CN104049049A - Method for synchronously detecting plurality of organophosphorus fire retardants in bottom mud - Google Patents
Method for synchronously detecting plurality of organophosphorus fire retardants in bottom mud Download PDFInfo
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Abstract
The invention discloses a method for synchronously detecting a plurality of organophosphorus fire retardants in bottom mud, belonging to the detection field of trace amount of organophosphorus fire retardants in the environment. The method comprises the main steps of firstly, extracting a target object in a sample through an accelerated solvent extraction instrument; purifying by a gel permeation chromatography; further purifying and enriching by adopting a solid-phase small extraction column; and finally, concentrating and making up to the constant volume and detecting and quantifying by using a gas chromatograph-mass spectrometer. According to the invention, a pre-treatment method for the organophosphorus fire retardants in the bottom mud is established and optimized, the automation degree is high and the repeatability is good; the gas chromatograph-mass spectrometer is used for carrying out quantitative detection, the detection limit is low and the sensitivity is high; the detection limit to nine types of the organophosphorus fire retardants are lower than 0.340 microgram per gram. According to the method, the synchronous analysis and detection on the plurality of trace amount of organophosphorus fire retardants in a complicated environment medium, namely the bottom mud, is realized; the sensitivity and the accuracy are achieved, and the method makes up the disadvantages of the technology in the field.
Description
Technical field
The present invention relates to a kind of detection method of Environmental Trace organophosphorous fire retardant, more particularly, relate to the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud.
Background technology
Organophosphorous fire retardant (Organic Phosphate Flame Retardants, OPFRs) there is flame retardant effect lasting, the feature such as good, water-fast, heat-resisting and resistance to migration, is widely used in the industries such as electronics, weaving, chemical industry, building materials with polymeric substrate compatibility.Being widely used of organophosphorous fire retardant, also can produce certain impact to the mankind and ecologic environment.Part organophosphorous fire retardant character is very stable, has bioaccumulation, and be in contact with it for a long time and can produce adverse influence to human body, as function of immune system is degenerated, reproductive system obstacle, subthyroidism, even part organophosphorous fire retardant has carcinogenicity.Different from other adjuvants, organophosphorous fire retardant is by mixing but not the mode of chemical bonding is added in material, is therefore easily diffused in environment by modes such as evaporation, wearing and tearing, diafiltrations.Soil is a large receptor of organophosphorous fire retardant, for example, the people such as the Elke Fries of Germany detect tricresyl phosphate (2-chloroethyl) ester (tri (2-chloroethyl) phosphate in soil, TCEP), tricresyl phosphate-(2-chloropropyl) ester (tri (1-chloro-2-propyl) phosphate, and tricresyl phosphate (butoxyethyl group) ester (Tris (2-butoxyethyl) phosphate, TBEP) TCPP).
There is very large difference in the physicochemical property of different organophosphorous fire retardants, for example, triethyl phosphate (Triethyl Phosphate, TEP) there are very strong polarity and high volatility, and tricresyl phosphate (2-ethyl) hexyl ester (Tri (2-ethylhexyl) Phosphate, TEHP) is insoluble in water and not volatile.This has brought certain difficulty to the synchronous detection analysis of multiple organophosphorous fire retardant.Bed mud matrix complexity, contains the impurity such as a large amount of organic matters and pigment, and its analytic process comprises the steps such as extraction, purification and instrumental analysis.The report detecting about organophosphorous fire retardant in bed mud is at present less.Extracting process mainly contains soxhlet extraction, using microwave-assisted and accelerated solvent extraction and follows the example of (Accelerated Solvent Extraction, ASE).Gel permeation chromatography (Gel Permeation Chromatography, GPC) is advanced large molecule removal technology, is widely used at present removing large molecular impurity in the complex environment samples such as biological sample and bed mud.Solid-Phase Extraction (Solid Phase Extraction, SPE) can selective adsorption object and the material of similar quality.GC-MS(gas chromatography-mass spectrography) (Gas Chromatography-Mass, GC-MS) is applicable to doing the qualitative and quantitative analysis of many mixture.
