WO2008014884A1 - Collecteur de mercure activé et procédé de détermination sélective d'espèces de mercure - Google Patents

Collecteur de mercure activé et procédé de détermination sélective d'espèces de mercure Download PDF

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Publication number
WO2008014884A1
WO2008014884A1 PCT/EP2007/006333 EP2007006333W WO2008014884A1 WO 2008014884 A1 WO2008014884 A1 WO 2008014884A1 EP 2007006333 W EP2007006333 W EP 2007006333W WO 2008014884 A1 WO2008014884 A1 WO 2008014884A1
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Prior art keywords
mercury
collector
activated
species
liquid medium
Prior art date
Application number
PCT/EP2007/006333
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German (de)
English (en)
Inventor
Michael Schuster
Kerstin Leopold
Lena Harwardt
Original Assignee
Analytik Jena Ag
Technische Universität München
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Analytik Jena Ag, Technische Universität München filed Critical Analytik Jena Ag
Priority to AU2007280776A priority Critical patent/AU2007280776A1/en
Priority to EP07786129A priority patent/EP2047233A1/fr
Publication of WO2008014884A1 publication Critical patent/WO2008014884A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1813—Specific cations in water, e.g. heavy metals

Definitions

  • the invention relates to a method for producing an activated mercury collector, an activated mercury collector obtainable by this method and a method for the selective determination of mercury species in liquid media.
  • GC gas or high performance liquid chromatography
  • HPLC high performance liquid chromatography
  • Derivatization or derivatization reaction is understood as meaning chemical reactions in which a derivative, ie a derived substance of similar structure, is formed.
  • Derivatives are substances which, instead of an atom, have another atom or a whole atomic group or in which one or more atoms / groups of atoms have been removed.
  • significant systematic errors in the determination of methylmercury may occur if derivatization with tetraethylborate as the derivatization reagent precedes.
  • IVA isotopic dilution analysis
  • a disadvantage of the cold vapor technique is that first an equilibrium between liquid and gaseous phase must be set and by a more or less incomplete phase transfer an error in the determination of the mercury species contained in the liquid phase occurs. This error is also difficult to quantify because the completeness of the phase transfer depends on a large number of parameters, such as the size of the mercury drops in the liquid medium, the temperature, the strength and duration of the inert gas flow, etc.
  • inorganic and organic mercury For the distinction of inorganic and organic mercury, it was proposed to carry out a selective reduction of the inorganic mercury to Hg 0 in a part of the sample, followed by a direct, direct measurement. Subsequently, in a second part of the sample, total mercury is measured by the method described above.
  • the chromatographic methods for the separation of all species require a great deal of work and equipment and can only achieve a determination in the ultratrace range by coupling several methods and devices.
  • the object of the invention is therefore to provide a mercury collector and a method for the determination of mercury species, in particular to provide a method for the selective determination of inorganic and organic mercury species, which overcome the disadvantages of the prior art.
  • the total mercury content of a sample can be determined in a simple and rapid manner; the sum of elemental mercury, inorganic mercury ions and organic mercury species, without the need for prior derivatization or chemical transformation of the individual mercury species.
  • the above object is further achieved by a method for the selective determination of inorganic and organic mercury species in a liquid medium, wherein A) for the determination of inorganic mercury species, the above method is performed with a non-activated mercury collector and then B) in the remaining liquid medium contained in the organic mercury species can be determined quantitatively.
  • A) for the determination of inorganic mercury species the above method is performed with a non-activated mercury collector and then B) in the remaining liquid medium contained in the organic mercury species can be determined quantitatively.
  • mercury species are understood to mean elemental mercury (hereinafter also referred to as Hg 0 ), inorganic mercury ions (essentially Hg 2 2+ and Hg 2+ ) and ionic and neutral compounds of mercury in various oxidation states, all of which are either dissolved, colloidally dissolved or undissolved.
  • Inorganic mercury species are understood to mean all of the abovementioned species which contain no Hg-C bond, ie elemental mercury and mercury ions without organic ligands.
  • Organic mercury species are understood to mean all the species mentioned which contain at least one Hg-C bond.
