CN113671068B - Method for analyzing environmental pollutant targeted exposure group in blood plasma and application thereof - Google Patents

Abstract

The invention discloses a method for analyzing an environmental pollutant target exposure component in blood plasma and application thereof. The method comprises the following steps: (1) Adding a recovery indicator to the plasma to obtain a mixture of plasma and recovery indicator; (2) Adding mixed solvent of ethyl acetate containing formic acid and n-hexane for extraction, adding ethyl acetate for extraction, and mixing extractive solutions; (3) Drying the extract by using nitrogen, adding methanol for redissolution, freezing, centrifuging, and taking supernatant to obtain a pretreated sample; (4) Adding an internal standard into the pretreated sample, and then carrying out quantitative analysis on the environmental pollutants by using a liquid chromatography-tandem mass spectrometry method and/or a gas chromatography-tandem mass spectrometry method. The method can realize the simultaneous detection of hundreds of different types of environmental pollutants in the plasma, has simple and convenient treatment method, short analysis time and low cost, and can improve the analysis efficiency to the maximum extent.

Description

Method for analyzing environmental pollutant targeted exposure group in blood plasma and application thereof

Technical Field

The invention relates to the fields of environmental science and organic matter analysis research, in particular to a method for analyzing an environmental pollutant targeted exposure group in blood plasma and application thereof.

Background

In daily life, a human body comes into contact with various chemical contaminants, such as plastic additives in plastic products, perfluoro compounds in furniture products, residual pesticides (organochlorine pesticides, organophosphorus pesticides) in vegetables and fruits, and the like. These contaminants may enter the body through ingestion, respiration, skin absorption, etc., and may be exposed to health hazards. Some contaminants have been shown to be neurotoxic, endocrine disruptive and reproductive toxic.

The use of chemical products promotes the development of society, but also pollutes the environment, so that the health of human bodies is damaged. Many studies have been made to show that human bodies are exposed to various environmental pollutants, but most studies on environmental pollutants in human plasma focus on single or one class of compounds, and studies on the mixed effect of multiple environmental pollutants are relatively lacking, and meanwhile, health hazards caused by the exposure of some novel additives or environmental pollutants to human bodies are still unknown, for example, in screens of electronic devices such as mobile phones and computers used in daily life, the release of some liquid crystal monomers can cause the human bodies to be exposed to the harmful substances. In order to realize the research on the mixed effect of various chemical pollutants, the premise is that various different environmental pollutants in blood plasma can be detected simultaneously, so a method for rapidly detecting different environmental pollutants in human blood needs to be developed. Because the pretreatment process of some current detection methods is complex, takes long time, has overhigh cost and has single type of detection compounds, the establishment of the simple, convenient, efficient and low-cost analysis method for the target exposure of the environmental pollutants in the human plasma is necessary, and technical conditions can be provided for the subsequent evaluation of the influence of various environmental pollutants on the health of human bodies.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a method for analyzing the environmental pollutants in the blood plasma by targeting exposure.

Another object of the present invention is to provide the use of the method for analyzing the environmental pollutants in blood plasma by targeted exposure.

The purpose of the invention is realized by the following technical scheme:

a method for analyzing environmental pollutants in plasma by targeting exposure, comprising the steps of:

(1) Adding the recovery rate indicator into the plasma, and uniformly mixing to obtain a mixture of the plasma and the recovery rate indicator;

(2) Adding an extraction solvent I into the mixture of the plasma and the recovery rate indicator obtained in the step (1) for extraction, centrifuging, taking the supernatant, and repeating the step for more than 1 time; adding an extraction solvent II for extraction to obtain an extract liquid; wherein the extraction solvent I is a mixed solvent of ethyl acetate containing formic acid and n-hexane; the extraction solvent II is ethyl acetate;

(3) Drying the extract obtained in the step (2) by using nitrogen, adding methanol for redissolution, freezing at the temperature of minus 40 +/-5 ℃, freezing and centrifuging, and taking supernatant to obtain a pretreated sample;

(4) Adding an internal standard into the pretreated sample obtained in the step (2), and then carrying out quantitative analysis on the environmental pollutants by using a liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and/or a gas chromatography-tandem mass spectrometry (GC-MS/MS).

The amount of the recovery indicator used in step (1) is calculated as 0.5-20 ng per 200. Mu.L of plasma.