M.Garcia-Lopez was at (Garcia-Lopez M. in 2009, Rodriguez I., Cela R., Pressurized liquid extraction of organophosphate triesters from sediment samples using aqueous solutions.Journal of Chromatography A, 2009, 1216 (42): 6986-6993.) ASE and the analytical approach of SPE coupling to organophosphorous fire retardant pre-treatment in bed mud sample have been reported, but because ASE extraction solvent in the method is selected water: acetonitrile (75/25, v/v), the TEHP recovery to low pole is not high, therefore be difficult to realize the synchronous detection to organophosphorous fire retardant in bed mud sample.
Summary of the invention
1. the technical matters that invention will solve
The object of the present invention is to provide the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud, set up a kind of effective ASE-GPC-SPE and combined the technology of carrying out pre-treatment, optimize each extraction, purified and detect Pretreatment, by with GC-MS coupling, can not synchronously detect multiple organophosphorous fire retardant in bed mud thereby overcome, and in complex environment, multiple organophosphorous fire retardant detects the problem of weak effect.
2. technical scheme
For achieving the above object, the present invention passes through the coupling of the multiple technologies such as accelerated solvent extraction, gel permeation chromatography purification, solid phase extraction concentration and gas chromatograph-mass spectrometer (GCMS) detection, thereby realizes synchronous extraction, purification, enrichment and the mensuration of multiple organophosphorous fire retardant in bed mud.Concrete technical scheme is as follows:
Step 1: the processing of bed mud sample, the bed mud sample that pre-freeze is crossed is placed in the freeze-drying of freeze-drying instrument, and the bed mud sample after freeze-drying is ground and cross 200 mesh sieves;
Step 2: accelerated solvent extraction extracts object with ethyl acetate under High Temperature High Pressure;
Step 3: gel permeation chromatography purifies, and according to molecular size range difference, partial impurities is removed;
Step 4: solid-phase extraction column purification enrichment, do further purification with solid phase extraction column, eluent is concentrated, solvent is replaced constant volume again, is transferred in sample introduction bottle to be measured;
Step 5: upper machine testing, by gas chromatograph-mass spectrometer (GCMS), sample is measured.
Further, in step 2, weighing bed mud sample is 5-10g, adds mark mixed solution in recovery instruction, equilibrate overnight; Weigh again 2-5g zeyssatite and bed mud sample stirs and evenly mixs.
In step 2, accelerated solvent extraction condition is: make extraction solvent with ethyl acetate, at 1500psi pressure, under 90 DEG C of extraction temperature conditions, heating, static extracting, circulates 2 times, be the solvent washing abstraction pool of abstraction pool volume 60% with volume, finally use nitrogen blowing 110s.
The eluting solvent using in step 3 is the potpourri of ethyl acetate and cyclohexane, and the volume ratio of ethyl acetate and cyclohexane is 1:1, and the acquisition time of efflux is 7.5-20min.
In step 4, solid-phase extraction column used is HLB post, and flow velocity keeps 4ml/min, the ethyl acetate that eluting solvent is 3-5ml.
In step 5, the heating schedule of gas chromatography is 50 DEG C of chromatographic column initial temperatures, keeps after 1min, with 25 DEG C/min temperature programme to 280 DEG C, keeps 3min; 280 DEG C of transmission line temperature.
What in step 5, gas chromatograph-mass spectrometer (GCMS) adopted is EI source, and scan mode is for selecting ion scan pattern.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, have and showing as follows effect:
(1) the present invention sets up and has optimized the ASE-GPC-SPE combination pre-treating method of organophosphorous fire retardant in bed mud sample, and carries out quantitative test with GC-MS.The feature of this method is that automaticity is high, and favorable reproducibility also can realize good extraction and clean-up effect to this complex environment medium of bed mud.
(2) Synchronization Analysis of the present invention 9 kinds of organophosphorous fire retardants, the absolute recovery of all types of target thing is 36.97%-94.14%, relative recovery is 87%-114%, relative standard deviation is 2%-15%, detecting of method is limited to 0.003-0.340 μ g/g, quantitatively be limited to 0.012-0.800 μ g/g, meet the requirement of quantitative test.