  • Natural waters contain mercury mainly in the form of mercury (II) ions (hereinafter also referred to as Hg 2+ ), elemental mercury (hereinafter also referred to as Hg 0 ) and mono- and dimethylmercury (hereinafter also referred to as MeHg).
  • II mercury
  • Hg 0 elemental mercury
  • MeHg mono- and dimethylmercury
  • the parallel determination of organic and inorganic mercury species and of the total mercury in liquid media is made possible.
  • the method of the invention is suitable for the determination of mercury species in natural aquatic samples, e.g. Drinking water, seawater, seawater, river water, rainwater,
  • traces of various mercury species can be deposited on a specially activated noble metal surface and thus enriched.
  • the activation of the noble metal surface is carried out according to the invention by the following cycle:
  • an activated mercury collector is obtained according to the invention.
  • Hg 0 elemental mercury
  • inorganic mercury ions especially Hg 2+ and Hg 2 2 *
  • R organic, ie carbon-containing, radical, for example an alkyl or aryl group.
  • impurities contained in the liquid medium and / or the organic residues of organic mercury species in the liquid medium serve as redox partners, and the activated surface of the mercury collector functions both as a catalyst and as a deposition partner.
  • the application of the mercury is preferably carried out by depositing elemental mercury (Hg 0 ) on the substrate surface.
  • the temperature of the substrate surface is in step a) preferably less than 100 ° C, more preferably less than 50 0 C, and most preferably 10-30 ° C.
  • an at least partial amalgamation generally takes place.
  • step b) the noble metal surface is heated at 300-1000 0 C, preferably at 500-950 0 C, more preferably at 700-900 0 C. In this case, the mercury is removed from the surface (thermodesorbed).
  • the subsequent cooling in step c) is preferably below 60 0 C, particularly preferably below 30 0 C, more preferably to 10-30 0 C and most preferably to room temperature (16-25 C C).
  • the roughness in the nanostructured area (nanorughness) of the noble metal surface is produced by the activation cycle of steps a) to c), which leads to the activation of the mercury collector.
  • step c) takes place in less than 30 minutes, preferably in less than 10 minutes and particularly preferably less than 2 minutes. It is assumed that a
  • Heating step b) is preferably carried out in less than 30 minutes, more preferably less than 10 minutes, and most preferably less than 2 minutes, so that the noble metal surface is not kept at high temperature for too long, which would favor surface restructuring.
  • a preferred embodiment of the invention provides that the steps a) to c) are repeated in order to increase the activation of the noble metal surface. Particularly preferably, the steps a) to c) are repeated at least twice and even more preferably repeated three to five times.
  • the surface of the substrate preferably comprises gold or a gold alloy.
  • gold or a gold alloy With these metals, particularly active mercury collectors can be produced.
  • gold alloys those with other noble metals are preferred, for example, ruthenium, rhodium, palladium, osmium, iridium, platinum and silver. Particularly preferred are gold-platinum alloys.
  • the substrate used to make the activated mercury collector may be of noble metal or may comprise a support coated with noble metal.
  • the suitable, preferred and particularly preferred noble metals described above are also suitable for the substrate, preferred and particularly preferred.
  • Substrate and support may be in various forms, with those forms having a high surface area per volume being preferred, for example a grid, a mesh, a wire mesh, a fiber aggregate, a particle aggregate or a powder.
  • the substrate is preferably a grid of gold or a gold alloy or a carrier coated with gold or a gold alloy.
  • the carrier can be, for example, a particle accumulation or a powder, which are coated with the noble metal, in particular gold or a gold alloy.
  • the support comprises a zeolite or graphite, which are characterized by a large active surface area.
  • the invention further relates to an activated mercury collector, which is obtainable by the method described above.
  • the activated mercury collector comprises a substrate having a surface containing noble metal and having passed through the above-described activation cycle with steps a) to d).
  • the surface of the mercury collector preferably has a roughness in the nanostructure area (nanoroughness). Further, it is preferred that the surface of the activated mercury collector consists of gold or a gold alloy, in particular a gold-platinum alloy.
