/D, E/I, I/D, where E is the sum of the optical densities of the hydrocarbon fraction in the infrared region of the spectrum; D is the optical density of the hydrocarbon fraction in the ultraviolet region of the spectrum; I - intensity of luminescence of the hydrocarbon fraction. When Vozniknovenie spectroscopy to determine the intensity of the absorption bands of hydrocarbons, resins and asphaltenes oil samples and identify the source of contamination by coincidence or difference of the intensity ratio of the absorption bands. Effect: increase the reliability of the identification of the sources of oil pollution while reducing the complexity of their receipt. 1 C.p. f-crystals, 4 tab., 1 Il. The invention relates to the field of ecology, and is intended to establish the perpetrators of unauthorized discharges of oil and oil products in water.There is a method of identifying sources of oil pollution, including infrared and fluorescence spectroscopy, liquid and gas chromatography, including in combination with mass spectrometry (1).The disadvantages of this method are the omission of the processes of degradation of crude oil and petroleum products during their entry into water bodies, as well as the use for identification only sophisticated analytical methods that are not always available and justified from an economic point of view.Known, selected as a prototype, how to identify the sources of oil pollution (2), which take samples of oil or oil products from the oil spill on the water surface and from vozmojnom weathering under a fan and a source of UV light for 4 hours; all the analyzed samples dissolved in heptane, dried and identification carried out by the methods of spectrofluorometry (SF), high performance liquid chromatography (HPLC) and capillary gas-liquid chromatography (KHJH).The known method takes into account the processes of degradation of the oil samples by artificial weathering and exposure to UV-light simulating the solar radiation.The disadvantage of this method is that the proposed method of weathering, as, in principle, any method of artificial weathering, can not adequately reproduce the natural conditions of degradation of oil spills, as these conditions in each case will differ significantly depending on weather conditions prevailing in the area of the spill (water and air temperature, wind strength, excitement, solar radiation). Also not taken into account the processes of transformation of the composition of oil spills that occur due to the dissolution of the oil components. All this ultimately reduces the reliability of the results identification of sources of oil pollution. The disadvantage of this method include the use of only complex, requiring a high liners shall obtain more reliable results, identify sources of oil pollution by reducing the complexity of their reception.This object is achieved in that the selected oil samples from the surface of the water and of the probable sources of contamination, remove one of them water-soluble components, remains dissolved in chloroform, and then using thin-layer chromatography share of oil samples for major oil fraction hydrocarbons, resins, asphaltenes, with complete removal of volatile compounds, measure the optical density of the eluates hydrocarbon fractions compare oil samples in the ultraviolet and infrared regions of the spectrum and the intensity of their luminescence, and identification is performed according to the coincidence or difference of the concentrations of hydrocarbons, resins and asphaltenes in the samples and the ratio of the optical characteristics of hydrocarbon fractions: E/D, E/I, I/D, where
E - the sum of the optical densities of hydrocarbon fractions in the infrared region of the spectrum;
D is the optical density of the hydrocarbon fraction in the ultraviolet region of the spectrum;
I - intensity luminescence hydrocarbon fraction.With the emergence of complex, controversial issues of identity composition of the compared samples additionally using infrared spectrosco deviceroot source pollution by coincidence or difference of the intensity ratio of the absorption bands.The positive effect of the proposed method is achieved by removal of comparable oil samples volatile and water-soluble components and use for identification of the optical characteristics of the fractions of oil pollution, resistant to degradation processes.The method is as follows.Take oil samples from the spill on the water surface, as well as from possible sources of contamination. From the samples to remove water-soluble components, remains dissolved in chloroform, and then using thin-layer chromatography share of oil samples for major oil fraction hydrocarbons, resins, asphaltenes and simultaneously removed from them volatile components. Then measure the optical density of the hydrocarbon fractions of all of the compared samples in the ultraviolet (E) and infrared (D) regions of the spectrum and the intensity (I) of the luminescence of these factions, and the identification is carried out by the coincidence or difference of the concentrations of hydrocarbons, resins and asphaltenes in the samples and the ratio of the optical characteristics of hydrocarbon fractions E/D, E/I, I/dIf you need additional identification meth is stoltenow all oil samples and identify the source of contamination by coincidence or difference of the intensity ratio of the absorption bands.Identification criteria, the obtained IR method separately