CN115598263A - Method for simultaneously determining contents of organic phosphate and conversion product thereof - Google Patents
Method for simultaneously determining contents of organic phosphate and conversion product thereof Download PDFInfo
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Abstract
A method for simultaneously determining the content of organophosphates and their conversion products, the method comprising: extracting, enriching and purifying a solid phase extraction small column, eluting a solvent, concentrating and fixing the volume, and measuring a target object to be measured by using a high performance liquid chromatography-triple quadrupole mass spectrometer. The method can simultaneously determine 15 Organic Phosphate Esters (OPEs) and 9 conversion products in three major types (chlorinated alkyl type, non-chlorinated alkyl type and aromatic type) by establishing and optimizing high performance liquid chromatography conditions and tandem mass spectrometry parameters, has good selectivity and sensitivity, can realize rapid identification and accurate quantification of trace OPEs and conversion products in drinking water, and makes up for the technical defects in the field at present.
Description
Technical Field
The invention relates to a detection method of a phosphate derivative, in particular to a method for simultaneously determining the contents of organic phosphate and a conversion product thereof.
Background
OPEs (organic phosphate esters) are a class of artificially synthesized phosphoric acid derivatives, and are widely applied to products such as electronic components, plastics, furniture, food packaging materials and the like as flame retardants and plasticizers. Since conventional brominated flame retardants such as polybromodiphenyl ether and hexabromocyclododecane have been banned by the stockholm convention, there is an increasing demand for OPEs in the global flame retardant market. The global consumption of OPEs-type flame retardants has reportedly increased from 18.6 million tons in 2001 to 100 million tons in 2018. The yield of OPEs flame retardants in 2020 of China reaches 29.4 million tons. As a class of industrial additive auxiliaries, OPEs have no firm chemical bonding effect with product materials and can easily enter the environment through volatilization, abrasion, leakage and other modes. It is vigilant that some OPEs have been shown to be carcinogenic, developmentally and neurotoxic and endocrine disrupting toxicities.
OPEs generally have a lower octanol-water partition coefficient (log Kow < 5) and thus a higher hydrophilicity. Currently, OPEs have been found to be present in a wide variety of water bodies, including influent and effluent from sewage treatment plants, surface water, ground water, precipitation, and the like. OPEs are susceptible to photodegradation and transformation in the environment, and also to metabolic transformation in organisms. The octanol-water partition coefficient of OPEs conversion products is lower than that of the corresponding parent OPEs, resulting in further increase of hydrophilicity and fluidity. This will make the occurrence of OPEs conversion products in aqueous environments more abundant and more difficult to remove by drinking water treatment procedures, possibly with additional impact on the health of aquatic ecosystems and the safety of drinking water. However, only a few studies have reported OPEs in drinking water, and detection analysis and occurrence of OPEs transformation products have been neglected. In addition, OPEs have phosphate groups as the core and haloalkyl, non-haloalkyl or aryl groups as side chains. According to different side chain groups, the OPEs have great difference in physical and chemical properties, and the congeners of the OPEs comprise a series of monomers from strong polarity to weak polarity to nonpolar, from water-soluble to water-insoluble, from volatile to nonvolatile and the like, so that great challenges are brought to the detection and analysis of the OPEs. How to develop a method for simultaneously detecting OPEs and conversion products thereof in drinking water has become a difficult problem which needs to be solved urgently by researchers.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a method for simultaneously determining the contents of OPEs and conversion products, so as to at least partially solve the above technical problems.
In order to achieve the above object, the present invention provides a method for simultaneously determining the contents of organic phosphate and conversion products, comprising the following steps:
extracting and enriching organic phosphate and a conversion product thereof contained in a water sample by using a solid-phase extraction column;
eluting the organic phosphate and the conversion product thereof from the solid phase extraction column by using a solvent;
and (3) determining a sample obtained by the elution post-treatment by using a high performance liquid chromatography-triple quadrupole mass spectrometer, and simultaneously obtaining the content numerical values of the organic phosphate and the conversion product thereof by using a reaction ion scanning mode SRM as a data acquisition mode.