  • the invention relates to the use of the activated mercury collector for the determination of traces of mercury in a liquid medium.
  • traces of elemental mercury from a liquid medium can be deposited quantitatively on a precious metal surface, in particular a gold-platinum surface, which is the described activation cycle has not gone through, and can be elemental mercury so separated from other dissolved mercury species.
  • the invention therefore relates to a method for determining traces of mercury in a liquid medium, comprising the steps of a) contacting the liquid medium with a mercury collector comprising a substrate having a surface containing precious metal, b) washing and drying the surface of the mercury collector c) releasing the mercury bound to the surface by eluting or heating the surface, and d) quantitating the released mercury.
  • a mercury collector an activated or an unactivated mercury collector can be used.
  • a non-activated mercury collector means a mercury collector comprising a substrate which has a surface which contains precious metals and has not passed through the activation cycle described above with steps a) to d).
  • the elemental mercury contained in the liquid medium can be selectively determined, since only this is deposited on the non-activated mercury collector.
  • no equilibrium between liquid and gaseous phase must be set so that the invention
  • Mercury collector preferably comprises gold or a gold alloy as precious metal. Particularly preferred is gold.
  • step a the mercury collector is introduced into a stream of the liquid medium, which takes place within a short time, an almost complete deposition of elemental mercury.
  • a volume flow of 1.5 to 15 ml / min is preferred.
  • the washing and / or elution can be carried out in the flow stream process.
  • the flow stream process can be carried out continuously or batchwise.
  • the activated or non-activated mercury collector can be used in the fluid flow process in the form of a wound-up network, whereby a particularly effective flow of the mercury collector and thus rapid quantitative separation can be achieved.
  • a reducing agent can be added to the liquid medium before contacting the liquid medium with the mercury collector (step a)) have proven mild reducing agents, which are understood as reducing agents which selectively reduce inorganic mercury ions, but not organic mercury species to elemental mercury, for example tin (II) salts, hydrochloric acid, ascorbic acid, citric acid, formaldehyde, hydroxylamine and formic acid, especially in the form of aqueous Solutions. Preference is given to aqueous solutions having a concentration of 2 to 5% by weight.
  • the reduction preferably takes place in a temperature range from 0 to 100 ° C., in particular from 20 to 80 ° C. This results in the reduction of the inorganic mercury ions, in particular Hg 2+ and Hg 2 2+ , to elemental mercury, which can then be deposited on the non-activated mercury collector in the method described above.
  • Dissolved inorganic mercury species (mainly Hg 2+ ) are quantitatively converted to elemental mercury with the mild reducing agents mentioned above (reaction equation I), with organic mercury species not undergoing a reaction (reaction equation II).
  • R alkyl, e.g. Methyl, ethyl, phenyl
  • Embodiment of the activated mercury collector used.
  • the mercury collector in step b For washing the mercury collector in step b), it is expediently rinsed with water, an aqueous solution or an organic solvent in order to remove any impurities. Preference is given to rinsing with ultrapure water, slightly acidified water, electrolyte-containing water, acetone, ethanol, methanol or a complexing agent-containing solution.
  • an inert gas stream is preferably passed over the surface of the mercury collector, for example an argon or nitrogen stream.
  • the inert gas stream and / or the Mercury collector can be heated, preferably up to 150 ° C, more preferably up to 120 0 C.
  • the release of the mercury bound to the surface in step c) can be effected by elution or heating.
  • elution complexing or oxidizing solutions can be used, by which the deposited mercury is brought into solution (chemisorption).
  • the released mercury can then be measured immediately or redeposited and then quantified.
  • heating the surface of the mercury collector or heating the entire mercury collector the deposited mercury is thermodesorbed. This can be recorded by means of a gas or liquid flow and fed to a meter, eg an AFS or AAS measurement.
  • the temperature in the heating step depends inter alia on the nature of the noble metal and is preferably 100-1000 ° C., more preferably 300-900 ° C.
  • the present invention also relates to a method for the selective determination of inorganic and organic mercury species in a liquid medium, wherein for the determination of inorganic mercury species, the method described above for the determination of mercury traces in a liquid medium is carried out and then the organic mercury contained in the remaining liquid medium - be determined quantitatively.
