CN106124643A - Tetrabromobisphenol A, decabromodiphenyl oxide and the method for HBCD three class bromide fire retardant content in detection aquatic products - Google Patents
Tetrabromobisphenol A, decabromodiphenyl oxide and the method for HBCD three class bromide fire retardant content in detection aquatic products Download PDFInfo
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Abstract
A kind of detect tetrabromobisphenol A in aquatic products, decabromodiphenyl oxide and the method for HBCD three class bromide fire retardant content, it is characterized in that: comprise the following steps, set up accelerated solvent extraction fast liquid chromatography tandem mass spectrum and measure tetrabromobisphenol A, decabromodiphenyl oxide and HBCD three class bromide fire retardant content in aquatic products, Aquatic product sample need to be detected through C18Chromatographic column separates, and mutually carries out gradient elution, mass spectrum multiple-reaction monitoring mode detection with methanol for flowing with water, and extraction standard corrects, and quantified by external standard method measures, confirmation.It is an advantage of the current invention that: detection method is easy and simple to handle, detection is quick and precisely, foundation can detect tetrabromobisphenol A in aquatic products, decabromodiphenyl oxide and the method for HBCD three class bromide fire retardant simultaneously, not only to ensureing that consumer is healthy and life security, promote that Aquatic Product Process Industry sustainable and healthy development has huge realistic meaning, it is possible to provide favourable technological reserve for food service industry supervision department and testing agency.
Description
Technical field
The present invention relates to field of detection of food safety, especially tetrabromobisphenol A, decabromodiphenyl oxide in a kind of detection aquatic products
Method with HBCD three class bromide fire retardant content.
Background technology
As important a member of food family, aquatic products are excellent with its low fat, high protein, nutritious, delicious flavour etc.
Selecting one of first-selected food just becoming domestic and international consumer, current China resident's Aquatic products consumption per capita is in non-staple food consumption
Core status.The export goods that aquatic products Ye Shi China is important simultaneously, contribute to important force for foreign exchange earning.Therefore, Aquatic product
Quality safety is for ensureing that people's health and life security, promotion aquatic products foreign trade have highly important meaning
Justice.Brominated flame-retardant (Brominated flame retardants) is the halogen organic fire-retardant that consumption figure is maximum in the world,
The brominated flame-retardant being presently using about 75 kinds, the most most importantly PBDE (Polybrominated
Diphenyl ethers, PBDEs), tetrabromobisphenol A (Tetrabromobisphenol A, TBBP-A) and HBCD
(Hexabromocyclododecane, HBCDs), be mainly used in building materials, printed circuit board (PCB), plastics, coating, electric wire and
In polyurethane foam.These materials can discharge lentamente from the product containing fire retardant.There is document report fire retardant residual
Stay be widely present in soil, deposit, house dust, water body, marine organisms, birds and blood of human body, emulsion, body fluid and
In fat, and there is the strongest cumulative bad, persistency, neurotoxicity and endocrine disruption characteristic.Due to tradition brominated flame-retardant
Huge toxicity, the most one after another by various countries be prevented or restricted from produce with use, wherein business pentabromo-and octabromodiphenyl ether in
Within 2009, being put into " Convention of Stockholm " controlling persistence organic pollutant, HBCDs was also put into this in 2013
About.HBCDs has been classified as the chemicals of priority acccess control by Britain and Japan, and Norway has completed country's assessment and listed in by HBCDs
The chemical substance that country prohibits the use of.And HBCDs is one is similar to persistence organic pollutant latency environment endocrine disruption
Thing, it can be accumulated in environmental and biological materials, produces environmental and biological materials and has a strong impact on, there are some researches show HBCDs to algae
Class, Mollusca, crustacean and fish body have obvious toxic action.
In recent years, due to PBDE (Polybrominated diphenyl ethers, PBDEs), tetrabromobisphenol A
(Tetrabromobisphenol A, TBBP-A) and HBCD (Hexabromocyclododecane, HBCDs)
Usage amount is big, residual period length, recall rate in the environment are high, and has bio-toxicity, has been subjected to international community's extensive concern.