(3) the present invention sets up and has optimized ASE-GPC-SPE extraction, purification and the GC-MS detection coupling of organophosphorous fire retardant in bed mud sample, has realized synchronous, quick, accurate, the sensitive quantitative detection of multiple organophosphorous fire retardant in bed mud.
Brief description of the drawings
Fig. 1 is the standard substance of the organophosphorous fire retardant elution curve on GPC post;
Fig. 2 is that in embodiment 2,9 kinds of organophosphorous fire retardants, the interior mark of recovery instruction and quantitatively interior targets select ion to sweep chromatogram.
Embodiment
The present invention carries out synchronous qualitative and quantitative detection with GC-MS to multiple organophosphorous fire retardant in bed mud sample, according to the characteristic ion (table 1) of retention time and selection, with spectrogram (Fig. 2) contrast of n-compound, can judge in bed mud sample, whether to contain this kind of compound; According to object and interior target peak area ratio, utilize external standard method to calculate the concentration of each organophosphorous fire retardant in bed mud sample.
Instrument and reagent:
Gas chromatograph: ThermoFisher company of the U.S.; Chromatographic column: (30m × 0.25mm × 0.25 μ m) for AglientDB-5MS chromatographic column; Carrier gas: helium (purity 99.999%).
Mass spectrometer: Thermo Fisher company of the U.S..
Organophosphorous fire retardant standard reserving solution: 9 kinds of organophosphorous fire retardants adopt ethyl acetate dilution, are mixed with respectively the standard reserving solution that concentration is 10 μ g/ml.
Organophosphorous fire retardant hybrid standard storing solution: respectively get 1ml and mix in 10mL volumetric flask in 9 kinds of organophosphorous fire retardant standard reserving solutions, with ethyl acetate dilution, be configured to the hybrid standard storing solution of 1 μ g/mL.
The interior mark recovery is mixed storing solution: in 4 kinds of recovery indicants, mark (TPrP-d21, TnBP-d27 and TPhP-d15) mixes storing solution (1 μ g/mL) by the mark recovery in ethyl acetate preparation.Due to bed mud matrix complexity, experiment selects TEP-d15, TPrP-d21, TnBP-d27 and TPhP-d15 as mark in recovery instruction, determine the relative recovery of all types of target compound, the experimental error that the nonrepeatability of minimizing instrument state and experimental implementation is brought, it is quantitatively more accurate to make.
PCB156-d3 storing solution: with ethyl acetate preparation internal standard compound PCB156-d3 storing solution (480ng/mL).
Embodiment 1
The present embodiment focuses on the optimization of analyzing organophosphorous fire retardant GC-MS assay method in standard solution.
Step 1, the preparation of standard model: the hybrid standard that preparation gradient is 5-500ng/L uses liquid.Be specially and get respectively a certain amount of organophosphorous fire retardant hybrid standard storing solution and the interior mark recovery with liquid-transfering gun and mix storing solution and be placed in sample introduction bottle, add again 240ng internal standard compound PCB156-d3, be diluted to 1mL with ethyl acetate, obtain the standard solution of respective concentration.
Step 2: above-mentioned each concentration hybrid standard uses liquid to carry out GC-MS detection, sets chromatographic condition and is: flow 1mL/min; 250 DEG C of injector temperatures, sample size 1 μ L, pulse Splitless injecting samples; 50 DEG C of chromatographic column initial temperatures, keep after 1min, with 25 DEG C/min temperature programme to 280 DEG C, keep 3min; 280 DEG C of transmission line temperature.Mass spectrum condition is: electron impact ion source (EI); Electron accelerating voltage 70eV; 250 DEG C of ion source temperatures; Scan mode is that ion scan (SIM) is selected in full scan (Full Scan) and segmentation; Entirely sweep scope: m/z50-500.
The GC-MS parameter of various organophosphorous fire retardants is in table 1.
