CN102507763A - Method for determining content of methylmercury in fish oil - Google Patents
Method for determining content of methylmercury in fish oil Download PDFInfo
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Abstract
The invention discloses a method for determining a content of methylmercury in fish oil, which comprises extracting a sample, performing chromatographic analysis, performing atomic fluorescence analysis, performing data acquisition on intensities of fluorescence emitted from mercury atoms by data processing software, and listing the collected data to conveniently and accurately detect the content of methylmercury in the fish oil. The invention has advantages that it simultaneously employs the chromatographic analysis and atomic fluorescence analysis, and carries out selection of a mobile phase, and control of the concentration and flow rate of the mobile phase in the chromatographic analysis, and selection of a reductant and an oxidant and control of the lamp current and carrier gas in the atomic fluorescence analysis, thus the content of methylmercury in the fish oil is determined rapidly and conveniently. In addition, the method has low reagent consumption, short analysis period, good stability and high accuracy, and is very practical.
Description
Technical field
The present invention relates to a kind of method of measuring methyl mercury content in the fish oil.
Background technology
Fish oil has other drug, the irreplaceable effect of health products aspect prevention human body diseases and the body-care; Its principal ingredient EPA has the cardiovascular effect of cleaning of dredging; DHA is that brain cell forms the indispensable material of growth, so fish oil has become dark popular health products.Yet, contain a large amount of methyl mercuries in some marine fishes, and methyl mercury is fat-soluble higher, is present in easily in the fish oil that extracts because marine pollution is serious day by day.Methyl mercury can be smoothly through the brain blood barrier of human body, people's nerve center is directly produced destruction, therefore be necessary fish oil is carried out the detection of methyl mercury, guarantee the edible safety of fish oil health products.
In the prior art; There is a kind of application number to disclose a kind of method that is used to detect organomercury compound for the Chinese invention patent that the CN200710177665.X name is called " a kind of method and equipment thereof that is used to separate and detect organo-mercuric compound content "; May further comprise the steps: at first the organic mercury in the testing sample is extracted; And in high performance liquid chromatography, separate; Moving phase in the high performance liquid chromatography comprises one or several in 2 mercapto ethanol, lower fatty acid and the lower aliphatic hydrochlorate, makes the chromatographic column effluent issue biochemical reaction at ultra violet lamp, and reaction solution is mixed with inert gas; Gas-liquid mixture is separated through gas-liquid separator; Detect to separate the gas phase of back sample through AFS and make high-efficient liquid phase chromatogram, according to organic mercury concentration with go out the typical curve between the peak area, go out the organic mercury concentration in the testing sample through the said calculated by peak area that goes out of gas phase in high performance liquid chromatography of separating the back sample.The invention provides a kind of method that can the multiple organic mercury in the testing sample successfully be carried out separation detection.But this invention can not determine the content of methyl mercury in the fish oil rapidly and accurately, determining whether and can directly eat, and can directly not produce destruction to people's nerve center, so this invention awaits further to improve.
