CN102183606A - Method for detecting estrogen, nonyl phenol, octyl phenol and bisphenol A in water body sediment together - Google Patents
Method for detecting estrogen, nonyl phenol, octyl phenol and bisphenol A in water body sediment together Download PDFInfo
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Abstract
The invention discloses a method for detecting estrogen, nonyl phenol, octyl phenol and bisphenol A in water body sediment based on an accelerated solvent extraction (ASE), liquid-liquid extraction (LLE) and liquid chromatography/tandem mass spectrum (LC/MS/MS) technology. The method comprises the following steps of: performing accelerated solvent extraction by using acetone as an extracting agent to extract the estrogen, the nonyl phenol, the octyl phenol and the bisphenol A in the water body sediment; dissolving residues generated after extract is blown by nitrogen by using 1mol/L sodium hydroxide solution, performing centrifugal collection on the supernate, and performing liquid-liquid extraction by using ethyl acetate under the condition that the pH is equal to 2; and performing concentration detection by using a 3200QTRAP type liquid chromatography/tandem mass spectrometer and an Agilent 1100 high performance liquid chromatography system of American Applied Biosystem Company and an automatic sample injector of American Agilent Company. The recovery rate is 59 to 94 percent, and the detection limit is 0.04ng/g.
Description
Technical field
The present invention relates to the quick solvent extraction-liquid-liquid extraction of a kind of employing-liquid chromatography/tandem mass spectrum coupling (ASE-LLE-LC/MS/MS) organic contaminant in the water body deposit is carried out the detection technique field, particularly relate to the co-detection method of trace estrogen in the sediment and nonylphenol thereof, octyl phenol, bisphenol-A.
Background technology
Natural estrogen oestrone (Estrone by people and animal ovary secretion, E1), 17 beta estradiols (17 β-Estradiol, E2) and estriol (Estriol, E3), and as synthetic estrogen 17 α-ethinyl estradiol (17 α-Ethinyl Estradiol of oral contraceptive principal ingredient, EE2), can enter in sewage disposal system or the agricultural land soil along with the fecaluria discharging.Estrogenic discharging is inevitably, and estrogen is subjected to extensive concern as typical incretion interferent over past ten years.States such as America and Europe show how tame sewage treatment plant estrogen concentrations and the investigation result of removing efficient, and residual the estrogen of ng/L concentration level in sewage disposal plant effluent and receiving water body shows that sewage treatment plant can not effectively remove the estrogen in the water inlet.The estrogen of livestock and poultry breeding industry discharging can be used or rainwash enters in soil and the water body by compost.The result of study of relevant fish reproduction abnormal occurrence shows, the estrogen of contained ng/L concentration level is to cause the feminize main cause material of reproduction abnormal occurrence of fish in sewage treatment plant's receiving water body.
Alkylphenol compounds is that a class has the interfering lipophilicity organic compound of endocrine, be mainly used in the production and the manufacturing of washing agent, lubricant, cosmetics, paint etc., as nonylphenol (Nonylphenol, NP), octyl phenol (Octylphenol, OP) etc.In environment, alkyl phenol mainly comes from the discharging of non-ionic surfactant APES production run.NPE and OPEO are two kinds of crucial non-ionics, in physical environment and sewage disposal process, be converted into nonylphenol and octyl phenol, enter in water body, atmosphere and the soil through processes such as sewage discharges again through action of microorganisms.(Bisphenol A BPA) is the important source material of producing polycarbonate and epoxy resin etc. to bisphenol-A.This material is widely used in the manufacturing of tableware and tableware, and electron device coats the production of thing, metallic beverage can protective seam, packaging material for food, tooth filling agent, napkin paper and dixie cup etc.For example, content of bisphenol A is 34～360ng/g in the articles for use such as dixie cup and napkin paper, and the content of bisphenol-A is 190～26000ng/g in the packing box that recycled writing paper is made.Above-mentioned substance has class estrogen active disturbing effect to biosome and exists extensively, thereby causes the concern of Chinese scholars.