The recovery rate indicator in the step (1) comprises Tris 2-butoxy- [13C2] -ethyl) Phosphate (Tris (2-butoxy- [13C2] -ethyl) Phosphate), tri-n-butyl Phosphate-d27 (Tri-n-butyl Phosphate-d 27), tris (2-chloroethyl) Phosphate-d12 (Tris (2-chloroethyl) Phosphate-d 12), tris (1, 3-dichloro-2-propyl) Phosphate-d15 (Tris (1, 3-dichloro-2-propyl) Phosphate-d 15), triethyl Phosphate-d15 (Triethyl Phosphate-d 15), triphenyl Phosphate-d15 (phenyl Phosphate-d 15) Bis (butoxyethyl) Phosphate-d8 (Bis (butoxyethyl) Phosphate-d 8), bis (1, 3-dichloro-2-propyl) Phosphate-d10 (Bis (1, 3-dichloro-2-propyl) Phosphate-d 10), bis (2-ethylhexyl) Phosphate-d34 (Bis (2-ethylhexyl) Phosphate-d 34), dibutyl Phosphate-d18 (Dibutyl Phosphate-d 18), di-o-tolyl Phosphate-d14 (Di-o-cresyl Phosphate-d 14), di-p-tolyl Phosphate-d14 (Di-p-cresyl Phosphate) -d 14), diphenyl Phosphate-d10 (Diphenyl Phosphate-d 10), dibenzyl phthalate-d4 (Dibenzyl phthalate-d 4), di-n-butyl phthalate-d4 (Di-n-butyl phthalate-d 4), diisobutyl phthalate-3,4,5,6-d4 (Di-iso-butyl phthalate-3,4,5,6-d 4), dicyclohexyl phthalate-3,4,5,6-d4 (Dicyclohexyl phthalate-3,4,5,6-d 4) Bis (2-ethylhexyl) phthalate-3,4,5,6-d4 (Bis (2-ethylhexyl) phthalate-3,4,5,6-d 4), diethyl phthalate-3,4,5,6-d4 (Diethyl phthalate-3,4,5,6-d 4), di-n-hexyl phthalate-3,4,5,6-d4 (Di-n-hexyl phthalate-3,4,5,6-d 4) Dimethyl phthalate-3,4,5,6-d4 (Dimethyl phthalate-3,4,5,6-d 4), di-n-pentyl phthalate-3,4,5,6-d4 (Di-n-pentyl phthalate-3,4,5,6-d 4), di-n-propyl phthalate-3,4,5,6-d4 (Di-n-propyl phthalate-3,4,5,6-d 4), monobenzyl phthalate-d4 (Mono-n-butyl phthalate-d 4), mono-n-butyl phthalate-d4 (Mono-n-butyl phthalate-d 4), bis (2-ethylhexyl) adipate-d8 (Bis (2-ethylhexyl) adipate-d 8), tributyl O-citrate-d 3 (Tributyl O-acetate) -d3 (Tributyl O-butyl phthalate-d 4), bisphenol A-d6 (Bisphenol A-d 6), bisphenol S-C12 (Bisphenol S-C12), triclosan-d3 (Triclosan-d 3), 2,4-dihydroxybenzophenone-13C6 (2, 4-dihydroxybenzophenone-13C 6), benzothiazole-d4 (benzothiazole-d 4), 1H-benzotriazole- (cyclo-d 4) (1H-benzotriazole- (ring-d 4)), 5-methylbenzotriazole-d 6 (5-triazine-d 6), benzophenone-d10 (Benzophenone-d 10), 2-Hydroxy-4-methoxybenzophenone-d5 (2-Hydroxy-4-methoxybenzophenone-d 5) Perfluoro-n- [ (13) C4] butyric acid (Perfluoro-n- [ (13) C4] butanoic acid), perfluoro-n- [1,2- (13) C2] hexanoic acid (Perfluoro-n- [1,2- (13) C2] hexanoic acid), perfluoro-1-hexane [ (18) O2] Sodium sulfonate (Sodium perfluor-1-hexanone [ (18) O2] sulfonate), perfluoro-n- [1,2,3,4- (13) C4] octanoic acid (Perfluoro-n- [1,2,3,4- (13) C4] octanoic acid), perfluoro-n- [1,2,3,4- (13) C4] nonanoic acid (Perfluoro-n- [1,2,3,4,5- (13) C5] nonanoic acid), sodium perfluorosulfonate-1- [1,2,3,4- (13) C4] octanesulfonate (Sodiumperfluoro-1- [1,2,3,4- (13) C4] octanesulfonate), perfluoro-N- [1,2- (13) C2] decanoic acid (Perfluo-N- [1,2- (13) C2] decanoic acid), perfluoro-N- [1,2- (13) C2] undecanoic acid (Perfluo-N- [1,2- (13) C2] undecanoic acid), perfluoro-N- [1,2- (13) C2] dodecanoic acid (Perfluo-N- [1,2- (13) C2] dodecanoic acid) Perfluoro-1- [13C8] octanesulfonamide (Perfluoro-1- [13C8] octanesulfonamide), N-methyl-d3-Perfluoro-1-octanesulfonamide (N-methyl-d 3-Perfluoro-1-octanesulfonamide), N-ethyl-d5-Perfluoro-1-octanesulfonamide (N-ethyl-d 5-Perfluoro-1-octanesulfonamide), 1H, 2H-Perfluoro-1- [1,2-13C2] -octane Sodium sulfonate (Sodium 1H,1H, 2H-Perfluoro-1- [1,2-13C2] -octane sulfonate (6 Imidacloprid-D4 (Imidacloprid-D4), thiacloprid-D4 (Thiacloprid-D4), thiamethoxam-D3 (Thiamexam-D3), carbendazim D3 (Carbendazim D3), carbofuran D3 (Carbofuran D3), 2, 4-dichlorophenoxy-3, 5, 6-D3-acetic acid (2, 4-D3), 2,4'-Dichlorodiphenyltrichloroethane-D8 (2, 4' -Dichlorodiphenyltrichloroethane-D8), 2- (4-chloro-2-methylphenoxyphenoxy) propionic acid-D3 (Mecoprop D3), thiabendazole D4 (Thiabendazole D4), decadeuterated Simazine (Simazine D10), terbutryn-D5 (Terbiuret 5), isoproturon D6 (Isoproturon D6), isoproturon 4 (Methylon D6), metosulam 4 (Methylon D6), metoclopramide (Methylon D4 (Methylon D6) and metosulindazoxystrobin 4.