for hydrocarbons, resins and asphaltenes are characterized by a better reproducibility than the original samples.Example 1. The proposed method was tested in oil spills in the port of Mariupol, when the sea was discharged bilge water. A possible source could be one of two ships (t/x): "Zadonsk" or "Ray."The samples were drawn oil from Zadonsk" and "Beam" as well as from the spill on the sea surface. The samples were weighed 10 g, was added 1 l of distilled water and shaken for 10 minutes, removing the thus water-soluble fractions. Surfaced any insoluble in water, the oil samples were collected and dissolved in chloroform. Aliquots of the resulting solutions oil samples by thin-layer chromatography was divided into separate factions - hydrocarbons, resins and asphaltenes. At this stage of the analysis is the complete removal of volatile components.Identification was carried out for the ratio of concentrations between the selected oil components. The results are presented in table 1.In addition, all selected hydrocarbon fractions were measured optical density in the street is entification held against the measured optical characteristics of E/D, E/I, I/dThe measurement results of the optical characteristics of the hydrocarbons extracted from falling into the sea of oil products and of the probable sources of contamination are presented in table 2.From tables 1, 2, it follows that bilge water entered the sea from the m/V "Zadonsk", since the optical characteristics of the bilge water t/x "Beam" is dramatically different from the bilge water t/x "Zadonsk and petroleum products, selected from the spill, while among themselves they do not differ.Example 2. The method was tested 2nd time in the sea in the port of Mariupol were discharged bilge water. A possible source of contamination could be court "Stripping station-1" or "Volgo-Balt-137".Studies were carried out analogously to example 1. In tables 3 and 4 presents the results of research on the relative content of the major oil components and optical characteristics of hydrocarbon fractions isolated from falling into the sea of oil products and of the probable sources.Received identification criteria indicate that the likely source of the contamination is the vessel "Stripping station 1 as physico-chemical characteristics of its volt-137".To confirm the source of contamination were used additional criteria of identification by infrared spectra. By the method of infrared spectroscopy (IR) were measured intensity of the absorption bands separately for hydrocarbons, resins and asphaltenes studied oil samples at various frequencies and graphs: on the x - axis (frequency) at which the measured intensity of absorption bands; on the y - axis relationship of the measured intensities of the absorption bands (E) to the reference intensity of the absorption band (Erap) (drawing), where schedule 1 to the hydrocarbon oil selected from the spill, schedule 2 - hydrocarbons bilge water vessel Stripping station-1", schedule 3 - hydrocarbons bilge water vessel Volgo-Balt-137", schedule 1a - resins and asphaltenes oil selected from the spill, schedule 2a - resins and asphaltenes bilge water vessel Stripping station-1", schedule 3A - resins and asphaltenes bilge water vessel Volgo-Balt-137".In the drawing it is seen that schedules 1 and 1A coincide with schedules 2 and 2A, and schedules 3 and 3A differ significantly. The obtained results confirm the conclusion that the source of pollution of the waters of the port of Mariupol was the of more reliable results, identify sources of oil pollution by using a more simple and cost-effective ways.Sources used
1. Vogt N. B., Stoegen C. F. //HRC-Journal of high resolution chromatography. - 1992. - Vol.15. - 5. - P. 293-298.2. Ordowski, S., Latief gg System identification of oil pollution of the sea //Oceanographic aspects of the protection of the seas and oceans from chemical contaminants /Materials Uses. the scientific. proc. , Odessa, 3-6 Oct. 1988. - M., 1990. - S. 38-43, prototip. 1. How to identify the sources of oil pollution, including oil-sampling from the surface of the water and of the probable sources of contamination, removal of volatile components from the sample of likely pollution sources, the dissolution of all sampling and analysis to identify, characterized in that after the oil-sampling previously removed from them water-soluble components, remains dissolved in the solvent used chloroform, and then using thin-layer chromatography share of oil samples for major oil fraction hydrocarbons, resins, asphaltenes and simultaneously removed from them volatile components, measure the optical density of the eluates hydrocarbon fractions compare oil samples in the ultraviolet and in the infrared regions of the spectrum and the intensity of their luminescence, Gemah samples and correlation to the optical characteristics of hydrocarbon fractions E/D, E/I, I/D, where E is the sum of the optical densities of the hydrocarbon fraction in the infrared region of the spectrum; D is the optical density of the hydrocarbon fraction in the ultraviolet region of the spectrum; I - intensity of luminescence hydrocarbon fraction.2. The method according to p. 1, wherein optionally the method of infrared spectroscopy register the intensity of the absorption bands of hydrocarbons, resins and asphaltenes oil samples and identify the source of oil pollution on the coincidence or difference of the intensity ratio of the absorption bands.