Based on the scheme, compared with the prior art, the detection method disclosed by the invention has at least one of the following beneficial effects:
the method provided by the invention adopts a method of combining solid-phase extraction with high performance liquid chromatography-tandem triple quadrupole mass spectrometry to simultaneously and rapidly determine the contents of various OPEs and conversion products; the method is characterized in that the analysis rate is improved and the analysis time is shortened by utilizing the high performance liquid chromatography, the background interference is effectively reduced by utilizing the extremely high sensitivity and the anti-interference performance of the triple quadrupole mass spectrum, and meanwhile, the complex steps of the sample pretreatment are simplified and the detection limit of the method is reduced by combining the solid phase extraction technology to simultaneously extract, enrich and purify the target object;
the method of the invention has the following excellent technical indexes: optimizing and finally determining the correlation coefficient (R) of the standard curve of various OPEs 2 ) The detection limit and the quantification limit of the method are respectively 0.11-8.75 ng/L and 0.38-29.18 ng/L between 0.9951-0.9992; standard Curve correlation coefficient (R) for various OPEs conversion products 2 ) Between 0.9950 and 0.9990, the detection limit and the quantification limit of the method are respectively 0.56 to 28.54 ng/L and 1.85 to 95.14 ng/L;
the method can simultaneously determine 15 OPEs and 9 conversion products in three categories (chlorinated alkyl type, non-chlorinated alkyl type and aromatic type) by establishing and optimizing the high performance liquid chromatography condition and the tandem mass spectrometry parameters, has good selectivity and sensitivity, can realize the rapid identification and accurate quantification of trace OPEs and conversion products in water, and makes up the technical defects in the field at present.
Drawings
FIG. 1 is a chromatogram of 15 OPEs and 9 internal isotope standards;
FIG. 2 is a chromatogram of 9 OPEs conversion products and 7 internal isotope standards.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
Gas Chromatography (GC) and Liquid Chromatography (LC) tandem mass spectrometry are currently common techniques for detecting ops. The gas chromatography is mainly suitable for analyzing volatile and weak-polarity OPEs, wherein a gas chromatography-nitrogen phosphorus detector (GC-NPD) and a gas chromatography-mass spectrometry (GC-MS; GC-MS/MS) are two commonly used detection technologies, but the technologies have the defects of trailing chromatographic peaks, poor stability and the like. Furthermore, the gas phase method is not suitable for the detection and analysis of certain OPEs with higher boiling points and less volatility (such as TEHP), so that the universality is lower. Compared with a gas phase method, the liquid phase method is more suitable for analyzing the OPEs with difficult volatilization, thermal instability and strong polarity, and the liquid phase chromatography and mass spectrum combined technology can directly detect the OPEs in a water sample without phase transfer.
However, the current LC-MS/MS detection method for OPEs and conversion products in drinking water still has many defects, including:
a. the quantity of the detected target OPEs is limited, is generally within 10, and does not contain OPEs conversion products;
b. the physical and chemical properties of the OPEs and the transformation products thereof have wide variation range, and a series of congeners including strong polarity, weak polarity, non-polarity and the like are included, so that sufficient OPEs and transformation products are difficult to extract and enrich by a single pretreatment method;
c. the polarity of the conversion products of OPEs is strong, while the reversed phase chromatography usually uses C18 column based on non-polar packing, so that it is difficult to perform chromatographic retention, thereby bringing difficulty in detecting the conversion products of OPEs by LC-MS/MS.