Summary of the invention
Technical matters to be solved by this invention is to above-mentioned prior art present situation a kind of method of measuring methyl mercury content in the fish oil that a kind of ability is quick, easy, accuracy is high to be provided.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the method for methyl mercury content in this mensuration fish oil is characterized in that: may further comprise the steps:
One, sample extraction: taking by weighing volume is A fish oil sample, and in its container of packing into, in container, adding volume is (9-11) %KOH+ (0.9-1.1) % thiocarbamide of B; Stirred 18-25 minute; Again the solution that stirs is put into hydro-extractor and carry out centrifugally, add volume then, stirred 9-15 minute for C concentration is that the HCl solution of 19-21% advances neutralization; With the neutralization after solution put into hydro-extractor centrifugal after; Getting supernatant liquor, is the filtering membrane filtration of 0.4-0.5 micron with supernatant through filtering holes again, promptly is mixed with sample liquid to be measured; The volume ratio of above-mentioned volume A, volume B and long-pending body C is A: B: C=1: 6: 2;
Two, stratographic analysis: adopt the C18 chromatographic column; Select the moving phase of C18 chromatographic column to be: acetonitrile+ammonium acetate+halfcystine; Wherein the concentration of acetonitrile is 4.8-5.2%, and the concentration of ammonium acetate is 0.45-0.55%, and the concentration of halfcystine is 0.09-0.11%; The flow velocity of control moving phase is 1.0mL/min; Through the C18 chromatographic column, the C18 chromatographic column is different with the adsorptive power of ethyl mercury to inorganic mercury, methyl mercury with sample liquid to be measured, and moving phase absorbs wash-out successively with inorganic mercury, methyl mercury and ethyl mercury;
Three, atomic fluorescence analysis: the liquid to be measured after the C18 chromatographic column is separated mixes with oxygenant earlier, again and air mixed, and through UV-irradiation; Organic mercury is oxidized to inorganic mercury, and in the reductive agent of acid medium, the mercury in the solution is reduced into atomic mercury by the potassium borohydride reduction agent again; By carrier gas mercury is brought in the atomizer; Mercury is under the hollow cathode light irradiation, and the ground state mercury atom is excited to high-energy state, is deactivating when getting back to ground state; Launch the fluorescence of mercury characteristic wavelength, the mercury fluorescence intensity is directly proportional with mercury content; Carry out data aggregation with atomic fluorescence couplet and data processing software again; Described reductive agent is that concentration is that 2.0% KBH4 and concentration are the mixed solution that 0.5% KOH forms, and described oxygenant is that concentration is that 1.0% K2S2O8 and concentration are the mixed solution of 0.5% KOH.
Four, detect conclusion: after the fluorescence intensity that the mercury atom that will from the atomic fluorescence analysis appearance, obtain sends is carried out data aggregation with data processing software; Again with the data of collecting through tabulation or plot the coordinate diagram analysis, can detect the content of methyl mercury in the fish oil exactly; Above-mentioned number percent is mass percent.
In the atomic fluorescence analysis appearance, the lamp current of said atomic fluorescence can be preferably 30mA; Shield gas flow speed is 600mL min-1; Flow rate of carrier gas can be preferably 300mL min-1.
As improvement, the filtering holes of the filtering membrane in the said step 1 can be preferably 0.45 micron.
Improve, described carrier gas may be selected to be argon gas or helium again.
Compared with prior art; The invention has the advantages that red, orange, green, blue, yellow (ROGBY) and atomic fluorometry are applied in the detection of methyl mercury content in the fish oil simultaneously, and through to the control of the selection of moving phase in the red, orange, green, blue, yellow (ROGBY) and concentration and to the control of flow rate of mobile phase, again in the atomic fluorometry to the control of selection, lamp current and the carrier gas of reductive agent and oxygenant; Can measure the methyl mercury content of fish oil quickly and easily; And reagent dosage used in the testing process is few, and analytical cycle is short, and this method detects good stability; Accuracy is high, is the method that detects methyl mercury content in a kind of very practical fish oil.
Description of drawings
Fig. 1 is the present invention does not add standard methyl mercury solution in a liquid to be measured coordinate diagram;
Fig. 2 is the coordinate diagram that has added standard methyl mercury solution among Fig. 1;
Fig. 3 is the linear analysis and the detection limit coordinate diagram of detection method of the present invention.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
To shown in Figure 3, the method that present embodiment is measured methyl mercury content in the fish oil may further comprise the steps (it is mass percent that following number percent is number percent) like Fig. 1:
One, sample extraction: take by weighing 0.5mL fish oil sample, in its container of packing into, in container, adding 3mm concentration is the 10%KOH+1% thiocarbamide; Stirred 20 minutes; Again the solution that stirs is put into hydro-extractor and carry out centrifugally, add 1mm concentration then and be 20% HCl solution and neutralize, stirred 20 minutes; With the neutralization after solution put into hydro-extractor centrifugal after; Getting supernatant liquor, is that 0.45 micron filtering membrane filters with supernatant through filtering holes again, and being settled to 10ml with deionized water, to process liquid to be measured subsequent use;
Two, stratographic analysis: choose liquid 100 μ L to be measured, put into chromatograph, select chromatograph moving phase to be: moving phase is acetonitrile+ammonium acetate+halfcystine; Wherein the concentration of acetonitrile is 5%, and the concentration of ammonium acetate is 0.5%, and the concentration of halfcystine is 0.1%; The control flow velocity is 1.0mL/min; Liquid to be measured is through the C18 chromatographic column, because the C18 post is different with the adsorptive power of ethyl mercury to inorganic mercury, methyl mercury, moving phase absorbs wash-out successively with inorganic mercury, methyl mercury and ethyl mercury;
Three, atomic fluorescence analysis: the liquid to be measured after the C18 chromatographic column is separated mixes with oxygenant earlier, again and air mixed, and through UV-irradiation; Organic mercury is oxidized to inorganic mercury, and in the reductive agent of acid medium, the mercury in the solution is reduced into atomic mercury by the potassium borohydride reduction agent again; By carrier gas mercury is brought in the atomizer; Mercury is under the hollow cathode light irradiation, and the ground state mercury atom is excited to high-energy state, is deactivating when getting back to ground state; Launch the fluorescence of mercury characteristic wavelength, the mercury fluorescence intensity is directly proportional with mercury content; Carry out data aggregation with atomic fluorescence couplet and data processing software again; Described reductive agent is that concentration is that 2.0% KBH4 and concentration are the mixed solution that 0.5% KOH forms, and described oxygenant is that concentration is that 1.0% K2S2O8 and concentration are the mixed solution of 0.5% KOH.In atomic fluorescence analysis, the lamp current of said atomic fluorescence is 30mA; Shield gas flow speed is 600mL min-1; Flow rate of carrier gas is 300mL min-1.Above-mentioned carrier gas is argon gas or helium.C18 chromatographic column in said is a known technology, all can consult on the net.Said shielding gas is and is used for atomic fluorescence analysis shielding gas commonly used.
Four, detect conclusion: after the fluorescence intensity that the mercury atom that will from the atomic fluorescence analysis appearance, obtain sends is carried out data aggregation with data processing software; Again with the data of collecting through tabulation or plot the coordinate diagram analysis, can detect the content of methyl mercury in the fish oil exactly; Above-mentioned number percent is mass percent.
When methyl mercury content is less than 0.2 μ g/L among the above-mentioned liquid 100 μ L to be measured; Can in liquid to be measured, add the methyl mercury standard solution; Make methyl mercury content in the liquid to be measured greater than 0.2 μ g/L; Because when the detection of methyl mercury, the content of methyl mercury detects effect and can lack nearly during less than 0.2 μ g/L.Be the absolute accuracy that guarantees to detect; Can in liquid to be measured, place the methyl mercury titer, make the total body burden of methyl mercury in the liquid to be measured greater than 0.2 μ g/L, then when the analytic process of detection architecture; Through calculating the addition of removing the methyl mercury titer, be methyl mercury content in the fish oil.The compound method of methyl mercury standard solution is: using deionized water preparation purity is 99.9% Hg2+ solution, is that 3.5-4.5 ℃ dark place is subsequent use in temperature.
Below in conjunction with embodiment the present invention is described further:
1. reagent and instrument
HPLC-AFS9230 liquid chromatography-atomic fluorescence combined instrument (Beijing Jitian Instrument Co., Ltd.); Methyl mercury (MeHg), ethyl mercury (EtHg) standard items (U.S. Sigma company), Hg2+ standard solution (national standard material center), standard items purity is 99.9%; NaOH, potassium borohydride, potassium persulfate, thiocarbamide, potassium chloride, ammonium acetate are that homemade analysis is pure, and hydrochloric acid and acetonitrile are guaranteed reagent, and experimental water is a secondary deionized water.
2. experimental technique
2.1 the preparation of standard stock solution
Standard inventory solution is contained in vial or the plastic bottle and preserves 4 ℃ of dark places all with deionized water preparation, and standard solution every day of low concentration is by dilution stock solution fresh.
2.2 sample extraction
Take by weighing 0.5mL fish oil sample, add 3mL alkali extracting solution (10%KOH+1% thiocarbamide), vortex mixed and extracted 20min is centrifugal then; Add 1mL acid extractants liquid (20%HCl) again, vortex mixed and extracted 10min, neutralization then; The centrifuging and taking supernatant is crossed 0.45 micron filter membrane, is settled to 10mL.