The plasma in the step (1) is human or animal plasma; preferably human or sheep blood plasma; more preferably human plasma.

The plasma in step (1) is preferably obtained by: and (4) centrifuging the collected blood, and taking supernatant to obtain the required plasma.

The centrifugation conditions are as follows: centrifuge at 3000rpm for 3 minutes.

The added recovery rate indicator in the step (1) is an isotope-labeled compound of the detected target compound, and can effectively correct the loss of the compound in the pretreatment process; in the invention, most target compounds have one-to-one corresponding recovery indicators, and the compounds which cannot be in one-to-one correspondence use the isotope labels corresponding to the same class of compounds.

The formula of the extraction solvent I in the step (2) is as follows: 298.2mL of ethyl acetate, 198.8mL of n-hexane and 3mL of formic acid (the volume ratio of ethyl acetate to n-hexane is 3, and formic acid accounts for 0.6% of the volume of the extraction solvent I

The extraction in the step (2) needs 360-degree rotation and oscillation so that the extraction is more sufficient.

The repetition frequency in the step (2) is more than 2 times; preferably 2 times.

The centrifugation conditions in the step (2) are as follows: centrifuging at 3000-4000 rpm for more than 3min; preferably, the following components are used: centrifugation is carried out at 3000rpm for 3min in order to precipitate the suspension and to facilitate the transfer of the extractant.

The freezing time in the step (3) is 12 hours or more.

The conditions of the refrigerated centrifugation in the step (3) are as follows: centrifuging at-10 deg.C and 15000rpm for more than 5 min.

In the step (3), the extract liquid needs to be blown to near dryness and then is frozen after being redissolved by methanol, so as to separate out the lipid, and then the low temperature needs to be kept in a freezing centrifuge for freezing and centrifuging, so as to lead the lipid precipitate to be beneficial to the transfer of supernatant, thereby achieving the purpose of removing the lipid and reducing the matrix effect.

The dosage of the internal standard in the step (4) is calculated according to 1-20 ng of each internal standard added into each 50 mu L of the pretreated sample.

The internal standard in the step (4) comprises a perfluorinated compound, a plasticizer (plastic additive), an organochlorine pesticide, an organophosphorus pesticide and an internal standard of a liquid crystal monomer.

The internal standard of the Perfluoro compound is Perfluoro-n- [13C8] caprylic acid (Perfluo-n- [13C8] octanoid acid M8PFOA.