Through intensive research and experiments, the inventors of the present invention propose a method for simultaneously determining the contents of various Organic Phosphates (OPEs) and their conversion products, which uses HPLC tandem triple quadrupole mass spectrometry to establish and optimize analytical detection methods of 15 types (TCEP, TCIPP, TDP, TEP, TPrP, TNBP, TIBP, TBOEP, TEHP, TPhP, EHDPP, CDPP, TMTP, TOTP and TPTP) and 9 types (BCIPP, BDIPP, DEP, BBOEP, DNBP, MNHP, BEHP and DOTP) of OPEs, and which uses 9 types of isotope labeled standards (TCEP-d 12, TCIPP-d18, TDP-d 15, TEP-d15, DNrP-d 21, TNBP-d27, TPTP-15, TPTP-d21 and TPTP) as well as a secondary isotope labeled standard for quantitative determination of selectivity of TPOPP-D, TPOPBP-12, TPIPD-d 18, TPIPD-d 15, TPIPD-D and BCHP, and its conversion products, and a secondary isotope labeled standard (TCEP-d 12, BTHP-D) as well as a quantitative determination method for quantitative determination of the selectivity of the secondary isotope conversion products in water and the quantitative determination of the secondary isotope identification of the target compounds.
Specifically, the invention discloses a method for simultaneously measuring the contents of Organic Phosphates (OPEs) and conversion products thereof, which comprises the following steps:
(1) Solid phase extraction column extraction: extracting and enriching the OPEs and the conversion products thereof contained in the water sample by using a solid-phase extraction column;
(2) And (3) solvent elution: eluting the target from the solid phase extraction column with a solvent, such as a polar solvent such as methanol;
(3) Concentration: concentrating the eluent, fixing the volume, and transferring to a sample injection vial for storage;
(4) And (3) computer detection: and (3) determining the sample by using a high performance liquid chromatography-triple quadrupole mass spectrometer in series connection, and selecting a reactive ion scanning mode SRM as a data acquisition mode.
Wherein, the water sample in the step (1) can be drinking water, reclaimed water, domestic or industrial wastewater and the like, and can also be other water samples needing to measure the content of trace phosphate, wherein the drinking water comprises tap water, purified water, mineral water and all water which can be drunk by human beings.
Wherein, the solid phase extraction column in step (1) can be hydrophilic and lipophilic solid adsorption column, such as preferably Woodward's Oasis HLB, with sample flow rate maintained at about 5mL/min, and drying for more than 30 min. In the prior art, the HLB solid-phase extraction column is mainly used for sample pretreatment, extracting semi-volatile or non-volatile compounds therein, or removing impurities in the sample that interfere with separation analysis. The method can improve the recovery rate of the analyte, more effectively separate the analyte from the interference component, shorten the sample pretreatment process, and is convenient to operate, time-saving and labor-saving. The HLB solid phase extraction column filler is an adsorbent which can be generally used for acidic, neutral and alkaline compounds, meets the extraction and enrichment requirements of OPEs congeners with greatly changed properties, and is applied to the extraction and enrichment of OPEs by a small amount of research. However, the current literature data does not find that the method is applied to the extraction and enrichment of OPEs conversion products, and the inventor finds that the HLB solid-phase extraction column can simultaneously extract and enrich 15 OPEs and 9 OPEs conversion products at one time through repeated tests, so that the pretreatment efficiency is greatly improved, and the accumulated error of multiple tests is avoided.
Wherein, when the high performance liquid chromatography is connected with a triple quadrupole mass spectrometer in series, for example, a Waters SunFire C18 reversed phase chromatographic column (the inner diameter is 4.6 mm multiplied by 150 mm long, the particle thickness is 3.5 μm) is adopted for chromatographic separation, and the temperature is kept at 40 ℃. The Waters SunFire C18 liquid chromatographic column has the advantage of excellent peak type to alkaline compounds under a formic acid system, and is particularly suitable for separating OPEs organic basic compounds.
Further preferably, the gradient elution is carried out with a binary mobile phase of methanol and water with the addition of 0.1% formic acid (v/v); further preferably, ESI is used as the ion source, and the ionization mode is a positive ion mode.