2.3 chromatographiccondition
Chromatographic column: Agela MP-C18 (150mm * 4.6mm, 5 μ m); Moving phase: 5% acetonitrile+0.5% ammonium acetate+0.1% halfcystine; Flow velocity: 1.0mL min-1; Sampling volume: 100 μ L.
2.4 atomic fluorescence condition of work
Reductive agent: 2%KBH4/0.5%KOH; Oxygenant: 1%K2S2O8/0.5%KOH; Current-carrying: 7%HCl; Lamp current: 30mA; Carrier gas: 600mL min-1; Carrier gas: 300mL min-1.
3. result and discussion
3.1 the linear analysis and the detection limit of method
Prepare a series of methyl mercury standard solution (0,1.0,2.0,4.0,8.0,10.0 μ g/L), the drawing standard curve, the result sees Fig. 3.The linear range of typical curve is 0-10.0 μ g/L, and its linear related coefficient is 0.9993.Under the condition determination of methyl mercury, blank sample introduction METHOD FOR CONTINUOUS DETERMINATION 10 times, 3 times of pairing concentration values of standard deviation of its measured value are the detection limit of methyl mercury: 0.2 μ g/L.
3.2 the selection of extract
Form complete extraction from sample of mercury is come out is the key takeaway of morphological analysis, should guarantee the efficient extracted to guarantee that again the form of mercury in leaching process can not transform mutually.Extracting at present the more of usefulness is HCl, and complexing agent is halfcystine, thiocarbamide etc.To the characteristics of fish oil sample, this experiment combination uses alkali extracting solution (10%KOH+1% thiocarbamide), acid extractants liquid (20%HCl) that sample is extracted [5], and the extraction ratio of methyl mercury can be up to more than 90%.
3.3 the selection of moving phase
In RPLC, often select the reaction of suitable complexing agent and ion-pairing agent and mercury compound for use, its effect be with sample in mercury form non-polar compound and then on the ODS post, separate.Complexing agent commonly used comprises: sodium diethyldithiocarbamate (SDDC), SPDC, pyrrolidine aminodithioformic acid (APDC), dithizone and 2 mercapto ethanol (ME).Ion-pairing agent commonly used comprises: halfcystine, TBAB (TBABr), potassium bromide, sodium bromide and sodium chloride etc.The concentration of complexing agent (APDC, halfcystine) is to the separation of mercury compound and remain with very big influence.If the concentration of complexing agent is too low, its with the complex reaction of mercury compound carry out not exclusively, the silicon hydroxyl of remnants interaction on charged not complex compound and the C18 post and on the post that causes absorbing phenomenon can reduce the repeatability of sample introduction.But the excessive concentration of complexing agent, its background absorption on UV-detector also increase thereupon, mercury complex can not be detected or detectability very high.Take all factors into consideration above each side factor, the moving phase of this experimental selection is 5% acetonitrile+0.5% ammonium acetate+0.1% halfcystine (using preceding through the 0.45mm membrane filtration).
3.4 the recovery and precision test
In the fish oil sample, add an amount of methyl mercury standard solution, carry out the mark-on recovery test, the recovery is (result sees table 1,2) between 96.7%-104.7%.Get 6 parts of fish oil samples and handle by 2.2.2, last machine is measured, and obtaining 6 replicate determination relative standard deviation RSD (n=6) is 3.5%.
The test of table 1. recovery of standard addition
The test of table 2. precision
4. conclusion
The liquid chromatography that this experiment is set up-atomic fluorescence coupling (LC-AFS) measure the method for methyl mercury content in the fish oil easy and simple to handle, save time, reagent dosage is few, analytical cycle is short, can integrate with the internationalization detection.This method empirical tests is in 0-10.0 μ g/L concentration range, and linear dependence is good, coefficient R=0.9993, and the interpolation recovery of high 3 concentration is all more than 90% in hanging down, and RSD＜5% satisfies the methodology requirement, is applicable to methyl mercury Determination on content in the fish oil.