The GC-MS parameter list of the various organophosphorous fire retardants of table 1
Taking object and interior target peak area ratio as ordinate, taking sample concentration as horizontal ordinate, draw and obtain typical curve.Result shows: typical curve related coefficient (R
2) be 0.9853-0.9972, detecting of definite method is limited to 0.003-0.340 μ g/g thus, is quantitatively limited to 0.012-0.800 μ g/g, and concrete outcome is in table 2.
Table 2 organophosphorous fire retardant standard model testing result table
OPFRs recovery testu in embodiment 2 bed mud samples
Step 1: get 6 parts of 5g bed mud sample that freeze-drying is sieved, wherein add the OPFRs hybrid standard storing solution containing 100ng in 5 parts, add containing mark in four kinds of recovery instructions of 100ng and mix storing solutions.In portion, only add in addition mark in recovery instruction to mix storing solution, blank in contrast.
Step 2, packs 6 duplicate samples in ASE abstraction pool into, makees extraction solvent with ethyl acetate, at 1500psi pressure, under 90 DEG C of extraction temperature conditions, heating 5min, static extracting 5min, circulate 2 times, with 60% solvent washing abstraction pool of abstraction pool volume, finally use nitrogen blowing 110s.Extracted rear collection extract (about 60mL), rotary evaporation, to 1mL, then adds ethyl acetate: cyclohexane (1:1, v/v) mixed solvent, be settled to 10mLGPC bottle, and treat that next step GPC purifies.
Step 3, GPC purifies: the solution system being made by step 2 injects the GPC post that Biobead S-X3 filler is housed by 5.0mL proportional valve, eluent is ethyl acetate: cyclohexane (1:1, v/v), flow rate pump 4.7mL/min, discard the flow point of 0-7.5min, collect the flow point of 7.5-20.0min, with 20.0-23.0min flow point flushing GPC post.After the flow point rotary evaporation of the 7.5-20.0min of collection is concentrated, be dissolved to about 0.6mL, be diluted to 200mL with ultrapure water, add a methyl alcohol, treat that next step SPE purifies.
Step 4, SPE purifies: choose HLB pillar as purifying pillar, first with 3mL methyl alcohol activation pillar, with 3mL ultrapure water balance pillar, then cross post with the flow velocity loading of 4mL/min, low vacuum is drained SPE pillar, use 3mL eluent ethyl acetate, collect eluent, nitrogen blows to 100 μ L, add interior mark PCB156-d324ng, then be settled to 1mL with ethyl acetate.
Step 5, GC-MS detects: according to embodiment 1 step 2,9 kinds of organophosphorous fire retardants in bed mud sample are carried out to quantitative test.
Can determine organophosphorous fire retardant and interior target chromatographic peak (seeing Fig. 2) according to retention time and quota ion.Experimental result is, the absolute recovery of all types of target thing is 36.97%-94.14%, and relative recovery is 87%-114%, and relative standard deviation is 2%-15%, meets the requirement of quantitative test, the results are shown in Table 2.
In embodiment 3 bottom mud in Taihu Lakes, organophosphorous fire retardant sampling analysis detects
Step 1: sample collection and processing, when sampling, adopt grab bucket-type dredger to gather sediments, and freezing preservation at once.Transport back behind laboratory, in-20 DEG C of refrigerator freezings, adopt freeze drier to carry out freeze drying, grind with mortar, cross 100 order metallic screens, to be analyzed in-20 DEG C of preservations.
Step 2: the bed mud sample of each some position is got 5g, according to the step 2 in embodiment 2 to step 4 sample-pretreating method, sample is carried out to pre-treatment.
Step 3: the sample solution of handling is carried out to GC-MS qualitative and quantitative detection according to the step 5 in embodiment 2.Survey five some positions OPFRs concentration in table 3.
The concentration table of OPFRs in the bottom mud in Taihu Lake of a table 35 point position sampling
Note: nd: do not detect.