  • the method for the selective determination of inorganic and organic mercury species in a liquid medium thus comprises the steps
  • A) for the determination of inorganic mercury species a) contacting the liquid medium with a non-activated mercury collector, comprising a substrate having a surface containing precious metal, b) washing and drying the surface of the mercury collector, c) releasing the surface-bound Mercury by elution or heating of the surface, and d) quantitative determination of the released mercury,
  • a reducing agent is added to the liquid medium for common detection of elemental mercury and inorganic mercury ions prior to step a).
  • the determination of the organic mercury species in step B) can be carried out by conventional methods, for example adding an oxidizing agent to the liquid medium, then excess oxidizing agent is optionally subsequently destroyed with a mild reducing agent, for example hydroxylamine, and the inorganic mercury species generated by oxidation, in particular Hg 2+ , can be quantitatively determined by known methods of the prior art, for example by atomic fluorescence spectrometry, atomic absorption spectrometry or mass spectrometry.
  • a reducing agent may be added to reduce the inorganic mercury species produced from the organic mercury species to elemental mercury. These can then be quantified, preferably by the method described above using the non-activated or activated mercury collector.
  • step B) of the above-described method for the selective determination of inorganic and organic mercury species in a liquid medium preferably comprises the steps
  • the method for the selective determination of different mercury species and of total mercury is subdivided into the sub-steps, which are explained in more detail below, and which can be used in different orders or only one part for analysis as required.
  • the mercury collector (activated or not activated) is also abbreviated to collector.
  • inorganic mercury species to elemental mercury:
  • suitable mild reducing agents such as tin (II) salt solution (eg 2 wt .-% SnCl 2 ), aqueous hydrochloric acid solution (eg 5 wt .-% HCl) or aqueous ascorbic acid (eg Wt% ascorbic acid)
  • tin (II) salt solution eg 2 wt .-% SnCl 2
  • aqueous hydrochloric acid solution eg 5 wt .-% HCl
  • aqueous ascorbic acid eg Wt% ascorbic acid
  • the Hg 0 contained in the solution is adsorbed and / or amalgamated by contact with a suitable surface, such as a gold-platinum surface.
  • the separation and enrichment can in the temperature range of 0-100 0 C, preferably in
  • Range of 20-80 0 C take place. It can be batched or integrated online into a flow system by passing the sample over the surface at a volumetric flow in the range of typically 1.5-15 ml min -1 .
  • Separation of the inorganic mercury is referred to below as a selective or non-activated collector.
  • This step can be described schematically in the following way:
  • the Hg species contained in the solution are adsorbed and / or amalgamated by contact with a suitable surface, such as a pretreated, activated gold-platinum surface.
  • a suitable surface such as a pretreated, activated gold-platinum surface.
  • the separation and enrichment may be in the temperature range of 0-100 C. C., preferably in the range of 20-80 0 C. It may be batched or integrated into a flow system online by passing the sample over the surface at a volumetric flow in the range of typically 1.5 - 15 ml min -1 Mercury is referred to below as an activated collector.
  • organic mercury species remaining in solution can either be destroyed (eg oxidatively by addition of 1-10 wt.% BrCl solution, the excess of which is mixed with a hydroxylamine solution of 0.1 wt. % is rendered harmless) and then their concentration are determined by known methods with or without prior enrichment (eg AFS, AAS) or they are measured directly by suitable known methods (eg mass spectrometry).
  • AFS oxidatively by addition of 1-10 wt.% BrCl solution, the excess of which is mixed with a hydroxylamine solution of 0.1 wt. % is rendered harmless
  • the organic mercury species remaining in solution can be enriched on an activated surface.
  • Rinsing the Collector (s) The arrangement for separating the inorganic Hg is treated with a suitable liquid medium such as e.g. ultrapure water, slightly acidified water, electrolyte-containing water, acetone, ethanol, methanol, or a complexing-containing solution.