Wherein, when the high performance liquid chromatography-triple quadrupole mass spectrometer is used for measuring the OPEs transformation products, a Thermo Acclaim Mixed-Mode HILIC-1 liquid chromatography column (with the inner diameter of 2.1 mm multiplied by 150 mm and the particle thickness of 3.0 mu m) is adopted for chromatographic separation, and the column temperature is set to be 35 ℃.
The advantages are that: the Acclaim Mixed-Mode HILIC-1 chromatographic column has a Mixed-Mode stationary phase, a hydrophobic alkyl chain on the surface and a glycol group at the tail end. The hydrophobic groups enhance reversed phase retention and the terminal diol groups promote hydrophilic interactions, which enhances tunable selectivity, allowing the Acclaim Mixed-Mode HILIC-1 to separate mixtures that cannot be separated on C18 columns, especially to retain highly polar compounds such as OPEs conversion products.
Further preferably, the gradient elution is performed with ultrapure water to which 10 mM ammonium acetate is added and methanol (v/v = 2/3) as a mobile phase.
Further preferably, ESI is used as the ion source, and the ionization mode is a negative ion mode.
The present invention will be further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto. It is to be understood that the embodiments described hereinafter are only some embodiments of the invention, and not all embodiments; all embodiments obtained by a person skilled in the art without making any inventive effort based on the following embodiments of the present invention belong to the scope of protection of the present invention.
The specific method used in the following examples is a method for simultaneously and rapidly determining the contents of various OPEs and conversion products in water, and comprises the following steps:
solid-phase extraction column extraction: extracting and enriching the OPEs and the conversion products in the water sample by using a solid-phase extraction column;
and (3) elution: eluting the target object from the solid phase extraction column by using methanol;
concentration: concentrating and fixing the volume of the eluent, and transferring the eluent into a sample injection small bottle for storage;
and (3) computer detection: and (3) determining the sample by using a high performance liquid chromatography-triple quadrupole mass spectrometer.
The solid phase extraction cartridge is Oasis HLB (6 mL,150 mg), and before use, the cartridge is washed and activated with 5mL each of acetonitrile and methanol, and then equilibrated with 5mL of ultrapure water.
The elution process was performed with two 5mL portions of methanol solution.
The conditions of the high performance liquid chromatography-mass spectrum are as follows:
high performance liquid chromatograph: ultimate 3000 HPLC, dionex corporation;
the OPEs chromatographic separation conditions were:
the column was a Waters SunFire C18 column (4.6 mm. Times.150 mm, 3.5 μm), the column temperature was 40 ℃ and the flow rate of the mobile phase (A: ultrapure water, B: methanol, each supplemented with 0.1% (v/v) formic acid) was set to 1 mL/min, and the mobile phase gradient was set as follows: 0-2 min 10% B,5.5 min up to 65% B,9.5 min up to 80% B,11.5 min 100% B, 3.5 min hold, 16 min down to 10% B, 2.5 min hold. The injection volume was 10. Mu.L.
The chromatographic separation conditions of the OPEs conversion products are as follows:
the column was an Acclaim Mixed-Mode Hilic-1 column (2.1 mM. Times.150 mM, 3.0 μm), the column temperature was 35 ℃ and the mobile phase (A: acetonitrile, B: ultrapure water/methanol (v/v = 2/3) with 10 mM ammonium acetate added), the flow rate was set to 0.35 mL/min and the mobile phase gradient was set as follows: 3% B in 0-3 min, 15% B in 5 min, hold for 6 min, 3% B in 11.2 min and hold for 15 min. The injection volume was 20. Mu.L.
Mass spectrometry: TSQ Quantiva triple quadrupole mass spectrometry of Thermo corporation; an ion source: ESI; the collision gas and the atomization gas respectively select high-purity argon and high-purity nitrogen; the data acquisition mode is as follows: and (6) SRM.
