CN103389349B - Method for detecting content of malachite green and metabolin thereof in aquiculture environment water body - Google Patents
Method for detecting content of malachite green and metabolin thereof in aquiculture environment water body Download PDFInfo
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Abstract
The invention relates to a method for detecting the content of malachite green and a metabolin thereof in an aquiculture environment water body, and belongs to the technical field of environmental quality and safety detection. According to the invention, the water body is pretreated and then enriched and purified by utilizing a multi-walled carbon nanotube solid phase extraction column and qualitatively and quantitatively analyzed by utilizing a liquid phase chromatography-tandem mass spectrometer. The method disclosed by the invention has the advantages of convenience for operation, better repeatability, accurate nature determination and higher recovery rate and can be used for fast analyzing the content of the malachite green and the metabolin thereof in the aquiculture environment water body.
Description
Technical field
The invention belongs to environment security detection technique field, relate to a kind of culture environment of aquatic products water body Malachite Green and metabolite content detection method thereof.
Background technology
Malachite green belongs to a kind of industrial dye, in aquaculture through being commonly used to sterilization for the treatment of saprolegniasis, cheek mildew and environment etc.Research shows that malachite green and metabolic product procrypsis malachite green thereof eliminate slowly in animal body, residence time is long, and there is carcinogenic, teratogenesis and mutagenesis, American-European a lot of country and China Ministry of Agriculture No. 235 file of bulletin are all classified malachite green to ban use of medicine as, are defined in animal derived food and must not detect.In aquaculture at present, the phenomenon of Misuse malachite green has obtained effective control of government agencies at all levels, but still have minority fisherman using malachite green, adding once malachite green is widely used, part culture environment of aquatic products has been caused to pollution, cause the remaining malachite green class medicine of meeting in part breeding environment water body, for follow-up aquaculture brings potential safety hazard.In addition, in the market circulation link of part aquatic products, also can need because of the keep-alive of fish body, some illegal molecules add malachite green in supporting water body temporarily.The aquatic products that in actual testing, often discovery is not used malachite green class medicine to carry out disease treatment yet also can detect the existence of malachite green and its residues.The existence of above situation makes troubles to a certain extent the work of tracing to the source of fish quality problem.Therefore monitor culture environment of aquatic products water body Malachite Green and metabolite content level thereof and there is positive effect to understanding breeding environment safety case, investigation aquatic products Malachite Green pollution source and fish quality supervision.At present less for the research of the trace malachite green and its residues detection method in culture environment of aquatic products water body.How by Sample Pretreatment Technique and instrument analysis technology effectively, the key that set up that a kind of example enrichment degree is high, the recovery is high, favorable reproducibility and the high culture environment of aquatic products water body Malachite Green class method for detecting residue of degree of accuracy becomes research.
Carbon nano-tube (Carbon nanotubes, CNTS) is as novel functional material, at physics, chemistry and the field such as biological, is widely applied.CNTS has very strong adsorptive power, can be combined with object molecule by noncovalent interaction power such as π-π acting force, Van der Waals force and hydrophobic interactions, there is high-specific surface area, good advantages such as chemistry, mechanical stability and thermal stability, can be used as good gas chromatography, Capillary Electrophoresis and performance liquid chromatographic column packing material, also can be used as sorbing material for being enriched with organic pollutants, metallic ion and biomacromolecule.The superperformance having due to CNTS material and cheap price advantage, the multi-walled carbon nano-tubes (MWCNTS) in existing bibliographical information CNTS is in the pre-treatment of the samples such as water body organophosphorus, organochlorine, agricultural chemicals and purifying at present.Multi-wall carbon nano-tube tube material is also had to positive meaning for detection of veterinary drugs in food work for expanding residue of veterinary drug pretreatment technology more.The detection technique of malachite green has liquid chromatography and liquid chromatograph mass spectrography.After propane sulfonic acid cation exchange solid-phase extraction column or aluminium oxide Solid-Phase Extraction column purification, realize liquid chromatography-fluoroscopic examination, the detection of liquid chromatography-ultraviolet and liquid chromatography-mass spectrometry analyzing and testing.Liquid phase chromatography complex pretreatment, consuming time, detect limit for height and be unfavorable for accurate quantitative analysis and qualitative analysis.Culture environment of aquatic products aqueous samples complicated component, and pollutant load is lower, if Impurity removal is bad in sample pretreatment process, directly understand the measurement result of interference Instrument, by carbon nanomaterial efficient and with low cost, for Sample Pretreatment Technique, be therefore object of the present invention.