Sewage disposal plant effluent and agricultural run-off are two main paties that incretion interferents such as estrogen enter river, water body in lake.In recent years, many scholars have launched the investigation to estrogen in the natural water and nonylphenol, octyl phenol, bisphenol A concentration pollution situation, find all to have in the water bodys such as most rivers and lake the existence of the horizontal above-mentioned substance of ng/L.Yet it is many to pay close attention to the estrogenic research of aqueous phase at present both at home and abroad, less relatively for the investigation of estrogen content in the water body deposit.Because estrogenic hydrophobic property, the estrogen tendency exists in sediment in the water body, and the variation of environmental baseline can cause estrogenic release in the sediment, causes the water body estrogen concentrations to raise.Therefore, to the investigation of estrogen content in the water body deposit, its ecological risk assessment is had great importance.Estrogenic content not only is subjected to the influence of water pollution source strength in the sediment, and is closely related with factors such as the sedimental content of organic matter, particle size, and it is also very big that different estrogenic content differ, and it analyzes the estrogen of difficulty greater than aqueous phase.Dimension, how by effective sample pre-treatments technology and instrument analysis technology, set up a kind of recovery height, favorable reproducibility, degree of accuracy and precision height, measure the co-detection method of estrogen that trace in the water body deposit exists and nonylphenol, octyl phenol, bisphenol-A simultaneously, become the key of research.
In recent years, estrogenic instrument detecting technology is greatly improved, and as gas chromatography-mass spectrography (GC/MS), gas chromatography-tandem mass spectrum coupling (GC/MS/MS), liquid chromatograph mass spectrography (LC/MS) etc., has higher sensitivity and degree of accuracy.But because sediment sample matrix complexity, if Impurity removal is bad in the sample pretreatment process, the directly measurement result of interference Instrument, even damage instrument.Therefore, how from sediment sample, extract estrogen efficiently and purify, become the bottleneck that trace estrogen is analyzed in the sediment.
Summary of the invention
The objective of the invention is at sediment sample matrix complexity, the estrogen trace exists in the sediment, problems such as the pretreatment technology difficulty is big, intend a kind of recovery height of exploitation, highly sensitive, analytical technology accurately and rapidly, realize quantitative measurement estrogen in the sediment sample and nonylphenol, octyl phenol, bisphenol-A.
Technical scheme of the present invention is as follows:
A kind of method that detects trace estrogen and nonylphenol in the water body deposit sample, octyl phenol, bisphenol-A is characterized in that this method comprises the steps:
(1) sediment sample pre-service
The sediment sample of gathering is carried out freeze drying, is extractant with acetone, with the estrogen in the quick solvent extraction extraction sediment and nonylphenol, octyl phenol, bisphenol-A; Adopt Rotary Evaporators to be concentrated into about 1ml then, dry up with nitrogen; With alkali lye ultrasonic dissolution residue, centrifugal and supernatant regulated about PH=2, with the estrogen in the ethyl acetate extraction aqueous solution and nonylphenol, octyl phenol, bisphenol-A, and extract dried up under nitrogen, with acetonitrile: (v: v) whirlpool mixes water=1: 1 behind the constant volume, and concentration determination is waited in refrigeration.
(2) condition of utilizing liquid chromatography-tandem mass spectrometry analysis estrogen and nonylphenol, octyl phenol, the coupling of bisphenol A concentration liquid chromatography-tandem mass spectrometry to select: 3200QTRAP type liquid chromatography/tandem mass spectrometer, be furnished with electro-spray ionization source (ESI) and Analyst 1.4.1 data processing software, U.S. AppliedBiosystem company; Agilent 1100 highly effective liquid phase chromatographic systems comprise the quaternary infusion pump, automatic sampler, U.S. Agilent company.
Chromatographic column: Nova-Pak C18 (3.9mm * 150mm * 4 μ m), Waters company.Ion gun: electro-spray ionization source (ESI), the negative ion mode detects; Ion injection electric :-4500V; Temperature: 450 ℃; Gas 1 (GS1, N in the source
2) pressure: 45psi; Gas 2 (GS2, N
2) pressure: 45psi; Gas curtain gas (N
2) pressure: 20psi; Scan mode is multiple reaction monitoring (MRM); Collision gas (N
2) pressure: Medium.Adopting methyl alcohol and ammoniacal liquor (pH=10) is moving phase, and condition of gradient elution sees table 1 for details.