Mass spectral parameters for OPEs determination:
an ionization mode: a positive ion mode; spraying voltage: 3.5kV; the temperature of the ion transmission tube and the spray cone is set to 350 ℃; sheath gas: 40; auxiliary gas: 25.
mass spectrometric parameters determined for OPEs conversion products:
an ionization mode: a negative ion mode; spraying voltage: 2.5kV; the temperature of the ion transmission tube is 330 ℃; the temperature of a spray cone is 350 ℃; sheath gas: 30, of a nitrogen-containing gas; auxiliary gas: 20.
TABLE 1 LC-MS/MS parameters for OPEs and conversion products
| Compound full scale | Abbreviations | Retention time (min) | Parent ion | Daughter ions (quantitative/qualitative) | Collision energy (V) | Lens voltage (V) |
| Phosphoric acid triethyl ester | TEP | 8.13 | 183.1 | 99.0/127.0 | 18.4/10.3 | 36.7 |
| Phosphoric acid tripropyl ester | TPrP | 10.95 | 225.2 | 99.0/141.1 | 17.5/10.3 | 40.1 |
| Phosphoric acid triisobutyl ester | TIBP | 12.76 | 267.2 | 99.0/155.1 | 16.4/10.3 | 39.1 |
| Phosphoric acid tributyl ester | TNBP | 12.82 | 267.2 | 99.0/155.1 | 18.3/10.3 | 46.1 |
| Phosphoric acid tris (butoxyethyl) ester | TBOEP | 12.96 | 399.3 | 299.1/199.1 | 10.3/14.5 | 61.6 |
| Phosphoric acid tris (2-ethylhexyl) ester | TEHP | 15.99 | 435.4 | 99.0/211.1 | 17.3/10.3 | 54.0 |
| Phosphoric acid triphenyl ester | TPhP | 12.44 | 327.2 | 152.1/215.1 | 37.0/26.0 | 91.3 |
| Phosphoric acid toluene Diphenyl ester | CDPP | 12.76 | 341.2 | 152.1/229.0 | 34.1/26.1 | 91.6 |
| Trim-cresyl phosphate | TMTP | 13.21 | 369.2 | 169.1/243.0 | 44.5/27.7 | 104.9 |
| Tri-o-tolyl phosphate | TOTP | 13.21 | 369.2 | 169.1/243.0 | 44.9/25.8 | 94.8 |
| Phosphoric acid tri-p-tolyl ester | TPTP | 13.21 | 369.2 | 169.1/243.0 | 42.0/27.6 | 96.0 |
| 2-ethylhexyl diphenyl phosphate | EHDPP | 13.39 | 363.3 | 251.0/153.0 | 10.3/29.2 | 40.6 |
| Phosphoric acid tris (2-chloroethyl) ester | TCEP | 8.78 | 285.1 | 99.0/222.9 | 21.8/10.3 | 65.3 |
| Phosphoric acid tris (2-chloro)Propyl) ester | TCIPP | 11.05 | 327.1 | 99.0/175.0 | 21.8/10.3 | 46.1 |
| Phosphoric acid tris (1, 3-dichloro-2-propyl) ester | TDCIPP | 12.46 | 431.0 | 99.0/208.9 | 24.3/14.7 | 71.0 |
| Triethyl phosphate-d 15 | TEP-d15 | 8.05 | 198.3 | 102.0/134.0 | 19.9/10.3 | 42.4 |
| Phosphoric acid tripropyl ester-d 21 | TPrP-d21 | 10.81 | 246.3 | 102.0/150.1 | 19.3/10.3 | 45.6 |
| Tributyl phosphate-d 27 | TNBP-d27 | 12.77 | 294.4 | 102.0/166.1 | 19.7/10.3 | 49.5 |