The method of multiple organophosphorous fire retardant in a kind of synchronous detection bed mud described in embodiment 1-3, sets up and has optimized the ASE-GPC-SPE combination pre-treating method that detects organophosphorous fire retardant in bed mud sample.The feature that this pre-treating method and GC-MS detect the embodiment of coupling is that automaticity is high, and favorable reproducibility, has realized synchronous, quick, accurate, the sensitive quantitative detection of multiple organophosphorous fire retardant in bed mud.Test known ethyl acetate by recovery of standard addition 9 kinds of organophosphorous fire retardants in bed mud are had to the higher recovery, also can realize good extraction and clean-up effect to this complex environment medium of bed mud.
Claims (8)
1. a synchronous method that detects multiple organophosphorous fire retardant in bed mud:
Step 1: the processing of bed mud sample, the bed mud sample that pre-freeze is crossed is placed in the freeze-drying of freeze-drying instrument, and the bed mud sample after freeze-drying is ground and cross 200 mesh sieves;
Step 2: accelerated solvent extraction extracts object with ethyl acetate under High Temperature High Pressure;
Step 3: gel permeation chromatography purifies, and according to molecular size range difference, partial impurities is removed;
Step 4: solid-phase extraction column purification enrichment, do further purification with solid phase extraction column, eluent is concentrated, solvent is replaced constant volume again, is transferred in sample introduction bottle to be measured;
Step 5: upper machine testing, by gas chromatograph-mass spectrometer (GCMS), sample is measured.
2. the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud according to claim 1, is characterized in that in step 2, weighing bed mud sample is 5-10g, adds mark mixed solution in recovery instruction, equilibrate overnight; Weigh again 2-5g zeyssatite and bed mud sample stirs and evenly mixs.
3. the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud according to claim 1, it is characterized in that in step 2, accelerated solvent extraction condition is: make extraction solvent with ethyl acetate, at 1500psi pressure, under 90 DEG C of extraction temperature conditions, heating, static extracting, circulates 2 times, be the solvent washing abstraction pool of abstraction pool volume 60% with volume, finally use nitrogen blowing 110s.
4. according to the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud described in any one in claim 1-3, the potpourri that the eluting solvent that it is characterized in that using in step 3 is ethyl acetate and cyclohexane, the volume ratio of ethyl acetate and cyclohexane is 1:1, and the acquisition time of efflux is 7.5-20min.
5. according to the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud described in any one in claim 1-3, it is characterized in that in step 4, solid-phase extraction column used is HLB post, flow velocity keeps 4mL/min, the ethyl acetate that eluting solvent is 3-5mL.
6. according to the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud described in any one in claim 1-3, the heating schedule that it is characterized in that gas chromatography in step 5 is 50 DEG C of chromatographic column initial temperatures, keep after 1min, with 25 DEG C/min temperature programme to 280 DEG C, keep 3min; 280 DEG C of transmission line temperature.
7. according to the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud described in any one in claim 1-3, what it is characterized in that in step 5, gas chromatograph-mass spectrometer (GCMS) adopts is EI source, and scan mode is for selecting ion scan pattern.
8. the method for multiple organophosphorous fire retardant in a kind of synchronous detection bed mud according to claim 1, is characterized in that:
In step 2, accelerated solvent extraction condition is: at 1500psi pressure, and under 90 DEG C of extraction temperature conditions, heating, static extracting;
The eluting solvent using in step 3 is the potpourri of ethyl acetate and cyclohexane, and the volume ratio of ethyl acetate and cyclohexane is 1:1, and the acquisition time of efflux is 7.5-20min;
In step 4, solid-phase extraction column used is HLB post, and flow velocity keeps 4mL/min, and eluting solvent is ethyl acetate;
In step 5, the heating schedule of gas chromatography is 50 DEG C of chromatographic column initial temperatures, keeps after 1min, with 25 DEG C/min temperature programme to 280 DEG C, keeps 3min; 280 DEG C of transmission line temperature; What gas chromatograph-mass spectrometer (GCMS) adopted is EI source, and scan mode is for selecting ion scan pattern.
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