PBDE (Polybrominated diphenyl ethers, PBDEs), tetrabromobisphenol A at present
(Tetrabromobisphenol A, TBBP-A) and HBCD (Hexabromocyclododecane, HBCDs)
Manufacturer concentrates on the provinces such as Shandong, Hebei and Jiangsu, and total domestic demand amount the most constantly increases, but current domestic relevant
PBDE (Polybrominated diphenyl ethers, PBDEs), tetrabromobisphenol A
(Tetrabromobisphenol A, TBBP-A) and HBCD (Hexabromocyclododecane, HBCDs) ring
The research work of border problem is the most at the early-stage, is formed without organized systematic study so far, particularly lacks water environment many
Bromo biphenyl ether (Polybrominated diphenyl ethers, PBDEs), tetrabromobisphenol A (Tetrabromobisphenol
A, TBBP-A) and HBCD (Hexabromocyclododecane, HBCDs) complete survey evaluation, also lack simultaneously
Corresponding detection technique and control strategy.About PBDE (Polybrominated diphenyl ethers, PBDEs),
Tetrabromobisphenol A (Tetrabromobisphenol A, TBBP-A) and HBCD (Hexabromocyclododecane,
HBCDs) research report detected is concentrated mainly on water body example and environmental sample aspect, and the method related to mainly includes gas phase color
Spectrum/MS, liquid chromatography/mass spectrometry combination method and high performance liquid chromatography/tandem mass spectrum combination method etc..Due to HBCDs 3
Kind of main isomer can occur thermal rearrangement more than 160 DEG C, debrominate is degraded more than 240 DEG C, thus limit gas chromatogram/
The popularization and application of MS.Relevant document report employing gas chromatogram-electron capture detection (GC-ECD), gas chromatogram-
Mass spectrum (GCMS) carrys out trace tetrabromobisphenol A in test atmosphere sample, and GC-ECD method no doubt has well response to bromine atoms, but
It is to still have some deficits on selectivity；And GC-MS has preferable selectivity, but this detection method detection limit is poor, and needs numerous
Trivial pretreatment and the derivatization of sample.In recent years, along with High Performance Liquid Chromatography/Mass Spectrometry series connection (LC-MS/MS) technology fast
Speed development, LC-MS/MS become PBDE in environment (Polybrominated diphenyl ethers, PBDEs),
Tetrabromobisphenol A (Tetrabromobisphenol A, TBBP-A) and HBCD (Hexabromocyclododecane,
HBCDs) method measuring emerging employing.At present the most only for tetrabromobisphenol A in water (Tetrabromobisphenol A,
TBBP-A) and the pertinent literature report that simultaneously measures of HBCD (Hexabromocyclododecane, HBCDs), also
Have no the relevant report simultaneously analyzing 3 based flame retardants such as HBCD, tetrabromobisphenol A and PBDE.
At present, to PBDE (Polybrominated diphenyl ethers, PBDEs), tetrabromobisphenol A
(Tetrabromobisphenol A, TBBP-A) and HBCD (Hexabromocyclododecane, HBCDs) enter
Row detection is analyzed the main difficulty existed and is included: the specificity that PBDE is analyzed by ESI ionization is more weak, is more vulnerable to complexity
The interference of substrate, causes meeting sample determination requirement.And owing to some seafood oils is high, original pre-treating method
Need the plenty of time.
Summary of the invention
The technical problem to be solved is to provide a kind of easy and simple to handle for above-mentioned prior art present situation, detection
Tetrabromobisphenol A, decabromodiphenyl oxide and HBCD three class bromide fire retardant content in detection aquatic products fast and accurately
Method.
The present invention solves the technical scheme that above-mentioned technical problem used: tetrabromobisphenol A, ten bromines in this detection aquatic products
Biphenyl Ether and the method for HBCD three class bromide fire retardant content, it is characterised in that: comprise the following steps, set up and accelerate
Solvent extraction-fast liquid chromatography-tandem mass spectrum measures tetrabromobisphenol A, decabromodiphenyl oxide and HBCD in aquatic products
Three class bromide fire retardant content, need to detect Aquatic product sample through C18Chromatographic column separates, and mutually carries out gradient with methanol for flowing with water
Eluting, mass spectrum multiple-reaction monitoring mode detection, extraction standard corrects, and quantified by external standard method measures, confirmation.
As improvement, described mass spectrum multiple-reaction monitoring pattern: utilize flow injection pump continuous sample introduction, in the negative ion mode
Carry out full scan, to select adaptive molecular ion peak and ionization mode.
Improving further, described mass spectrum multiple-reaction monitoring pattern, for negative electrospray pattern；Δ EMV600V, is dried gas
Temperature is 300 DEG C；Flows of dry gases is 7L/min；Nebulizer pressure is 30psi；Sheath temperature is 300 DEG C；Sheath throughput
For 10L/min；Capillary voltage is 2000V；Spray nozzle voltage is 1900V.
Improve further, chromatographic condition: Waters ACQUITY UPLC BEH-C18Chromatographic column, chromatographic column specification is:
2.1mm × 100mm, 1.7 μm；It is 40 DEG C that chromatographic column controls；Sample size is 10 μ L；Flow velocity is 0.3mL/min；Mobile phase A is water,
Mobile phase B is methanol.