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of ester perfluorinated derivative by using a chemical reaction. This reaction represents the fluorination reaction of the parent compound as a raw, the reaction of chemical conversion of fragment of ester perfluorinated derivative to yield another ester perfluorinated derivative or the interaction reaction of carboxylic acid with alcohol under condition that at least one or reagent, i. e. carboxylic acid or alcohol, represents a perfluorinated compound wherein indicated perfluorinated derivative of ester represents a compound comprising a fragment of the formula (1):
with a boiling point 400°C, not above. The reaction time for carrying out abovementioned chemical reaction is sufficient to provide the required yield of ester perfluorinated derivative and wherein this yield of ester perfluorinated compound is determined by the gas chromatography method by using a nonpolar column. Also, invention relates to a method for pyrolysis of ester perfluorinated derivative with a boiling point 400°C, not above, to yield the dissociation product wherein this product represents a derivative of acyl fluoride or ketone and wherein pyrolysis time is sufficient to provide the required degree of conversion of ester perfluorinated derivative and wherein the indicated conversion degree of ester perfluorinated derivative is determined by gas chromatography method by using a nonpolar column. Also, invention relates to a method for analysis of ester perfluorinated derivative with a boiling point 400°C, not above, that involves analysis of ester perfluorinated derivative in a sample containing ester perfluorinated derivative by gas chromatography method by using a nonpolar column wherein ester perfluorinated derivative represents compound comprising a fragment of above given formula (1).
EFFECT: improved method of synthesis.
8 cl, 1 dwg, 2 ex
FIELD: instrument engineering.
SUBSTANCE: device for generating flow of vapor-gas mixture with preset concentration of vapor has vessel partially filled with fluid, second vessel provided with branch pipes for supply and removal of gas, and vapors of fluid pipeline-leak. One of vessels is connected with gas discharge forcer; fluid vapors pipeline-leak connects both vessels. Vessel, partially filled with fluid, is mounted inside second vessel. Pipeline-line, connecting both vessels, is totally placed inside second vessel. Device is also provided with additional discharge forcer for adjusting concentration of fluid vapor in second vessel. Granulated filler is introduced into vessel partially filled with fluid. Device is also provided with gas analyzer for providing gas concentration in space of second vessel.
EFFECT: higher precision of keeping of preset concentration of vapor; improved efficiency of vapor concentration control and adjustment.
FIELD: instrument engineering.
SUBSTANCE: invention is designed for calibrating gas analyser detectors, according to which there prepared is calibration substance solution with concentration A=By/k (%) as per Henry constant value k (mg/m %) at calibration temperature and as per the specified value of calibration substance mass concentration in calibration steam/gas mixture By (mg/m). After the solution has been introduced into the vessel in quantity enough for fully saturated equilibrium calibration steam/gas mixture to appear above the solution surface, the sensor calibration is carried out by means of mixture; at that, mixture concentration is changed by means of direct proportional change of solution concentration by diluting concentrated reference solution of calibration substance with analytical accuracy up to the specified concentration value A (%). There also proposed is the device for realising this method, which includes a solution point for preparing calibration solution with analytical accuracy, vessel with thermostatic device for obtaining steam/gas mixture with constant concentration corresponding to Henry law; at that, solution point includes graduated dose metre, graduated diluter, mixer with a reducer, capacity with solvent, and reference container with reference solution, which is stabilised with a gate valve meant for multiple use of container, and vessel with thermostatic device consists of thermometre and heat-insulating cover plate with an inlet branch pipe containing a normally closed return valve and a pusher for valve opening.