Claims (4)
1. method of measuring methyl mercury content in the fish oil is characterized in that: may further comprise the steps:
One, sample extraction: taking by weighing volume is A fish oil sample, and in its container of packing into, in container, adding volume is (9-11) %KOH+ (0.9-1.1) % thiocarbamide of B; Stirred 18-25 minute; Again the solution that stirs is put into hydro-extractor and carry out centrifugally, add volume then, stirred 9-15 minute for C concentration is that the HCl solution of 19-21% advances neutralization; With the neutralization after solution put into hydro-extractor centrifugal after; Getting supernatant liquor, is the filtering membrane filtration of 0.4-0.5 micron with supernatant through filtering holes again, promptly is mixed with sample liquid to be measured; The volume ratio of above-mentioned volume A, volume B and long-pending body C is: A: B: C=1: 6: 2;
Two, stratographic analysis: adopt the C18 chromatographic column; Select the moving phase of C18 chromatographic column to be: acetonitrile+ammonium acetate+halfcystine; Wherein the concentration of acetonitrile is 4.8-5.2%, and the concentration of ammonium acetate is 0.45-0.55%, and the concentration of halfcystine is 0.09-0.11%; The flow velocity of control moving phase is 1.0mL/min; Through the C18 chromatographic column, the C18 chromatographic column is different with the adsorptive power of ethyl mercury to inorganic mercury, methyl mercury with sample liquid to be measured, and moving phase absorbs wash-out successively with inorganic mercury, methyl mercury and ethyl mercury;
Three, atomic fluorescence analysis: the liquid to be measured after the C18 chromatographic column is separated mixes with oxygenant earlier, again and air mixed, and through UV-irradiation; Organic mercury is oxidized to inorganic mercury, and in the reductive agent of acid medium, the mercury in the solution is reduced into atomic mercury by the potassium borohydride reduction agent again; By carrier gas mercury is brought in the atomizer; Mercury is under the hollow cathode light irradiation, and the ground state mercury atom is excited to high-energy state, is deactivating when getting back to ground state; Launch the fluorescence of mercury characteristic wavelength, the mercury fluorescence intensity is directly proportional with mercury content; Carry out data aggregation with atomic fluorescence couplet and data processing software again; Described reductive agent is that concentration is that 2.0% KBH4 and concentration are the mixed solution that 0.5% KOH forms, and described oxygenant is that concentration is that 1.0% K2S2O8 and concentration are the mixed solution of 0.5% KOH.
Four, detect conclusion: after the fluorescence intensity that the mercury atom that will from the atomic fluorescence analysis appearance, obtain sends is carried out data aggregation with data processing software; Again with the data of collecting through tabulation or plot the coordinate diagram analysis, can detect the content of methyl mercury in the fish oil exactly; Above-mentioned number percent is mass percent.
2. the method for methyl mercury content in the mensuration fish oil according to claim 1: it is characterized in that: in the atomic fluorescence analysis appearance, the lamp current of said atomic fluorescence is 30mA; Shield gas flow speed is 600mL min-1; Flow rate of carrier gas is 300mL min-1.
3. the method for methyl mercury content in the mensuration fish oil according to claim 1 is characterized in that: the filtering holes of the filtering membrane in the said step 1 is 0.45 micron.
4. the method for methyl mercury content in the mensuration fish oil according to claim 1 and 2 is characterized in that: described carrier gas is argon gas or helium.
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Cited By (3)
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| CN106501382A (en) * | 2015-09-08 | 2017-03-15 | 通威股份有限公司 | The extraction of mercury compound and detection method in a kind of flesh of fish |
| CN107677744A (en) * | 2017-09-28 | 2018-02-09 | 遵义市产品质量检验检测院 | The detection method of form mercury in a kind of animal tissue cell |
| CN115166115A (en) * | 2022-07-20 | 2022-10-11 | 宁波工程学院 | Sample pretreatment method for detecting various mercury morphological contents in fish meat and detection method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106501382A (en) * | 2015-09-08 | 2017-03-15 | 通威股份有限公司 | The extraction of mercury compound and detection method in a kind of flesh of fish |
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| CN107677744A (en) * | 2017-09-28 | 2018-02-09 | 遵义市产品质量检验检测院 | The detection method of form mercury in a kind of animal tissue cell |
| CN115166115A (en) * | 2022-07-20 | 2022-10-11 | 宁波工程学院 | Sample pretreatment method for detecting various mercury morphological contents in fish meat and detection method |
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Application publication date: 20120620 |