Summary of the invention
The object of the invention is to overcome the deficiency of existing analytical approach, can find a kind of breeding environment water body Malachite Green quick, accurate and with low cost and the assay method of metabolin thereof, to realize the quantitative and qualitative analysis of culture environment of aquatic products water body Malachite Green and metabolin thereof, measure.
The inventive method comprises the following steps: (1) sample pretreatment, (2) solid phase extraction concentration purify, (3) liquid chromatography-Mass Spectrometer Method, the method for operating of each step is as follows:
(1) sample pretreatment: accurately pipette water sample 20～50mL after filtering, add the deuterated procrypsis malachite green of the deuterated malachite green of 10ng and 10ng, adding chromatographically pure formic acid to make its volume fraction is 0.04～0.10%.
(2) solid phase extraction concentration purifies: in 3mL tygon solid phase extraction column (the special-purpose void column of SPE) bottom, first place one deck aperture 20 μ m silica sand filter core sieve plates, add 20～60mg multi-wall carbon nano-tube tube material (diameter 40～60nm, length 5～15 μ m, purity > 95%, ash content≤2%, specific surface area is 40～300m
2/ g), place again one deck 20 μ m filter core sieve plates above, by regulate upper strata filter core sieve plate downwards compression degree control multi-walled carbon nano-tubes depth of packing at 0.5～0.6cm; The multi-walled carbon nano-tubes solid-phase extraction column completing first, with 5mL methyl alcohol and 5mL pure water rinse activation, is then all transferred to pretreated water sample in solid-phase extraction column, and coutroi velocity is at 1.0mL/min; In solid-phase extraction column, add the drip washing of 5mL pure water again, discard above whole efflux; In the most backward solid-phase extraction column, add 5% formic acid acetonitrile 4～6mL to carry out wash-out, collect eluent in 10mL test tube.
(3) liquid chromatography-Mass Spectrometer Method: eluent, after nitrogen dries up at 45～55 ℃, fully dissolves with 2mL initial composition mobile phase; Get 1mL sample liquid, through 0.22 μ m organic phase filtering with microporous membrane, in sample flasket, under liquid chromatography-mass spectrum condition of having set, detect, carry out qualitative and quantitative analysis.Chromatographic condition: C
18chromatographic column (50mm * 2.1mm, 1.7 μ m), 40 ℃ of column temperatures, sample size 10 μ L, mobile phase composition is with formic acid, to adjust 5 mmol/L ammonium acetate buffer solution and the acetonitriles of pH to 4.5, flow velocity 0.3 mL/min, condition of gradient elution, 0～3.0min, 50%～5%(ammonium acetate buffer solution, linear change), 3.0～5.0min, 5%～50%(ammonium acetate buffer solution, linear change); Mass spectrum condition: electron spray positive ion mode (ESI
+), capillary voltage 3.50 kv, 120 ℃ of ion source temperatures, 380 ℃ of desolventizing temperature degree, desolventizing airshed 600 L/h, taper hole airshed 50 L/h, multiple-reaction monitoring (MRM) scan pattern; Drawing standard working curve, calculates malachite green and procrypsis malachite green content with inner mark method ration.
Beneficial effect of the present invention: the present invention has set up the detection method of culture environment of aquatic products water body Malachite Green and metabolin thereof; Adopt cheap multi-wall carbon nano-tube tube material to carry out example enrichment purification as solid phase extraction column stuffing, good purification, has reduced impurity effectively to measuring the interference of process; Adopt liquid chromatography-mass spectroscopy to carry out the monitoring of many reactive ions, there is higher sensitivity and degree of accuracy; Compare with existing measuring technology, the present invention does not need commercialization PRS cation exchange or the aluminium oxide solid-phase extraction column that price is more expensive in detecting malachite green and its residues process, method can be carried out qualitative and quantitative measurement simultaneously, operation is simple, consuming cost is low, the malachite green and its residues content in can express-analysis culture environment of aquatic products water body.