EFFECT: decrease of calibration substance losses; accuracy and reproducibility of metrological performance, and meeting requirements of industrial and ecological safety.
6 cl, 2 dwg
SUBSTANCE: vapour-gas mixture source has a mixer which has connecting pieces for inlet and outlet of the vapour-gas mixture. The vapour-gas mixture source also has a diffusion pipe filled with working fluid and an auxiliary pipe designed for filling the diffusion pipe with working fluid. Part of the diffusion pipe is filled with substance which retains the working fluid. The level of working fluid in the auxiliary pipe is lower than the level of substance in the diffusion pipe. The substance which retains the working fluid used can be sand, granular material with particle size between 10 and 10000 mcm, porous substances, e.g. ceramic metal etc.
EFFECT: more accurate measurement and maintenance of concentration of the vapour-gas mixture coming out of the source, provision for constant diffusion flow of vapour of working fluid into the mixer.
11 cl, 2 dwg
SUBSTANCE: invention relates to laboratory methods of analysis and deals with method of quantitative determination of manganese, lead and nickel in bile by method of atomic-absorption analysis with atomisation in flame. Essence of method lies in the following: sampling of bile is carried out during duodenal probing, after that it is frozen, and unfrozen at room temperature, homogenisation of bile by mixing being performed already at partial soft unfreezing. After that, sampling of homogenised bile is carried out for preparation for analysis, concentrated nitric acid is introduced into it with volume ratio 1:1, mixture is kept at room temperature, then heated and further mixture is kept for not less than 2.5 hours at room temperature. In order to obtain analyte, to obtained mixture added is concentrated hydrogen peroxide in volume ratio 1:1 to volume of bile sample volume, analyte is heated, after that cooled to room temperature. After that by method of atomic-absorption spectrometry, using graduated diagram, quantitative content of particular type of metal: manganese, lead and nickel is determined in analyte.
EFFECT: invention allows increasing accuracy of quantitative determination of manganese, lead and nickel in bile.
FIELD: engines and pumps.
SUBSTANCE: proposed method is based on application of simplified model of intake of admixtures into cabin which allows for only oil decomposition products in gas turbine engine. Major portion of air samples, 95-97%, required for identification and quantitative determination of oil decomposition products, is sampled on surface from device simulating oil decomposition conditions including air temperature and pressure at point of sampling from engine compressor, and oil stay time in hot zone.
EFFECT: decreased time of in-flight experiments and that of surface analysis of samples.
1 cl, 1 ex, 1 tbl, 1 dwg
SUBSTANCE: invention relates to analytical chemistry, particularly to methods of determining benzoic acid, and describes a method for quantitative determination of benzoic acid from a methyl derivative thereof - methyl ether in aqueous matrices with determination sensitivity of 5.0·10-5 mg/cm3 with determination error of not more than 25%. The method is characterised by that quantitative determination of benzoic acid is carried out using a chromatographic method with flame-ionisation detection and includes the following steps: extraction concentration of an analyte with benzene in water samples acidified with 25% sulphuric acid solution to pH 1-3 while adding sodium chloride until a saturated solution is obtained, conducting a benzoic acid methylation reaction with diazomethane to obtain a derivative - methyl ether of benzoic acid and determining the formed methyl ether of benzoic acid by a chromatographic method with flame-ionisation detection.
EFFECT: method provides high sensitivity, selectivity and easy implementation during quantitative determination of benzoic acid in aqueous media and enables use thereof in practice in factory analytical laboratories, central laboratories of chemical companies and chemical-toxicology laboratories.
1 ex, 3 tbl
SUBSTANCE: device for preparing control gas mixtures comprises a gas mixer, at least one channel for supplying target gas to the gas mixer, at least two channels for supplying the diluent gas to the gas mixer, and the channel for output of the gas mixture from the gas mixer. And in each channel for supplying gas to the gas mixer the mass flow controller of gas and a solenoid valve are mounted successively, at least in one channel for supplying the diluent gas to the gas mixer the gas humidifier and the solenoid valve are mounted successively. In each of the channels equipped with the gas humidifier at least one bypass pipeline with the additional solenoid valve is mounted. and the output of the gas flow controller of this channel is connected to the input of the additional pipeline which output is connected to the output of the last solenoid valve, and at the input of the target gas and the input of the diluent gas at least one filter is mounted, which outputs are connected to the inputs of manually operated valves.