| Phosphoric acid tris (2-ethylhexyl) ester-d 51 | TEHP-d51 | 16.10 | 486.8 | 102.0/230.1 | 20.0/10.3 | 57.4 |
| Triphenyl phosphate-d 15 | TPhP-d15 | 12.38 | 342.2 | 160.1/223.1 | 39.7/27.6 | 70.8 |
| Phosphoric acid tri-p-tolyl ester-d 21 | TPTP-d21 | 13.16 | 390.3 | 174.1/251.1 | 48.6/30.5 | 78.0 |
| Phosphoric acid tris (2-chloroethyl) ester-d 12 | TCEP-d12 | 8.74 | 297.1 | 102.0/130.0 | 23.7/16.8 | 61.9 |
| Phosphoric acid tris (2-chloropropyl) ester-d 18 | TCIPP-d18 | 10.96 | 345.2 | 102.0/183.0 | 22.7/12.8 | 50.5 |
| Phosphoric acid tris (1, 3-dichloro-2-propyl) ester-d 15 | TDCIPP-d15 | 12.43 | 446.1 | 102.0/215.9 | 25.7/16.1 | 65.6 |
| Phosphoric acid diethyl ester | DEP | 9.01 | 153.1 | 79.0/125.0 | -25.2/-10.3 | -44.1 |
| Dibutyl phosphate | DNBP | 8.55 | 209.2 | 79.0/153.0 | -29.1/-15.7 | -61.9 |
| Phosphoric acid mono butyl ester | MNBP | 9.01 | 153.2 | 79.1/97.0 | -17.2/-15.3 | -39.6 |
| Bis (2-butoxy-ethyl) phosphate | BBOEP | 8.49 | 297.2 | 79.1/197.1 | -30.9/-20.1 | -83.9 |
| Phosphoric acid di (2-ethylhexyl) ester | BEHP | 8.10 | 321.3 | 79.1/209.1 | -33.4/-21.9 | -93.0 |
| Phosphoric acid di (2-chloropropyl) ester | BCIPP | 1.62 | 249.1 | 35.2/249.1 | -10.3/-10.3 | -32.0 |
| Phosphoric acid di (1, 3-dichloro-2-propyl) ester | BDCIPP | 1.49 | 318.9 | 35.2/318.9 | -10.3/-10.3 | -39.4 |
| Phosphoric acid diphenyl ester | DPhP | 1.62 | 249.2 | 93.1/155.0 | -30.7/-23.3 | -81.4 |
| Phosphoric acid di-o-tolyl ester | DOTP | 1.70 | 277.1 | 107.1/169.0 | -31.7/-25.7 | -88.3 |
| Dibutyl phosphate-d 18 | DNBP-d18 | 8.59 | 227.3 | 79.0/163.1 | -30.4/-17.7 | -69.0 |
| Phosphoric acid mono butyl ester-d 9 | MNBP-d9 | 8.58 | 162.2 | 79.1/98.0 | -18.8/-16.7 | -39.1 |
| Phosphoric acid bis (2-butoxy-ethyl) ester-d 8 | BBOEP-d8 | 8.53 | 305.2 | 79.1/230.2 | -31.6/-22.2 | -86.9 |
| Di (2-ethylhexyl) phosphate-d 34 | BEHP-d34 | 8.12 | 355.7 | 79.1/227.2 | -36.9/-25.4 | -104.9 |
| Di (2-chloropropyl) phosphate-d 12 | BCIPP-d12 | 1.63 | 261.2 | 35.2/261.1 | -10.3/-10.3 | -39.0 |
| Phosphoric acid bis (1, 3-dichloro-2-propyl) ester-d 10 | BDCIPP-d10 | 1.49 | 329.0 | 35.2/328.9 | -10.8/-10.3 | -42.0 |
| Diphenyl phosphate-d 10 | DPhP-d10 | 1.63 | 259.2 | 98.2/179.1 | -32.0/-23.3 | -86.4 |
The present invention will be described with reference to specific examples. The conditions of the high performance liquid chromatography-mass spectrometry are consistent with the technical scheme.