Table 1 eluent gradient condition
(3) drafting of typical curve is carried out quantitative measurement with external standard method
The drafting of described external standard method typical curve: utilize 4 kinds of estrogen of the accurate weighing of analytical balance and nonylphenol, octyl phenol, bisphenol-A, be dissolved in the trifluoroacetic acid aqueous solution, be configured to the standard solution of series concentration, adopt the liquid chromatography-tandem mass spectrometry coupling to analyze, it with concentration respectively horizontal ordinate, peak area is that ordinate returns, and obtains 7 typical curves, is used for the amount of working sample analyte.
(4) mensuration of the sample and the recovery
Gather sediment sample to be measured, 1 pair of pedotheque carries out pre-service set by step, 2 carry out the liquid chromatography-tandem mass spectrometry coupling and detect set by step again, and the typical curve that obtains with step 3 relatively, finally obtains the content of estrogen and nonylphenol in the sediment sample to be measured, octyl phenol, bisphenol-A by converting.
Adopt same pedotheque, the addition of pressing 10ng/g adds standard solution, carries out above-mentioned pre-service and measures estrogen content, carries out the recovery according to following formula and calculates:
The R-recovery, %;
C-adds the estrogen content of standard solution sediment sample, ng/g;
C
0-do not add the estrogen content of standard solution sediment sample, ng/g.
The temperature that quick solvent extraction method of the present invention is selected is 60 ℃, and pressure is 1500pis, static extraction 2 times, each 8min.
Alkali lye of the present invention is the NaOH solution of 1mol/L, and the concentration of hydrochloric acid of regulating PH is 4mol/l, and the liquid-liquid extraction solvent is an ethyl acetate.
The invention has the beneficial effects as follows and adopt quick solvent extraction to extract, effect of extracting is good, and is simple to operate, and rate of extraction is fast, and is safe and reliable; Adopt alkali lye ultrasonic-acid condition under the liquid-liquid extraction purification method, good purification, cost is low; Adopt the liquid chromatography-tandem mass spectrometry coupling to detect, detectability is low, has higher sensitivity and degree of accuracy.The invention provides that a kind of detectability is low, favorable reproducibility, highly sensitive, the recovery better, the analytical approach that operation is simple, can the express-analysis sediment in the content of estrogen and nonylphenol, octyl phenol, bisphenol-A.The recovery of this method and lowest detectable limit, as shown in table 2.
The recovery of table 2 this method and lowest detectable limit
Description of drawings
Fig. 1 is the chromatogram of 5 μ g/L standard solutions, and chromatogram is followed successively by: Fig. 1 a is that oestrone, Fig. 1 b are that 17 β estradiol, Fig. 1 c are that estriol, Fig. 1 d are that 17 α-ethinyl estradiol, Fig. 1 e are that nonylphenol, Fig. 1 f are that octyl phenol, Fig. 1 g are bisphenol-A;
Fig. 2 is the typical curve of estrogen and nonylphenol, octyl phenol, bisphenol-A;
Fig. 3 is the chromatogram of estrogen and nonylphenol in the actual river deposit sample, octyl phenol, bisphenol-A; Chromatogram is followed successively by: Fig. 3 a is that oestrone, Fig. 3 b are that 17 beta estradiols, Fig. 3 c are that estriol, Fig. 3 d are that 17 α ethinyl estradiols, Fig. 3 e are that nonylphenol, Fig. 3 f are that octyl phenol, Fig. 3 g are bisphenol-A.
Embodiment
Below in conjunction with example and accompanying drawing technical scheme of the present invention is further described.