  • a suitable liquid medium such as e.g. ultrapure water, slightly acidified water, electrolyte-containing water, acetone, ethanol, methanol, or a complexing-containing solution.
  • Drying of the collector (s) The arrangement for the separation of Hg is passed through with a suitable gaseous medium, such as argon or nitrogen, and dried.
  • a suitable gaseous medium such as argon or nitrogen
  • the gas can be used in a temperature range of 0-150 0 C, preferably between 20-120 ° C.
  • Thermodesorption of mercury The enriched in the collectors Hg is released by heating the collector again as Hg 0 and can be in a gas or Liquid flow are absorbed.
  • the collector is heated to a temperature in the range of 100-1000 0 C for this purpose.
  • Chemisorption of Mercury The Hg enriched in the collectors is purified by elution with suitable solutions, e.g. releasing complexing and / or oxidizing solutions.
  • thermodesorbed mercury The released Hg 0 can be fed directly by means of a gas flow to a measuring device (eg AFS or AAS measurement) or re-enriched and then measured.
  • a measuring device eg AFS or AAS measurement
  • Measurement of chemisorbed mercury The released Hg can either be redeposited on an activated gold surface and measured after thermodisorption or, after reduction to Hg 0 by means of a gas flow, fed directly to a measuring device (eg AFS or AAS measurement) or re-enriched and then measured become.
  • a measuring device eg AFS or AAS measurement
  • the advantage of the method according to the invention is the selective separation of different mercury species from a solution on a noble metal surface, which is used for separation and subsequent analysis.
  • the first part of the process the selective reduction of inorganic mercury species to elemental mercury, may also be omitted and the method used to determine dissolved elemental mercury already present in the sample.
  • the device which can be provided as an accessory for a complete analyzer (eg online device), according to an embodiment of the invention consists of a flow injection system, which includes, inter alia, a Q ⁇ arzglasrohr and a gold or a gold-platinum network and the rinsing, the Drying and heating included.
  • a flow injection system which includes, inter alia, a Q ⁇ arzglasrohr and a gold or a gold-platinum network and the rinsing, the Drying and heating included.
  • other glass-like and / or inert materials such as, for example, ceramic, glassy carbon, metals, plexiglass or plastics, as well as materials coated with inert materials, may also be used instead of quartz glass, depending on the temperature range and temperature resistance.
  • the flow system is coupled to an atomic fluorescence spectrometer (AFS), which enables the determination of mercury in very low concentrations.
  • AFS atomic fluorescence spectrometer
  • the invention also includes the coupling with other analytical methods, such as atomic absorption spectrometry, atomic emission spectrometry or mass spectrometry.
  • a methylmercury standard solution is freshly prepared by dissolving methyl mercuric chloride in ultra-pure water and diluted to a concentration of 10 ng Hg I -1.
  • the content of elemental mercury is determined, as well as the inorganic and total mercury after addition of tin (II) chloride solution (2 wt .-%).
  • tin (II) chloride solution 2 wt .-%).
  • tin (II) chloride solution 2 wt .-%).
  • a part of the solution was admixed with a BrCl solution (0.5% by volume in 0.5% by volume HCl) for the oxidative decomposition of the Hg species.
  • the excess was reacted after 12 h with hydroxylamine solution (0.06 wt .-%) and then measured by standard cold vapor technique of Hg content.
  • FIG. It has been shown that methylmercury does not react with the reducing agent tin (II) chloride solution
  • Hg 0 standard solutions of different concentrations are prepared and examined for their Hg content before and after passing through the non-activated (selective) mercury collector (with gold surface).
  • the selective collector no measurement signal appears in the AFS measurement (all Hg 0 from the solution was separated), while without the collector, the measurement signals increase in accordance with the mercury concentration. The result is shown in FIG. The deposited mercury is released again by heating the collector and also measured. These signals also increase in accordance with the Hg concentrations of the starting solutions.
  • a methylmercury standard solution is made fresh by dissolving methylmercuric chloride in ultrapure water and diluted to a concentration of 10 ng Hg I -1 The solution is tested for its Hg content before and after passing (passing through) the non-activated mercury collector. In this case, methylmercury is not separated from the solution at the selective collector according to Example 2, since both with and without the use of the collector give similar readings in the solution. The result is shown in FIG.