Improve again, sample pretreatment:
One) sample preparation, weighs about 100g sample, pulverizes with grinder after being cut into small pieces again；
Two) extracting, weigh the 1g sample crushed in qualitative filter paper, sample claims to locate requirement and is accurate to 0.01g, after wrapping
Being placed in abstraction pool and be accelerated solvent extraction, extractant is acetone-hexane solution, sample cell temperature 120 DEG C, pressure
10.3MPa, heat time heating time 5min, static extracting time 10min, nitrogen purge time 100 seconds, cycle-index is 3 times, lavage specimens
The volume in product pond is 20%, and after extraction terminates, extract is evaporated near dry below 40 DEG C, is settled to 3mL with normal hexane,
To be clean；
Three) purify, by C18Sample solution with after 2mL dichloromethane and the activation of 2mL methanol, is crossed post, first by chromatographic column successively
With 12mL normal hexane drip washing, then using 5mL methanol-eluted fractions, collect eluent, it is 1: 1 that nitrogen adds methanol with water mixing ratio after drying up
Solution be settled to 1mL, stir, filter through 0.22 μm syringe filters, measure for fast liquid chromatography-tandem mass spectrum.
As improvement, described accelerated solvent extraction, according to the physical property of detection sample, is 100 μ g/ by adding concentration
Kg solution recovery experiment, and to select acetone and normal hexane be Extraction solvent, the mixed volume of acetone and normal hexane is than for=1: 1.
As improvement, the configuration of standard solution: the most accurately weigh with electronic balance tetrabromobisphenol A, decabromodiphenyl oxide, six
Bromine cyclododecane, described HBCD, in 100mL volumetric flask, is that solvent is accurately joined with methanol and the water of 1: 1 volume ratio
Making 1000 μ g/mL storing solutions, during use, methanol and aqueous solution stepwise dilution are to desired concn, and storing solution is lucifuge storage at 4 DEG C
Depositing, described storing solution is the longest when depositing is 1 month, and described HBCD has three kinds of isomers, be respectively as follows: α-HBCD, β-
HBCD、γ-HBCD。
As improvement, Specification Curve of Increasing, with precision relation: measure storing solution respectively appropriate, in order to 1: 1 volume ratio
Methanol is diluted to the standard working solution that concentration is 1.0,2.0,5.0,10,50 and 100 μ g/L, auto injection 10 μ with the solution of water
L, carries out HPLC-MS/MS analysis, with aquatic products determinand peak area Y under Selective reaction monitoring MRM pattern to corresponding water
Product determinand mass concentration X, the unit of X is μ g/L) use external standard method to draw standard curve, and the standard of 10 μ g/L is worked
Liquid, continuously repeats sample introduction 6 times, calculates the relative standard deviation of peak area, and result see table 1: as seen from the table, aquatic products determinand
When mass concentration is 1.0～100.0 μ g/L linearly well, correlation coefficient r >=0.9988, meet the requirement of quantitative analysis,
The RSD of the range of linearity, regression equation, correlation coefficient r and the peak area of 15 kinds of aquatic products determinands of table
Above-mentioned MRM refers to: mass spectrum multiple-reaction monitoring, and described HPLC-MS/MS refers to: supper-fast liquid chromatograph-
Tandem mass spectrum, the RSD of peak area refers to the area that inside oscillogram, crest and X-axis are surrounded.
Improve further, choose the 22 kinds of aquatic products come into the market, carry out stochastic sampling detection, if not finding positive sample
Product, then will expand examination scope using processing of aquatic products product as acquisition target；The response rate, detection limit and the determination of quantitative limit,
According to 3 times, 10 times of signal to noise ratios determine detection limit, quantitative limit respectively, add 5,50 and 100 μ g/kg 3 in negative sample substrate
The mixed standard solution of individual level, is processed by the method for specimen preprocessing, each horizontal replication 6 times, obtains 5 kinds of targets
The response rate of thing, detection limit and quantitative limit see table 2.The detection of object is limited to 1.0 μ g/kg and 2.0 μ g/kg, is quantitatively limited to
3.0 μ g/kg and 5.0 μ g/kg；And the response rate of 5 kinds of objects exists under 3 different levels adding concentration of standard solution
In the range of 83.6%～95.9%, fully meet tetrabromobisphenol A, decabromodiphenyl oxide and HBCD in domestic and international aquatic products
The requirement of three class bromide fire retardant detections,
The recovery of standard addition of 5 kinds of objects, RSDs, detection limit and quantitative limit in table 2 aquatic products
Described 22 kinds of aquatic products are: Blue Swimming Crab, rich and honour shrimp, Carnis Pseudosciaenae, Carnis Pseudosciaenae, Bombay duck, Nibea albiflora, baby croaker, fish,
Beautiful bald, Stromateoides argenteus, Trichiurus haumela, green grass or young crops account for fish, Spanish mackerel, Chinese herring, mackerel, squid, sepiellae seu sepiae, Thallus Laminariae (Thallus Eckloniae), Rhopilema esculenta, Acaudina molpadioides, razor clam and Conch Meretricis seu Cyclinae.