The internal standard of the positive mode of the plasticizer is coumaphos-d10 (coumaphos-d 10), and the internal standard of the negative mode is Bisphenol A-d16 (Bisphenol A-d16; BPA-d 16).

The inner standard of the organochlorine pesticide is Decachlorodiphenyl ether (Decachlorodiphenyl ether; DCDE).

The internal standard of the positive mode of the organophosphorus pesticide is coumaphos-d10 (coumaphos-d 10), and the internal standard of the negative mode is tert-butyl p-hydroxybenzoate-d 9 (tert-butyl paraben-d 9).

The internal standard of the liquid crystal monomer is Decachlorodiphenyl ether (Decachlorodiphenyl ether; DCDE).

And (4) performing the liquid chromatography-tandem mass spectrometry by using an ultra-high performance liquid chromatography-tandem mass spectrometry combined instrument.

The pollutants quantitatively analyzed for environmental pollutants by liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) in step (4) include at least one of Organophosphates (OPs), phthalates (PAEs), personal Care Products (PCPs), phenolic compounds, ultraviolet stabilizers (UV), photoinitiators, antioxidants (AO), plasticizers, perfluorinated compounds (PFCs), organophosphorus Pesticides (OPs), pyrethroids, neonicotinoids, carbamates, acid herbicides, azole pesticides, triazolone pesticides, urea pesticides, amides, strobilurin fungicides, and other insecticides.

The Organic Phosphate Esters (OPEs) comprise at least one of organic phosphate diesters and organic phosphate triesters.

The organic phosphate diesters (Organophosphate diesters) include Bis (1-chloro-2-propyl) phosphate (Bis- (1-chloro-2-propyl) phosphate), diphenyl phosphate (Diphenyl phosphate), dibutyl phosphate (Dibutyl phosphate), bis (1, 3-dichloro-2-propyl) phosphate (Bis (1, 3-dichloro-2-propyl) phosphate), di-p-tolyl phosphate (di-p-tolyl phosphate), bis (butoxyethyl) phosphate (Bis (butoxyethyl) phosphate), and Bis (2-ethylhexyl) phosphate (Bis (2-ethylhexyl) phosphate).

The Organophosphate triesters include Triethyl phosphate (Triethyl phosphate), tris (2-Chloroethyl) phosphate (Tris (2-Chloroethyl) phosphate), tripropyl phosphate (Tripropyl phosphate), tetrakis (2-Chloroethyl) dichloroisoamyl diphosphate (Tetrakis (2-Chloroethyl) dichloroisopropyldiphosphate), triphenyl phosphate (Triphenyl phosphate), tris (2, 3-dibromopropyl) phosphate (Tris (2, 3-dibromopropyl) phosphate), tributyl phosphate (Tributyl phosphate), cresyl phosphate (Cresyldiphenyl phosphate), tris (2-butoxyethyl) phosphate (Tris (2-butoxyethyl) phosphate) Tricresyl phosphate, resorcinol bis (diphenyl phosphate) (resorcinyl bis (diphenyl phosphate)), 2-Ethylhexyl diphenyl phosphate (2-Ethylhexyl-diphenyl phosphate), isodecyl diphenyl phosphate (Isodecyl diphenyl phosphate), tris (3, 5-dimethylphenyl) phosphate (Tris (3, 5-dimethylphenyl) phosphate), bisphenol A bis (diphenyl phosphate) (biphenol A bis (diphenyl phosphate)), tris (2-isopropylphenyl) phosphate (Tris (2-isopropylphenyl) phosphate), tris (2-Ethylhexyl) phosphate (Tris (2-Ethylhexyl) phosphate), t-Butylphenyl diphenyl phosphate (t-Butylphenyl diphenyl phosphate), 2-Isopropylphenyl diphenyl phosphate (2-Isopropylphenyl diphenyl phosphate), 4-Isopropylphenyl diphenyl phosphate (4-Isopropylphenyl diphenyl phosphate), bis (2-Isopropylphenyl) phenyl phosphate (Bis (2-Isopropylphenyl) phenyl phosphate), 2,4-Diisopropylphenyl diphenyl phosphate (2, 4-Diisopropylphenyl diphenyl phosphate), bis (4-Isopropylphenyl) phenyl phosphate (Bis (4-Isopropylphenyl) phenyl phosphate), tris (3, 4-dimethylphenyl) phosphate (Trosi (3, 4-dimethylphenyl) phosphate) Tris (4-t-Butylphenyl) phosphate (Tris (4-tert-Butylphenyl) phosphate), bis (2, 4-Diisopropylphenyl) phenylphosphate (Bis (2, 4-Diisopropylphenyl) phenyl phosphate), tris (3-Isopropylphenyl) phosphate (Tris (3-Isopropylphenyl) phosphate), tris (4-Isopropylphenyl) phosphate (Tris (4-Isopropylphenyl) phosphate), 2-t-Butylphenyl diphenylphosphate (2-t-Butylphenyl diphenyl phosphate), 4-t-Butylphenyl diphenylphosphate (4-t-Butylphenyl diphenyl phosphate), bis (2-t-Butylphenyl) phenylphosphate (Bis (2-t-butyl phenyl) and Bis (4-t-Butylphenyl) phenyl phosphate Based phosphate (Bis (4-tert-butyl) phenyl phosphate).