Preparation of the experiment and preparation of the Standard sample
1. Preparing a standard curve sample:
(1) OPEs: 15 OPES standards (TCEP, TCIPP, TDCIPP, TEP, TPrP, TNBP, TIBP, TBOEP, TEHP, TPhP, EHDPP, CDPP, TMTP, TOTP and TPTP) and 9 isotope standards (TCEP-d 12, TCIPP-d18, TDCIPP-d15, TEP-d15, TPrP-d21, TNBP-d27, TPhP-d15, TPTP-d21 and TEHP-d 15) are respectively prepared into mixed standard sample stock solution with the concentration of 1 mg/L by methanol, and the stock solution is used for preparing mixed standard use solution with the concentration of 0.1-500 ng/L, wherein the concentration of the isotope internal standard is 10 ng/L.
(2) OPEs conversion product: 9 OPES conversion product standards (BCIPP, BDCIPP, DEP, BBOEP, DNBP, MNBP, BEHP, DPhP and DOTP) and 7 isotope standards (BDCIPP-d 10, BCIPP-d12, DPhP-d10, BEHP-d34, BBOEP-d8, DNBP-d18 and MNBP-d 9) are respectively prepared into mixed standard stock solutions with the concentration of 1 mg/L by acetonitrile, and mixed standard use solutions with the concentration of 0.1 ng/L to 500 ng/L are prepared by using the stock solutions, wherein the concentration of the isotope internal standard is 10 ng/L.
2. Drawing a standard curve: the high performance liquid chromatography-triple quadrupole mass spectrometer is utilized to detect each concentration gradient mixed standard substance by using liquid mass according to the instrument conditions in the invention, and an internal standard curve is drawn by taking the area ratio of the selected ion pair chromatographic peak of the target substance and the corresponding isotope internal standard as the ordinate and the concentration of the corresponding target substance as the abscissa. The results show that: correlation coefficient (R) of standard curve of 15 OPEs 2 ) Between 0.9951 and 0.9992, the detection limit and the quantification limit of the instrument are respectively 0.11 to 8.75 ng/L and 0.38 to 29.18 ng/L; correlation coefficient (R) of standard curve for 9 OPEs conversion products 2 ) Between 0.9950 and 0.9990, the detection limit and the quantification limit of the instrument are 0.56-28.54 ng/L and 1.85-95.14 ng/L, respectively.
Example 1
6 parts of 1L purified water were taken, and 100. Mu.L of OPEs mixed standard (TCEP, TCIPP, TDCIPP, TEP, TPrP, TNBP, TIBP, TBOEP, TEHP, TPhP, EHDPP, CDPP, TMTP, TOTP and TPTP) at a concentration of 0.1 mg/L and 100. Mu.L of isotope mixed standard (TCEP-d 12, TCIPP-d18, TDCIPP-d15, TEP-d15, TPrP-d21, TNBP-d27, TPhP-d15, TPTP-d21 and TEHP-d 15) at a concentration of 0.1 mg/L were added to 3 parts thereof. Only 100. Mu.L of OPES isotope mixture standard substance with the concentration of 0.1 mg/L is added into the other 3 parts of purified water samples.
Sample treatment: performing solid phase extraction by using an Oasis HLB small column which is activated in advance and balanced, keeping the sample loading rate at about 5mL/min, and drying the SPE small column for more than 30min after sample loading; and (3) eluting the dried product according to the method in the invention, collecting the two eluates in the same collection bottle, blowing the eluates to be nearly dry by using high-purity nitrogen at a proper flow rate, metering the volume to be 1mL by using methanol, transferring the eluate to a sample injection vial, and storing the eluate in a refrigerator at the temperature of-20 ℃ for detection.
Instrumental determination and qualitative and quantitative determination: determining the chromatographic peaks of 15 OPEs and 9 isotope internal standards (see FIG. 1) and the chromatographic peaks of 9 OPEs conversion products and 7 isotope internal standards (see FIG. 2) according to retention time and characteristic ion pairs; and calculating the concentration of the sample by using an internal standard method according to the peak area ratio of the target substance to the corresponding internal standard. The recovery rate of 15 OPEs in purified water is between 70 and 103 percent (except TDCIPP 60.8 percent, CDPP 61.1 percent and TPhP 68.6 percent), and the recovery rate of 9 OPEs conversion products is between 81.8 and 116 percent.