(1) sediment sample pre-service
Gather good sediment sample and carry out the freeze drying processing earlier.Get the sample after the 5g freeze drying, carry out quick solvent extraction with 60ml acetone.The temperature that the quick solvent extraction method that is adopted is selected is 60 ℃, and pressure is 1500pis, static extraction 2 times, each 8min.With Rotary Evaporators extract is concentrated to about 1ml, be transferred in the 50ml centrifuge tube and under 37 ℃ of water bath condition nitrogen dry up.1mol/L NaOH solution with 15ml divides the ultrasonic dissolution residue three times, centrifugal then and shift supernatant to the 50ml centrifuge tube, regulate its PH=2 with the hydrochloric acid of 4mol/L, divide three liquid-liquid extraction under 300r/min concussion condition with 30ml ethyl acetate, the extraction time is 15min.Extract flows down slowly at nitrogen and dries up, and adding 1ml acetonitrile/water (v/v)=1: 1 is after whirlpool mixes, to be measured.
(2) utilize the liquid chromatography-tandem mass spectrometry coupling to analyze estrogen concentrations
The condition that the liquid chromatography-tandem mass spectrometry coupling is selected: 3200QTRAP type liquid chromatography-tandem mass spectrometry instrument, be furnished with electro-spray ionization source (ESI) and Analyst 1.4.1 data processing software, U.S. AppliedBiosystem company; Agilent 1100 highly effective liquid phase chromatographic systems comprise the quaternary infusion pump, automatic sampler, U.S. Agilent company.
Chromatographic column: Nova-Pak C18 (3.9mm * 150mm * 4 μ m), Waters company.Ion gun: electro-spray ionization source (ESI), the negative ion mode detects; Ion injection electric :-4500V; Temperature: 450 ℃; Gas 1 (GS1, N in the source
2) pressure: 45psi; Gas 2 (GS2, N
2) pressure: 45psi; Gas curtain gas (N
2) pressure: 20psi; Scan mode is multiple reaction monitoring (MRM); Collision gas (N
2) pressure: Medium.Adopting methyl alcohol and ammoniacal liquor (pH=10) is moving phase, and condition of gradient elution sees table 1 for details.
The liquid chromatography-tandem mass spectrometry coupling is limited to 200ng/L to the lowest detection of oestrone, 17 beta estradiols, 17 α-ethinyl estradiol and nonylphenol, octyl phenol, bisphenol-A, and the lowest detection of estriol is limited to 500ng/L.(3) drafting of typical curve is carried out quantitative measurement with external standard method
The drafting of described external standard method typical curve: utilize 4 kinds of estrogen of the accurate weighing of analytical balance and nonylphenol, octyl phenol, bisphenol-A, be dissolved in the trifluoroacetic acid aqueous solution, be configured to the standard solution of series concentration, adopt the liquid chromatography-tandem mass spectrometry coupling to analyze, it with concentration respectively horizontal ordinate, peak area is that ordinate carries out linear regression, obtains 7 typical curves, is used for the amount of working sample analyte.
(4) mensuration of sample recovery rate
Gather sediment sample to be measured, 1 pair of pedotheque carries out pre-service set by step, 2 carry out the liquid chromatography-tandem mass spectrometry coupling and detect set by step again, and with the above-mentioned typical curve that obtains relatively, finally obtain the content of estrogen and nonylphenol in the pedotheque to be measured, octyl phenol, bisphenol-A by converting.
Adopt same sediment sample to carry out freeze drying, the pedotheque of getting after the 5g freeze drying adds standard solution by the addition of 10ng/g, carries out pre-service and measures estrogen and nonylphenol, octyl phenol, content of bisphenol A, carries out the recovery and calculates.
Utilize the present invention to detect the implementation process of estrogen and nonylphenol in certain river deposit, octyl phenol, bisphenol-A:
Gather certain river deposit, the stainless steel lunch box and put into the insulation can that has ice cube of packing into is rapidly taken back the laboratory and is carried out Treatment Analysis.Get the sample after the 5g freeze drying, carry out quick solvent extraction with 60ml acetone.The temperature that the quick solvent extraction method that is adopted is selected is 60 ℃, and pressure is 1500pis, static extraction 2 times, each 8min.With Rotary Evaporators extract is concentrated to about 1ml, be transferred in the 50ml centrifuge tube and under 37 ℃ of water bath condition nitrogen dry up.1mo1/L NaOH solution with 15ml divides the ultrasonic dissolution residue three times, centrifugal then and shift supernatant to the 50ml centrifuge tube, regulate its PH=2 with the hydrochloric acid of 4mol/L, divide three liquid-liquid extraction under 300r/min concussion condition with 30ml ethyl acetate, the extraction time is 15min.Extract liquid flows down slowly at nitrogen and dries up, and adding 1ml acetonitrile/water (v/v)=1: 1 is after whirlpool mixes, to be measured.