Described RSDs i.e. refers to: the RSD of peak area refers to the area that inside oscillogram, crest and X-axis are surrounded.
Prior art is compared, and it is an advantage of the current invention that: the detection method of the present invention is easy and simple to handle, detects quick and precisely,
For three class bromide fire retardants, by comparing the pluses and minuses of accelerated solvent extraction and liquid-liquid extraction, optimization Test scheme, set up and close
Suitable extracting method, and ensuring method simple and fast there is outstanding versatility.The parameter of accelerated solvent extraction is examined
Examine and optimize, investigating pressure, extraction time, temperature, sample size and the parsing time shadow to three class bromide fire retardant extraction efficiencies
Ring, obtain optimum extraction condition；According to the character of three class bromide fire retardants, determine optimal sample purification condition, and then set up
Play good resolution, highly sensitive analysis method, to ensure the Stability and veracity of test result, reduce instrument and chromatograph
The infringement of post and pollution；Optimize detection method, by the test such as repeatability, linear, mark-on recovery, determine the method response rate, side
The method and technology indexs such as method minimum detection limit, method stability, sensitivity, the calibration curve range of linearity, meet and analyze requirement；Logical
Cross optimization liquid phase and the various parameter of mass spectrum and condition, it is achieved the sharp separation of three class bromide fire retardants and accurate quantitative analysis, form height
Flux detection method；Integrated common technology, extracts and purifies efficiently, and separating degree is good, the most accurate；Substrate is simple, it is to avoid three classes
Bromide fire retardant is disturbed by complex matrices, avoids the loss of component to be measured during extracting；Use adding of advanced person instant
Agent extraction-LC-MS-MS, sets up and can detect the method for three class bromide fire retardants in aquatic products simultaneously, enter
And perfect three class bromide fire retardant test sensitivity technology and method standard systems.The present invention is not only to ensureing that consumer is healthy
And life security, promote that Aquatic Product Process Industry sustainable and healthy development has huge realistic meaning, it is possible to for food service industry supervision department
Door and testing agency provide favourable technological reserve, and application prospect is wide.
Accompanying drawing explanation
Fig. 1 Yu Fig. 2 is the MRM spectrogram of 20 μ g/L TBBPA standard solution in the embodiment of the present invention；
Fig. 3 Yu Fig. 4 is 20 μ g/L α-HBCD in the embodiment of the present invention, the MRM spectrum of β-HBCD, γ-HBCD standard solution
Figure；
Fig. 5 Yu Fig. 6 is the MRM spectrogram of 20 μ g/L BDE209 standard solution in the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Tetrabromobisphenol A, decabromodiphenyl oxide and HBCD three class bromide fire retardant content in this detection aquatic products
Method, comprises the following steps, and sets up accelerated solvent extraction-fast liquid chromatography-tandem mass spectrum and measures tetrabromobisphenol in aquatic products
A, decabromodiphenyl oxide and HBCD three class bromide fire retardant content, need to detect Aquatic product sample through C18Chromatographic column separates,
Mutually carrying out gradient elution, mass spectrum multiple-reaction monitoring mode detection with methanol for flowing with water, extraction standard corrects, quantified by external standard method
Measure, confirmation.Described mass spectrum multiple-reaction monitoring pattern: utilize flow injection pump continuous sample introduction, carries out complete in the negative ion mode
Scanning, to select adaptive molecular ion peak and ionization mode.Described mass spectrum multiple-reaction monitoring pattern, for negative electrospray mould
Formula；Δ EMV600V, dry gas temperature is 300 DEG C；Flows of dry gases is 7L/min；Nebulizer pressure is 30psi；Sheath gas
Temperature is 300 DEG C；Sheath throughput is 10L/min；Capillary voltage is 2000V；Spray nozzle voltage is 1900V.Chromatographic condition:
Waters ACQUITY UPLC BEH-C18Chromatographic column, chromatographic column specification is: 2.1mm × 100mm, 1.7 μm；Chromatographic column controls
40℃；Sample size is 10 μ L；Flow velocity is 0.3mL/min；Mobile phase A is water, and Mobile phase B is methanol.