Accompanying drawing explanation
Accompanying drawing 1 is the standard solution chromatogram of 1.00 μ g/L;
The daughter ion scintigram that accompanying drawing 2 is malachite green;
Accompanying drawing 3 is the daughter ion scintigram of procrypsis malachite green.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described.
Liquid chromatography-the Mass Spectrometer Method of embodiment 1 aquaculture pond water body Malachite Green
(1) sample pretreatment: accurately pipette water sample 20mL after filtering, add deuterated malachite green and the deuterated procrypsis malachite green mixing inner mark solution 100 μ L of 100ng/mL, adding chromatographically pure formic acid to make its volume fraction is 0.04%.
(2) solid phase extraction concentration purifies: in 3mL tygon solid phase extraction column (the special-purpose void column of SPE) bottom, first place one deck aperture 20 μ m silica sand filter core sieve plates, add 20mg multi-wall carbon nano-tube tube material (diameter 40～60nm, length 5～15 μ m, purity > 95%, ash content≤2%, specific surface area is 40～300m
2/ g), place again one deck 20 μ m filter core sieve plates above, by regulate upper strata filter core sieve plate downwards compression degree control multi-walled carbon nano-tubes depth of packing at 0.5cm; The multi-walled carbon nano-tubes solid-phase extraction column completing first, with 5mL methyl alcohol and 5mL pure water rinse activation, is then all transferred to pretreated water sample in solid-phase extraction column, and coutroi velocity is at 1.0mL/min; In solid-phase extraction column, add the drip washing of 5mL pure water again, discard above whole efflux; In the most backward solid-phase extraction column, add 5% formic acid acetonitrile 4mL to carry out wash-out, collect eluent in 10mL test tube.
(3) liquid chromatography-Mass Spectrometer Method: eluent, after nitrogen dries up at 45 ℃, fully dissolves with 2mL acetonitrile-5mmol/L ammonium acetate buffer solution (1+1, v/v); Get 1mL sample liquid, through 0.22 μ m organic phase filtering with microporous membrane, in sample flasket, under liquid chromatography-mass spectrum condition of having set, detect, carry out qualitative and quantitative analysis.Chromatographic condition: C
18chromatographic column (50mm * 2.1 mm, 1.7 μ m), 40 ℃ of column temperatures, sample size 10 μ L, mobile phase composition is 5 mmol/L ammonium acetate buffer solution and acetonitriles, flow velocity 0.3mL/min, condition of gradient elution, 0～3.0min, 50%～5%(ammonium acetate buffer solution, linear change), 3.0～5.0min, 5%～50%(ammonium acetate buffer solution, linear change), obtain the chromatogram that appearance time is moderate, peak shape is sharp-pointed, degree of separation is good, appearance time malachite green 1.06min, procrypsis malachite green 3.01min(is shown in accompanying drawing 1); Mass spectrum condition: electron spray positive ion mode (ESI
+), capillary voltage 3.50 kv, 120 ℃ of ion source temperatures, 380 ℃ of desolventizing temperature degree, desolventizing airshed 600 L/h, taper hole airshed 50L/h, multiple-reaction monitoring (MRM) scan pattern; Malachite green quota ion is to 329.3/313.2, and qualitative ion pair 329.3/208.1(is shown in accompanying drawing 2), procrypsis malachite green quota ion is to 331.2/316.2, qualitative ion pair 331.2/239.2(is shown in accompanying drawing 3); Drawing standard working curve, calculates malachite green and procrypsis malachite green content with inner mark method ration.
(4) Specification Curve of Increasing
With acetonitrile-5mmol/L ammonium acetate buffer solution (1+1, v/v) compound concentration is respectively malachite green and the procrypsis malachite green mixed standard solution of 0.02 μ g/L, 0.05 μ g/L, 0.10 μ g/L, 0.25 μ g/L, 1.00 μ g/L, 2.00 μ g/L and 5.00 μ g/L, the deuterated malachite green of internal standard compound and deuterated procrypsis malachite green concentration are 5.00 μ g/L, then according to above-mentioned steps requirement (3), operate, according to internal standard method, require drawing standard curve.