Utilize the liquid chromatography-tandem mass spectrometry coupling to measure the estrogen of above-mentioned testing sample and nonylphenol, octyl phenol, bisphenol A concentration.The condition that the liquid chromatography-tandem mass spectrometry coupling is selected: 3200QTRAP type liquid chromatography-tandem mass spectrometry instrument, be furnished with electro-spray ionization source (ESI) and Analyst 1.4.1 data processing software, U.S. Applied Biosystem company; Agilent 1100 highly effective liquid phase chromatographic systems comprise the quaternary infusion pump, automatic sampler, U.S. Agilent company.Chromatographic column: Nova-Pak C18 (3.9mm * 150mm * 4 μ m), Waters company.Ion gun: electro-spray ionization source (ESI), the negative ion mode detects; Ion injection electric :-4500V; Temperature: 450 ℃; Gas 1 (GS1, N in the source
2) pressure: 45psi; Gas 2 (GS2, N
2) pressure: 45psi; Gas curtain gas (N
2) pressure: 20psi; Scan mode is multiple reaction monitoring (MRM); Collision gas (N
2) pressure: Medium.Adopting methyl alcohol and ammoniacal liquor (pH=10) is moving phase, and condition of gradient elution sees table 1 for details.Result of calculation is as shown in table 3.
The content (ng/g) of estrogen and nonylphenol, octyl phenol, bisphenol-A in the actual river deposit of table 3
Annotate: n.d. represents not detect.
Claims (1)
1. quick solvent extraction-liquid-liquid extraction-liquid chromatography/tandem mass spectrum coupling (ASE-LLE-LC/MS/MS) co-detection method of estrogen and nonylphenol, octyl phenol, bisphenol-A in the analyzing water body sediment is characterized in that, comprises the steps:
(1) sediment sample pre-treatment
The sediment sample of gathering is carried out freeze drying, is extractant with acetone, with the estrogen in the quick solvent extraction extraction sediment and nonylphenol, octyl phenol, bisphenol-A; Adopt Rotary Evaporators to be concentrated into about 1ml then, dry up with nitrogen; With alkali lye ultrasonic dissolution residue, centrifugal and supernatant regulated about PH=2, with the estrogen in the ethyl acetate extraction aqueous solution and nonylphenol, octyl phenol, bisphenol-A, and extract dried up under nitrogen, with acetonitrile: (v: v) whirlpool mixes water=1: 1 behind the constant volume, and cold a surname waits for concentration determination.
(2) utilize the liquid chromatography-tandem mass spectrometry coupling to analyze the concentration of estrogen and nonylphenol, octyl phenol and bisphenol-A
Utilize the 3200QTRAP type liquid chromatography/tandem mass spectrometer of U.S. Applied Biosystem company and the automatic sampler of Agilent 1100 highly effective liquid phase chromatographic systems and U.S. Agilent company to carry out the concentration detection.
Chromatographic column: Nova-Pak C18,3.9mm * 150mm * 4 μ m;
Gradient elution: adopting acetonitrile, 0.1% ammoniacal liquor and methyl alcohol is moving phase, the ratio of acetonitrile and methyl alcohol is raised to 10% by 7.5% respectively in 0-1.2min, 1.2-2.0min in be raised to 15%, 2.0-2.5min in be raised to 49%, 2.5-6.1min in be raised to 50%, 6.1-6.2min in reduce to 7.5%, maintain 7.5% in the 6.2-10min, above number percent is percent by volume.
(3) drafting of typical curve is carried out quantitative measurement with external standard method.
(4) mensuration of sample
With sediment sample to be measured, (1) carries out pre-treatment set by step, (2) carry out liquid chromatography-tandem mass spectrometry coupling detection more set by step, and the typical curve that obtains with step (3) relatively finally obtains the concentration of estrogen, nonylphenol, octyl phenol and bisphenol-A in the sediment sample to be measured by converting.
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