Sample pretreatment:
One) sample preparation, weighs about 100g sample, pulverizes with grinder after being cut into small pieces again；
Two) extracting, weigh the 1g sample crushed in qualitative filter paper, sample claims to locate requirement and is accurate to 0.01g, after wrapping
Being placed in abstraction pool and be accelerated solvent extraction, extractant is acetone-hexane solution, sample cell temperature 120 DEG C, pressure
10.3MPa, heat time heating time 5min, static extracting time 10min, nitrogen purge time 100 seconds, cycle-index is 3 times, lavage specimens
The volume in product pond is 20%, and after extraction terminates, extract is evaporated near dry below 40 DEG C, is settled to 3mL with normal hexane,
To be clean；
Three) purify, by C18Sample solution with after 2mL dichloromethane and the activation of 2mL methanol, is crossed post, first by chromatographic column successively
With 12mL normal hexane drip washing, then using 5mL methanol-eluted fractions, collect eluent, it is 1: 1 that nitrogen adds methanol with water mixing ratio after drying up
Solution be settled to 1mL, stir, filter through 0.22 μm syringe filters, measure for fast liquid chromatography-tandem mass spectrum.
Accelerated solvent extraction, according to the physical property of detection sample, is that 100 μ g/kg solution reclaim in fact by adding concentration
Testing, and to select acetone and normal hexane be Extraction solvent, the mixed volume of acetone and normal hexane is than for=1: 1.
The configuration of standard solution: the most accurately weigh tetrabromobisphenol A, decabromodiphenyl oxide, hexabromo ring 12 with electronic balance
Alkane, described HBCD is in 100mL volumetric flask, and methanol and water with 1: 1 volume ratio are that 1000 μ g/ accurately prepared by solvent
ML storing solution, during use, methanol and aqueous solution stepwise dilution are to desired concn, and storing solution lucifuge at 4 DEG C stores, described storage
Standby liquid is the longest when depositing is 1 month, and described HBCD has three kinds of isomers, be respectively as follows: α-HBCD, β-HBCD, γ-
HBCD。
Specification Curve of Increasing, with precision relation: measure storing solution respectively appropriate, in order to methanol and the water of 1: 1 volume ratio
Solution be diluted to the standard working solution that concentration is 1.0,2.0,5.0,10,50 and 100 μ g/L, auto injection 10 μ L, carry out
HPLC-MS/MS analyzes, and treats corresponding aquatic products with aquatic products determinand peak area Y under Selective reaction monitoring MRM pattern
Surveying thing mass concentration X, the unit of X is μ g/L) use external standard method to draw standard curve, and by the standard working solution of 10 μ g/L, even
Continuous repetition sample introduction 6 times, calculates the relative standard deviation of peak area, and result see table 1: as seen from the table, aquatic products determinand quality
When concentration is 1.0～100.0 μ g/L linearly well, correlation coefficient r >=0.9988, meet the requirement of quantitative analysis,
The RSD of the range of linearity, regression equation, correlation coefficient r and the peak area of 15 kinds of aquatic products determinands of table
Above-mentioned MRM refers to: mass spectrum multiple-reaction monitoring, and described HPLC-MS/MS refers to: supper-fast liquid chromatograph-
Tandem mass spectrum, the RSD of peak area refers to the area that inside oscillogram, crest and X-axis are surrounded.
Choose the 22 kinds of aquatic products come into the market, carry out stochastic sampling detection, if not finding positive, then will be with
Processing of aquatic products product, as acquisition target, expand examination scope；The response rate, detection limit and the determination of quantitative limit, according to 3 times, 10
Times signal to noise ratio determines detection limit, quantitative limit respectively, adds the mixed of 5,50 and 100 3 levels of μ g/kg in negative sample substrate
Standardization solution, is processed by the method for specimen preprocessing, each horizontal replication 6 times, obtains the recovery of 5 kinds of objects
Rate, detection limit and quantitative limit see table 2.The detection of object is limited to 1.0 μ g/kg and 2.0 μ g/kg, is quantitatively limited to 3.0 μ g/kg
With 5.0 μ g/kg；And under 3 different levels adding concentration of standard solution the response rate of 5 kinds of objects 83.6%～
In the range of 95.9%, fully meet tetrabromobisphenol A in domestic and international aquatic products, decabromodiphenyl oxide and HBCD three class bromine system
The requirement of fire retardant detection,
The recovery of standard addition of 5 kinds of objects, RSDs, detection limit and quantitative limit in table 2 aquatic products
Described 22 kinds of aquatic products are: Blue Swimming Crab, rich and honour shrimp, Carnis Pseudosciaenae, Carnis Pseudosciaenae, Bombay duck, Nibea albiflora, baby croaker, fish,
Beautiful bald, Stromateoides argenteus, Trichiurus haumela, green grass or young crops account for fish, Spanish mackerel, Chinese herring, mackerel, squid, sepiellae seu sepiae, Thallus Laminariae (Thallus Eckloniae), Rhopilema esculenta, Acaudina molpadioides, razor clam and Conch Meretricis seu Cyclinae.