Example 2
6 parts of 1L tap water were taken, and 100. Mu.L of OPEs mixture standard (TCEP, TCIPP, TDCIPP, TEP, TPrP, TNBP, TIBP, TBOEP, TEHP, TPhP, EHDPP, CDPP, TMTP, TOTP and TPTP) at a concentration of 0.1 mg/L and 100. Mu.L of OPEs isotope mixture standard (TCEP-d 12, TCIPP-d18, TDCIPP-d15, TEP-d15, TPrP-d21, TNBP-d27, TPhP-d15, TPTP-d21 and TEHP-d 15) at a concentration of 0.1 mg/L were added to 3 parts of the tap water. Only 100. Mu.L of OPES isotope mixture standard with a concentration of 0.1 mg/L was added to 3 additional samples of tap water.
Sample handling and instrumental analysis were performed as in example 2. The recovery rate of 15 OPEs in tap water is between 70.0% and 98.8% (except TPhP 64.3%, CDPP 60.2%, TIBP 65.2% and EHDPP 63.5%), and the recovery rate of 9 OPEs conversion products is between 80.8% and 107%.
As can be seen from the above examples, the method of the present invention can simultaneously detect 15 OPEs and 9 OPEs at a time, and both the detection limit and the detection accuracy are much higher than those of the detection methods in the prior art, and the literature does not find any solution describing that the OPEs conversion products can be simultaneously detected.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for simultaneously determining the contents of organic phosphate and a conversion product is characterized by comprising the following steps:
extracting and enriching organic phosphate and a conversion product thereof contained in a water sample by using a solid-phase extraction column;
eluting the organic phosphate and the conversion product thereof from the solid phase extraction column by using a solvent;
and (3) determining a sample obtained by the elution post-treatment by using a high performance liquid chromatography-triple quadrupole mass spectrometer, and simultaneously obtaining the content numerical values of the organic phosphate and the conversion product thereof by using a reaction ion scanning mode SRM as a data acquisition mode.
2. The method of claim 1, wherein the solid phase extraction cartridge is a hydrophilic and lipophilic solid adsorption cartridge.
3. The method of claim 2, wherein the solid phase extraction cartridge is selected from Oasis HLB solid adsorption cartridge;
and the sample loading flow rate of the solid phase extraction column is kept at 4-6 mL/min, and the sample is dried for more than 30 min.
4. The method of claim 1, wherein the hplc-triple quadrupole mass spectrometer is used for chromatographic separation using a Waters sunface C18 liquid chromatography column in the determination of organophosphates.
5. The method of claim 4, wherein the HPLC-triple quadrupole mass spectrometer is used for measuring the organophosphate by adding a binary mobile phase of methanol and water containing 0.1 vol% formic acid.
6. The method as claimed in claim 4, wherein the HPLC-triple quadrupole mass spectrometer uses ESI as the ion source and the ionization mode is positive ion mode in the measurement of the organophosphate.
7. The method of claim 1, wherein the hplc-triple quadrupole mass spectrometer is used for chromatographic separation using a Thermo Acclaim Mixed-Mode HILIC-1 liquid chromatography column in the determination of the organophosphate conversion product.
8. The method according to claim 7, wherein the HPLC-triple quadrupole mass spectrometer is used for measuring the organophosphate conversion product by performing gradient elution with ultrapure water and methanol as a binary mobile phase to which 10 mM ammonium acetate is added, wherein the volume ratio of the ultrapure water to the methanol is 2:3.
9. the method of claim 7, wherein the HPLC-triple quadrupole mass spectrometer uses ESI as an ion source and the ionization mode is a negative ion mode in the determination of the organophosphate conversion product.
10. The method according to claim 1, wherein the water sample is a drinking water sample.
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