EFFECT: possibility of operational automated obtaining the dry or moist gas mixture, and reliable obtaining of the given values of concentrations of gas mixtures at the output of the device.
SUBSTANCE: each blood sample is analysed twice. A fresh blood sample is centrifuged at 2,000 rpm for 5 min. The samples are separated in plasma fractions and formed elements. A solid-phase plasma extraction is performed by sequential passing of 100% acetonitrile, plasma, distilled water, 50% acetonitrile solution under vacuum through a cartridge with Oasis HLB 3 cc sorbent. The cartridge with the sorbent is dried under vacuum, and 100% methylene chloride is passed through the sorbent. An aliquot portion of the produced extract is chromatographed. Producing the extract of formed elements is ensured by dispersed solid-phase extraction: by adding 100% acetonitrile thereto and agitating intensively. That is followed by adding a number of QuECHeRS salts for extraction, agitating, centrifuging for 10 minutes at 2,000 rpm; that is accompanying by forming 3 layers; an upper layer is transferred to another test tube, which contains a number of QuECHeRS salts for purification; the layers are centrifuged at 2,000 rpm; the upper layer is sampled. Plasma and formed elements extracts are analysed by Agilent 1200 liquid chromatograph with a fluorimetric detector on Zorbax column 50 mm long and having an inner diameter of 4.6 mm with Eclipse PAH C18 sorbent at column temperature 27°C; a movable phase is presented by mixed acetonitrile and water at flow rate 1.5 cm3/min and optimising elution in the gradient mode (supplying the movable phase of 60 vl % to 68 vl % of acetonitrile for 1 min, increasing 60 vl % to 68 vl % of acetonitrile for 3 min, increasing 68 vl % to 70 vl % for 0.5 min, increasing acetonitrile 70 vl % to 90 vl % for 1.5 min, increasing acetonitrile 90 vl % to 100 vl % for 4.5 min, supplying 100% acetonitrile for 1.5 min, reducing acetonitrile to 60 vl % and supplying 60% acetonitrile for 4 min to balance the column). An excitation wavelength of the fluorimetric detector makes 265 nm, and an emission wavelength makes 412 nm. A calibration chart is used to quantify benz(a)pyrene in plasma and formed elements separately, while the results are summed up.
EFFECT: invention provides high sensitivity of the method and ensures selectivity in a combination with its accessibility for routine analyses.
3 cl, 6 tbl, 1 ex
SUBSTANCE: invention relates to medicine, namely to experimental pharmacology, and can be used for quantitative determination of carnosine in tissues and physiological liquids. Determination of carnosine in biological materials is carried out by highly-selective mass spectrometry method using electrospray ionization. At that, deproteinization of blood plasma should be preliminary carried out using 10 % aqueous solution of trichloroacetic acid. Then aliquot of internal standard solution of L-alanyl-carnosine is added to deproteinizated sample. And separation of extraction products is performed at reversed-phase chromatographic column 4.6×150 mm with temperature separation of 35 °C and eluent feed rate 0.7 ml/min. Used eluent is 10 mM ammonium acetate, acidified with glacial acetic acid to pH 3.7, and mixture of acetonitrile with 10 mM ammonium acetate in ratio of 90:10, taken in ratio of 10:90, respectively. Detection of carnosine is carried out by four child ions with m/z 110.0, 156.1, 180.0, 210.1, formed as result of molecular ion carnosine disintegration with m/z 227.1. Concentration of carnosine is calculated by chromatographic peak carnosine area relation to L-alanyl-carnosine internal standard peak area.
EFFECT: invention provides highly selective and sensitive gas chromatography/mass-spectrometric method for quantitative determination of carnosine in biological substrates.
1 cl, 6 dwg, 2 tbl, 1 ex