Described RSDs i.e. refers to: the RSD of peak area refers to the area that inside oscillogram, crest and X-axis are surrounded.
Sample pretreating method is studied:
Relatively accelerated solvent extraction access method and the pretreating effect of traditional method, optimization Test scheme, set up suitable mesh
Mark thing extracting method, and simple, the quick and versatility of ensuring method.And the parameter of automatic head space investigated and optimizes,
Investigating pressure, extraction time, temperature, tetrabromobisphenol A, decabromodiphenyl oxide and HBCD are extracted by sample size with the time of parsing
Take the impact of efficiency, confirm optimum extraction condition.
According to the character of three class bromide fire retardants, the most different purification styles, determine optimal sample purification condition, enter
And set up good resolution, highly sensitive analysis method, with ensure the Stability and veracity of test result and reduce right
Instrument and the infringement of chromatographic column and pollution.
Detection method optimizes: by the test such as repeatability, linear, mark-on recovery, determining the method response rate, method minimum is examined
The method and technology indexs such as rising limit, method stability, sensitivity, the calibration curve range of linearity, meet and analyze requirement.
Use liquid chromatography tandem mass spectrometry to measure three class bromide fire retardants, by optimize liquid phase and the various parameter of mass spectrum and
Condition, it is achieved the sharp separation of three class bromide fire retardants and accurate quantitative analysis, forms high-flux detection method.
Integrated common technology, sets up that high efficiency extraction and purification, high flux, separating degree be good, three class bromine systems resistance the most accurately
The method for quick of combustion agent.
Set up three class bromide fire retardant pollution situation data base in aquatic products.
Choose the typical marine products fabricated product that Along Zhejiang Coast aquatic products processing enterprise produces, carry out Aquatic product by the method set up
The detection of three class bromide fire retardants and analysis in product, set up pollution situation data base, and research affect in aquatic products three class bromine systems and hinders
The principal element that combustion agent is formed, for aquatic products processing, preserve, transport and during trade, the monitoring of three class bromide fire retardants carries
Technical support.
After the present invention practices successfully, can be that processing of aquatic products manufacturing enterprise successfully manages international trade technology barriers and does
Good technical support and service, greatly instant aquatic product processing and outlet, increase the economic benefit of enterprise, can increase warp every year
Ji income more than 500,000 yuan, year tax increase gold more than 100,000 yuan.Meanwhile, the present invention can also increase the health service revenue of testing agency, presses
According to annual detection 200 batches, the 500 yuan of calculating of charge of every batch, this income is 100,000 yuan every year.
The optimization of flowing phase
Difference flowing is selected to carry out the separating degree of chromatographic peak and the comparison of sensitivity and research mutually.Because Electrospray Mass Spectrometry
Ionization is to ionize at solution state, the composition of flowing phase and additive therein except affect the retention time of target compound with
Outside peak shape, have an effect on Ionization Efficiency, thus affect detection sensitivity.Test while meeting preferable chromatographic isolation, than
Compared with methanol-water and the impact of acetonitrile-water both flowing relative target compound ions degree.Result shows, works as flowing
When being methanol-water mutually, response value is apparently higher than the response value (about 2～4 times) being the phase time that flows with acetonitrile-water.Therefore, select
Methanol-water is flowing phase.
In addition to investigating flowing phase composition, also compares flowing and add one for methanol-water in flowing mutually at this respectively mutually
The additive impacts on target compound Ionization Efficiency such as quantitative ammonium acetate and ammonia.Result shows: a certain amount of when adding
Ammonium acetate or ammonia after, the response value of target compound decreases on the contrary, and therefore, experiment finally determines and makees with methanol-water
For flowing phase.
The optimization of extraction conditions
According to the physical property of object, by recovery testu (in sample, spiked levels is 100 μ g/kg) contrast extraction
Take agent methanol, acetonitrile, acetone, dichloromethane, normal hexane and the extraction efficiency of relevant mixed solution.It was found that methanol and
During dichloromethane extraction, impurity content is higher, and matrix interference is relatively large；The extraction efficiency of acetonitrile compares methanol, dichloromethane
Alkane is slightly higher, but compared with acetone and normal hexane, dissolubility is poor.Final selection acetone and normal hexane are as Extraction solvent.And warp
Cross and repeatedly test discovery, acetone: normal hexane=1: the extraction yield of 1 (V/V) solution is higher up to 92%.