(5) the mensuration of the method recovery
By the concentration of 0.002 μ g/L, 0.005 μ g/L, 0.010 μ g/L, 0.10 μ g/L and 0.20 μ g/L, in pond waters, add respectively the mixed standard solution of malachite green and procrypsis malachite green, each interpolation level is done respectively 6 Duplicate Samples; According to step (1)～(4) carry out liquid chromatography-Mass Spectrometer Method, and with typical curve comparison obtained above, by converting, finally obtain the concentration of water body Malachite Green to be measured and procrypsis malachite green.The method recovery is at 84～112%, RSD < 15%.
Liquid chromatography-the Mass Spectrometer Method of embodiment 2 aquaculture pond water body Malachite Greens
(1) sample pretreatment: accurately pipette water sample 40mL after filtering, add deuterated malachite green and the deuterated procrypsis malachite green mixing inner mark solution 100 μ L of 100ng/mL, adding chromatographically pure formic acid to make its volume fraction is 0.08%.
(2) solid phase extraction concentration purifies: in 3mL tygon solid phase extraction column (the special-purpose void column of SPE) bottom, first place one deck aperture 20 μ m silica sand filter core sieve plates, add 40mg multi-wall carbon nano-tube tube material (diameter 40～60nm, length 5～15 μ m, purity > 95%, ash content≤2%, specific surface area is 40～300m
2/ g), place again one deck 20 μ m filter core sieve plates above, by regulate upper strata filter core sieve plate downwards compression degree control multi-walled carbon nano-tubes depth of packing at 0.55cm; The multi-walled carbon nano-tubes solid-phase extraction column completing first, with 5mL methyl alcohol and 5mL pure water rinse activation, is then all transferred to pretreated water sample in solid-phase extraction column, and coutroi velocity is at 1.0mL/min; In solid-phase extraction column, add the drip washing of 5mL pure water again, discard above whole efflux; In the most backward solid-phase extraction column, add 5% formic acid acetonitrile 5mL to carry out wash-out, collect eluent in 10mL test tube.
(3) liquid chromatography-Mass Spectrometer Method: eluent, after nitrogen dries up at 50 ℃, fully dissolves with 2mL acetonitrile-5mmol/L ammonium acetate buffer solution (1+1, v/v); Get 1mL sample liquid, through 0.22 μ m organic phase filtering with microporous membrane, in sample flasket, under liquid chromatography-mass spectrum condition of having set, detect, carry out qualitative and quantitative analysis.Chromatographic condition: C
18chromatographic column (50mm * 2.1 mm, 1.7 μ m), 40 ℃ of column temperatures, sample size 10 μ L, mobile phase composition is 5 mmol/L ammonium acetate buffer solution and acetonitriles, flow velocity 0.3mL/min, condition of gradient elution, 0～3.0min, 50%～5%(ammonium acetate buffer solution, linear change), 3.0～5.0min, 5%～50%(ammonium acetate buffer solution, linear change); Mass spectrum condition: electron spray positive ion mode (ESI
+), capillary voltage 3.50 kv, 120 ℃ of ion source temperatures, 380 ℃ of desolventizing temperature degree, desolventizing airshed 600 L/h, taper hole airshed 50 L/h, multiple-reaction monitoring (MRM) scan pattern; Malachite green quota ion is to 329.3/313.2, qualitative ion pair 329.3/208.1, and procrypsis malachite green quota ion is to 331.2/316.2, qualitative ion pair 331.2/239.2; Drawing standard working curve, calculates malachite green and procrypsis malachite green content with inner mark method ration.
(4) Specification Curve of Increasing
With acetonitrile-5mmol/L ammonium acetate buffer solution (1+1, v/v) compound concentration is respectively malachite green and the procrypsis malachite green mixed standard solution of 0.02 μ g/L, 0.05 μ g/L, 0.10 μ g/L, 0.25 μ g/L, 1.00 μ g/L, 2.00 μ g/L and 5.00 μ g/L, the deuterated malachite green of internal standard compound and deuterated procrypsis malachite green concentration are 5.00 μ g/L, then according to above-mentioned steps requirement (3), operate, according to internal standard method, require drawing standard curve.