  • Methylmercury standard solutions of different concentrations are prepared fresh in ultrapure water. A specific volume of each solution will be activated over the
  • FIGS. 5a and 5b show an exemplary embodiment of the mercury collector according to the invention and FIG. 6 shows an exemplary flow system.
  • a few milliliters of a seawater sample (see Fig. 6 "Sample") contains the inorganic and organic mercury species in a concentration of 0.1-100 ng I “1 , in particular in the range of 1- 20 ng l “ 1 (volume flow 7 ml min "1 ), at 70 0 C first in the flow system with stannous chloride solution (2 wt .-% SnCl 2 , volume flow 2.5 ml min " 1 , see Fig. 6 "selective reducing agent”) are added (see. FIG.
  • the organic mercury species remaining in the solution are mixed with a bromine chloride solution (BrCl 4% by weight, volume flow 2.5 ml min -1 , cf., FIG. 6 "Oxidizing agent for decomposing the organyls") (compare FIG ”) and so oxidatively destroyed (see Fig. 6" RC2 ").
  • the excess oxidizing agent is mixed with a hydroxylamine solution (0.1% by weight, volume flow 2.5 ml min -1 , see Fig. 6 "Auxiliary reagent") (see Fig. 6 "T3") and harmless (See Fig. 6 "RC3".) Thereafter, the solution for measuring mercury is transported to a CV-AFS.
  • the collector is first rinsed with ultrapure water (volume flow 15 ml min '1 , rinsing solution, see Fig. 6 "T4") and then with argon (volume flow 250 ml min “1 , see Fig. 6" carrier gas "; Fig. 6 "T4") dried. Thereafter, the amalgamated mercury is thermally desorbed at a temperature in the range of 350-1000 ° C.
  • the heating of the collector is achieved by applying a voltage (400 V) to a heating wire, which is mounted as a spiral around the collector.
  • An argon gas stream (volume flow 250 ml min '1 , see Fig.
  • carrier gas transports the mercury vapor via a droplet separator made of quartz glass and a drying section (25 cm water-permeable membrane tube, see Fig. 6 "membrane for dehumidification”) to the measuring cuvette AFS device in which the mercury measurement takes place.

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Abstract

L'invention concerne un procédé de fabrication d'un collecteur de mercure activé, comprenant les étapes suivantes : a) dépôt de mercure sur une surface d'un substrat comprenant un métal précieux, b) chauffage de la surface à 300 - 1000 °C, c) refroidissement de la surface en dessous de 100 °C, d) éventuellement répétition des étapes a) à c). L'invention concerne en outre un collecteur de mercure activé obtenu selon ce procédé et un procédé de détermination sélective d'espèces de mercure dans un milieu liquide.
PCT/EP2007/006333 2006-08-02 2007-07-17 Collecteur de mercure activé et procédé de détermination sélective d'espèces de mercure WO2008014884A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2007280776A AU2007280776A1 (en) 2006-08-02 2007-07-17 Activated mercury collector and method for the selective determination of mercury species
EP07786129A EP2047233A1 (fr) 2006-08-02 2007-07-17 Collecteur de mercure activé et procédé de détermination sélective d'espèces de mercure

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DE102006035959 2006-08-02
DE102006035959.3 2006-08-02

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CN112326573A (zh) * 2020-11-03 2021-02-05 广西中检食品检测有限公司 直接测汞仪快速测定调味品中汞含量的方法
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US11198922B1 (en) 2020-10-29 2021-12-14 Mercury Clean Up, LLC Mercury collection system
WO2022093232A1 (fr) * 2020-10-29 2022-05-05 Mercury Clean Up, LLC Système de collecte de mercure
CN112326573A (zh) * 2020-11-03 2021-02-05 广西中检食品检测有限公司 直接测汞仪快速测定调味品中汞含量的方法
CN112326573B (zh) * 2020-11-03 2024-03-08 广西中检食品检测有限公司 直接测汞仪快速测定调味品中汞含量的方法

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