The optimization of Mass Spectrometry Conditions
Use multiple-reaction monitoring (MRM) pattern, utilize flow injection pump continuous sample introduction, the most entirely sweep
Retouch, to select suitable molecular ion peak and ionization mode.Result shows, under Negative electrospray ionization ionization pattern, and target chemical combination
The quasi-molecular ion [M-H] of thing full scan-[M-Br+O]-More stable, [M-H]-Ionic strength ratio [M-Br+O]-From
Sub-intensity is big.Therefore [M-H] of target compound is selected in experiment-For the parent ion of collision induced dissociation, to testing compound
Collision energy and various voltage parameter are optimized, and the mass spectral analysis parameter after the ion pair of each compound and optimization is shown in Table 2,
The MRM spectrogram of each target compound is shown in Fig. 1～6.
Described Psi is a kind of pressure unit, i.e. 1mpa=145psi.BDE209 in form is decabromodiphenyl oxide.
Described Δ EMV is to represent: the voltage of electron multiplier.
Described sheath gas refers to: is used in mass spectrum being atomized, going solvent gas to be generally nitrogen in sheath gas, sheath gas, rises and help stream
The dynamic effect gasified mutually.Described 5 kinds of objects refer to: TBBPA, α-HBCD, β-HBCD, γ-HBCD, the response rate of BDE209.
TBBPA represents: tetrabromobisphenol A, and BDE209 represents: decabromodiphenyl oxide, HBCD HBCD three class bromine.Wherein α-HBCD,
β-HBCD, γ-HBCD are the three kinds of isomers representing HBCD.
Claims (9)
1. one kind is detected tetrabromobisphenol A in aquatic products, decabromodiphenyl oxide and HBCD three class bromide fire retardant content
Method, it is characterised in that: comprise the following steps, set up accelerated solvent extraction-fast liquid chromatography-tandem mass spectrum and measure aquatic products
Middle tetrabromobisphenol A, decabromodiphenyl oxide and HBCD three class bromide fire retardant content, need to detect Aquatic product sample through C18Color
Spectrum post separates, and mutually carries out gradient elution, mass spectrum multiple-reaction monitoring mode detection with methanol for flowing with water, and extraction standard corrects,
Quantified by external standard method measures, confirmation.
Method the most according to claim 1, it is characterised in that: described mass spectrum multiple-reaction monitoring pattern: utilize flow injection
Pump continuous sample introduction, carries out full scan in the negative ion mode, to select adaptive molecular ion peak and ionization mode.
Method the most according to claim 2, it is characterised in that: described mass spectrum multiple-reaction monitoring pattern, for anion EFI
Mist pattern；Δ EMV600V, dry gas temperature is 300 DEG C；Flows of dry gases is 7L/min；Nebulizer pressure is 30psi；
Sheath temperature is 300 DEG C；Sheath throughput is 10L/min；Capillary voltage is 2000V；Spray nozzle voltage is 1900V.
Method the most according to claim 3, it is characterised in that: chromatographic condition: Waters ACQUITY UPLC BEH-C18
Chromatographic column, chromatographic column specification is: 2.1mm × 100mm, 1.7 μm；It is 40 DEG C that chromatographic column controls；Sample size is 10 μ L；Flow velocity is
0.3mL/min；Mobile phase A is water, and Mobile phase B is methanol.
Method the most according to claim 4, it is characterised in that: sample pretreatment:
One) sample preparation, weighs about 100g sample, pulverizes with grinder after being cut into small pieces again；
Two) extracting, weigh the 1g sample crushed in qualitative filter paper, sample claims to locate requirement and is accurate to 0.01g, wraps and is placed on
Being accelerated solvent extraction in abstraction pool, extractant is acetone-hexane solution, sample cell temperature 120 DEG C, pressure 10.3MPa,
Heat time heating time 5min, static extracting time 10min, nitrogen purge time 100 seconds, cycle-index is 3 times, rinse sample cell body
Amassing is 20%, and after extraction terminates, extract is evaporated near dry below 40 DEG C, is settled to 3mL with normal hexane, to be clean；
Three) purify, by C18Sample solution with after 2mL dichloromethane and the activation of 2mL methanol, is crossed post, is first used by chromatographic column successively
12mL normal hexane drip washing, then use 5mL methanol-eluted fractions, collect eluent, it is 1: 1 that nitrogen adds methanol with water mixing ratio after drying up
Solution is settled to 1mL, stirs, and filters through 0.22 μm syringe filters, measures for fast liquid chromatography-tandem mass spectrum.