(5) the mensuration of the method recovery
By the concentration of 0.002 μ g/L, 0.005 μ g/L, 0.010 μ g/L, 0.10 μ g/L and 0.20 μ g/L, in pond waters, add respectively the mixed standard solution of malachite green and procrypsis malachite green, each interpolation level is done respectively 6 Duplicate Samples; According to step (1)～(4) carry out liquid chromatography-Mass Spectrometer Method, and with typical curve comparison obtained above, by converting, finally obtain the concentration of water body Malachite Green to be measured and procrypsis malachite green.The method recovery is at 78～103%, RSD < 15%.
Liquid chromatography-the Mass Spectrometer Method of embodiment 3 aquaculture pond water body Malachite Greens
(1) sample pretreatment: accurately pipette water sample 50mL after filtering, add deuterated malachite green and the deuterated procrypsis malachite green mixing inner mark solution 100 μ L of 100ng/mL, adding chromatographically pure formic acid to make its volume fraction is 0.10%.
(2) solid phase extraction concentration purifies: in 3mL tygon solid phase extraction column (the special-purpose void column of SPE) bottom, first place one deck aperture 20 μ m silica sand filter core sieve plates, add 60mg multi-wall carbon nano-tube tube material (diameter 40～60nm, length 5～15 μ m, purity > 95%, ash content≤2%, specific surface area is 40～300m
2/ g), place again one deck 20 μ m filter core sieve plates above, by regulate upper strata filter core sieve plate downwards compression degree control multi-walled carbon nano-tubes depth of packing at 0.6cm; The multi-walled carbon nano-tubes solid-phase extraction column completing first, with 5mL methyl alcohol and 5mL pure water rinse activation, is then all transferred to pretreated water sample in solid-phase extraction column, and coutroi velocity is at 1.0mL/min; In solid-phase extraction column, add the drip washing of 5mL pure water again, discard above whole efflux; In the most backward solid-phase extraction column, add 5% formic acid acetonitrile 6mL to carry out wash-out, collect eluent in 10mL test tube.
(3) liquid chromatography-Mass Spectrometer Method: eluent, after nitrogen dries up at 55 ℃, fully dissolves with 2mL acetonitrile-5mmol/L ammonium acetate buffer solution (1+1, v/v); Get 1mL sample liquid, through 0.22 μ m organic phase filtering with microporous membrane, in sample flasket, under liquid chromatography-mass spectrum condition of having set, detect, carry out qualitative and quantitative analysis.Chromatographic condition: C
18chromatographic column (50mm * 2.1mm, 1.7 μ m), 40 ℃ of column temperatures, sample size 10 μ L, mobile phase composition is 5mmol/L ammonium acetate buffer solution and acetonitrile, flow velocity 0.3mL/min, condition of gradient elution, 0～3.0min, 50%～5%(ammonium acetate buffer solution, linear change), 3.0～5.0min, 5%～50%(ammonium acetate buffer solution, linear change); Mass spectrum condition: electron spray positive ion mode (ESI
+), capillary voltage 3.50 kv, 120 ℃ of ion source temperatures, 380 ℃ of desolventizing temperature degree, desolventizing airshed 600 L/h, taper hole airshed 50 L/h, multiple-reaction monitoring (MRM) scan pattern; Malachite green quota ion is to 329.3/313.2, qualitative ion pair 329.3/208.1, and procrypsis malachite green quota ion is to 331.2/316.2, qualitative ion pair 331.2/239.2; Drawing standard working curve, calculates malachite green and procrypsis malachite green content with inner mark method ration.
(4) Specification Curve of Increasing
With acetonitrile-5mmol/L ammonium acetate buffer solution (1+1, v/v) compound concentration is respectively malachite green and the procrypsis malachite green mixed standard solution of 0.02 μ g/L, 0.05 μ g/L, 0.10 μ g/L, 0.25 μ g/L, 1.00 μ g/L, 2.00 μ g/L and 5.00 μ g/L, the deuterated malachite green of internal standard compound and deuterated procrypsis malachite green concentration are 5.00 μ g/L, then according to above-mentioned steps requirement (3), operate, according to internal standard method, require drawing standard curve.