6. according to described method arbitrary in claim 1 to 5, it is characterised in that: described accelerated solvent extraction, according to detection sample
The physical property of product, is 100 μ g/kg solution recovery experiments by adding concentration, and to select acetone and normal hexane is Extraction solvent,
Acetone is=1: 1 with the mixed volume ratio of normal hexane.
7. according to described method arbitrary in claim 1 to 5, it is characterised in that: the configuration of standard solution: divide with electronic balance
The most accurately weigh tetrabromobisphenol A, decabromodiphenyl oxide, HBCD, described HBCD in 100mL volumetric flask,
Methanol and water with 1: 1 volume ratio are that 1000 μ g/mL storing solutions accurately prepared by solvent, and during use, methanol is the dilutest with aqueous solution
Releasing to desired concn, storing solution lucifuge at 4 DEG C stores, and described storing solution is the longest when depositing is 1 month, described hexabromo ring 12
Alkane has three kinds of isomers, is respectively as follows: α-HBCD, β-HBCD, γ-HBCD.
8. according to described method arbitrary in claim 1 to 5, it is characterised in that: Specification Curve of Increasing, and precision relation:
Measuring storing solution respectively appropriate, being diluted to concentration in order to the methanol of 1: 1 volume ratio and the solution of water is 1.0,2.0,5.0,10,50
With the standard working solution of 100 μ g/L, auto injection 10 μ L, carry out HPLC-MS/MS analysis, selecting instead with aquatic products determinand
Should monitor the peak area Y under MRM pattern is μ g/L to corresponding aquatic products determinand mass concentration X, the unit of X) use external standard
Method draws standard curve, and by the standard working solution of 10 μ g/L, continuously repeats sample introduction 6 times, and the relative standard calculating peak area is inclined
Difference, result see table 1: as seen from the table, linearly good when aquatic products determinand mass concentration is 1.0～100.0 μ g/L, phase relation
Number r >=0.9988, meets the requirement of quantitative analysis,
The RSD of the range of linearity, regression equation, correlation coefficient r and the peak area of 15 kinds of aquatic products determinands of table
Above-mentioned MRM refers to: mass spectrum multiple-reaction monitoring, and described HPLC-MS/MS refers to: supper-fast liquid chromatography-tandem
Mass spectrum, the RSD of peak area refers to the area that inside oscillogram, crest and X-axis are surrounded.
Method the most according to claim 8, it is characterised in that: the mensuration of sample: choose the 22 kinds of aquatic products come into the market,
Carrying out stochastic sampling detection, if not finding positive, then will expand examination using processing of aquatic products product as acquisition target
Scope；The response rate, detection limit and the determination of quantitative limit, according to 3 times, 10 times of signal to noise ratios determine detection limit respectively, and quantitative limit, at the moon
Property sample substrate in add the mixed standard solution of concentration in 5,50 and 100 μ g/kg tri-, at the method for specimen preprocessing
Reason, every kind of concentration level replication 6 times, obtain the response rate of 5 kinds of objects, detection limit and quantitative limit see table 2.Object
Detection be limited to 1.0 μ g/kg and 2.0 μ g/kg, be quantitatively limited to 3.0 μ g/kg and 5.0 μ g/kg；And it is molten 3 different addition standards
The response rate of the lower 5 kinds of objects of level of liquid concentration, in the range of 83.6%～95.9%, fully meets in domestic and international aquatic products
Tetrabromobisphenol A, decabromodiphenyl oxide and the requirement of HBCD three class bromide fire retardant detection,
The recovery of standard addition of 5 kinds of objects, RSD in table 2 aquatic productss, detection limit and quantitative limit
Described 22 kinds of aquatic products are: Blue Swimming Crab, rich and honour shrimp, Carnis Pseudosciaenae, Carnis Pseudosciaenae, Bombay duck, Nibea albiflora, baby croaker, fish, jade
Bald, Stromateoides argenteus, Trichiurus haumela, green grass or young crops account for fish, Spanish mackerel, Chinese herring, mackerel, squid, sepiellae seu sepiae, Thallus Laminariae (Thallus Eckloniae), Rhopilema esculenta, Acaudina molpadioides, razor clam and Conch Meretricis seu Cyclinae.Institute
State RSDs i.e. to refer to: the RSD of peak area refers to the area that inside oscillogram, crest and X-axis are surrounded.
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| CN107024555A (en) * | 2017-04-26 | 2017-08-08 | 华南农业大学 | A kind of method of HBCD in extraction and determination plant soil system |
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