(5) the mensuration of the method recovery
By the concentration of 0.002 μ g/L, 0.005 μ g/L, 0.010 μ g/L, 0.10 μ g/L and 0.20 μ g/L, in pond waters, add respectively the mixed standard solution of malachite green and procrypsis malachite green, each interpolation level is done respectively 6 Duplicate Samples; According to step (1)-(4) carry out liquid chromatography-Mass Spectrometer Method, and with typical curve comparison obtained above, by converting, finally obtain the concentration of water body Malachite Green to be measured and procrypsis malachite green.The method recovery is 81-114%, RSD < 15%.
Above-described embodiment is to explanation of the present invention, is not limitation of the invention, any scheme after simple change of the present invention is all belonged to protection scope of the present invention.
Claims (2)
1. culture environment of aquatic products water body Malachite Green and metabolite content detection method thereof, is characterized in that the method comprises that sample pretreatment, solid phase extraction concentration purify and these three steps of liquid chromatography-Mass Spectrometer Method, wherein:
Described sample pretreatment, by the following step operation: accurately pipette water sample 20～50mL after filtering, add the deuterated procrypsis malachite green of the deuterated malachite green of 10ng and 10ng, adding chromatographically pure formic acid to make its volume fraction is 0.04～0.10%;
Described solid phase extraction concentration purifies, operation by the following step: first place one deck aperture 20 μ m silica sand filter core sieve plates in 3mL tygon solid phase extraction column bottom, add 20～60mg multi-wall carbon nano-tube tube material, place again one deck 20 μ m filter core sieve plates above, by regulate upper strata filter core sieve plate downwards compression degree control multi-walled carbon nano-tubes depth of packing at 0.5～0.6cm; The multi-walled carbon nano-tubes solid-phase extraction column completing first, with 5mL methyl alcohol and 5mL pure water rinse activation, is then all transferred to pretreated water sample in solid-phase extraction column, and coutroi velocity is at 1.0mL/min; In solid-phase extraction column, add the drip washing of 5mL pure water again, discard above whole efflux; In the most backward solid-phase extraction column, add 5% formic acid acetonitrile 4～6mL to carry out wash-out, collect eluent in 10mL test tube;
Described liquid chromatography-Mass Spectrometer Method, by the following step operation: eluent, after at 45～55 ℃, nitrogen dries up, fully dissolves with 2mL initial composition mobile phase; Get 1mL sample liquid, through 0.22 μ m organic phase filtering with microporous membrane, in sample flasket, under liquid chromatography-mass spectrum condition of having set, detect, carry out qualitative and quantitative analysis;
Chromatographic condition: C
1840 ℃ of chromatographic column column temperatures, sample size 10 μ L, mobile phase composition is 5mmol/L ammonium acetate buffer solution and acetonitrile, flow velocity 0.3 mL/min;
In condition of gradient elution: 0～3.0min, ammonium acetate buffer solution volumetric concentration is down to 5% by 50% linearity; In 3.0～5.0min, ammonium acetate buffer solution volumetric concentration rises to 50% by 5% linearity;
Mass spectrum condition: electron spray positive ion mode, capillary voltage 3.50kv, 120 ℃ of ion source temperatures, 380 ℃ of desolventizing temperature degree, desolventizing airshed 600 L/h, taper hole airshed 50 L/h, multiple-reaction monitoring scan pattern; Malachite green quota ion is to 329.3/313.2, qualitative ion pair 329.3/208.1, and procrypsis malachite green quota ion is to 331.2/316.2, qualitative ion pair 331.2/239.2; Drawing standard working curve, calculates malachite green and procrypsis malachite green content with inner mark method ration.
2. the detection method of a kind of culture environment of aquatic products water body Malachite Green content according to claim 1, it is characterized in that: described multi-walled carbon nano-tubes material diameter is 40～60nm, length is 5～15 μ m, purity > 95%, ash content≤2%, specific surface area is 40～300m
2/ g.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110187040A (en) * | 2019-06-26 | 2019-08-30 | 渤海大学 | A kind of sample-pretreating method detected simultaneously for freshwater aquiculture water body Malachite green residues liquid chromatogram-visible light and fluorescence |
| CN110187040B (en) * | 2019-06-26 | 2021-08-17 | 渤海大学 | Sample pretreatment method for simultaneously detecting malachite green residue in freshwater aquaculture water body by liquid chromatography-visible light and fluorescence |
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