The phthalate esters (PAEs) comprise at least one of phthalate monoesters and phthalate diesters.

The monoesters of phthalic acid (phthalates) include mono (monoethyl) Phthalate, mono (isopropyl) Phthalate, mono (butyl) Phthalate, mono (n-pentyl) Phthalate, mono (n-cyclohexyl) Phthalate, mono (hexyl) Phthalate, mono (benzyl) Phthalate, mono (2-heptyl) Phthalate mono octyl Phthalate (monooctyl Phthalate), monoethylhexyl Phthalate (monooethylhexylphthalate), monoisononyl Phthalate (monoolsononyl Phthalate), mono (2-ethyl-5-oxyhexyl) Phthalate (mono (2-ethyl-5-oxyhexyl) Phthalate), mono (2-ethyl-5-hydroxyhexyl) Phthalate (mono (2-ethyl-5-hydroxyhexyl) Phthalate) and mono (2-ethyl-5-carboxypentyl) Phthalate (mono (2-ethyl-5-carboxypentyl) Phthalate).

The terephthalic diesters (phthalates) include dimethyl isophthalate, dimethyl Phthalate, diethyl Phthalate, diallyl Phthalate, dipropyl Phthalate, di-n-propylphthalate Diisopropyl Phthalate (diisopropylphthalate), diisobutyl Phthalate (diisobutylphthalate), dibutyl Phthalate (dibutyl Phthalate), isobutylcyclohexyl Phthalate (isobutyylcyclohexyl Phthalate), diallyl Phthalate (diisopropylphthalate), diisopentyl Phthalate (diisopropylphthalate) butyl benzyl Phthalate, diphenyl isophthalate, diphenyl Phthalate, dihexyl Phthalate, bis (4-methyl-2-pentyl) Phthalate dibenzyl Phthalate (dibenzyl Phthalate), diheptyl Phthalate (diisoheptyl Phthalate), dinonyl Phthalate (dinonyl Phthalate), behenyl Phthalate (behenyl Phthalate), and bis (2-ethylhexyl) adipate.

The class of Personal Care Products (Personal Care Products) includes methyl Paraben (methyl Paraben), butyl Paraben (butyl Paraben), benzyl Paraben (benzyl Paraben), ethyl Paraben (ethyl Paraben), propyl Paraben (propyl Paraben), n-heptyl Paraben (hexyl Paraben), and Triclosan (Triclosan).

The phenolic compound comprises at least one of bisphenol analogs.

The bisphenols include bisphenol A (bisphenol A), bisphenol E (bisphenol E), bisphenol B (bisphenol B), bisphenol C (bisphenol C), bisphenol AF (bisphenol AF), bisphenol F (bisphenol F), bisphenol M (bisphenol M), bisphenol P (bisphenol P), bisphenol G (bisphenol G), bisphenol Z (bisphenol Z), bisphenol S (bisphenol S), bisphenol AP (bisphenol AP), bisphenol BP (bisphenol BP), and bisphenol PH (bisphenol PH).

The ultraviolet stabilizer (UV) includes at least one of benzophenones, benzothiazoles, benzotriazoles, and other classes of UV stabilizers.

The Benzophenone ultraviolet stabilizer (Benzophenone UV stabilizers) comprises 2,4-dihydroxybenzophenone (2, 4-dihydroxybenzophenone), 2', 4' -tetrahydroxybenzophenone (2, 2',4,4' -tetrahydroxybenzophenone), 2-hydroxy-4-methoxybenzophenone (2-hydroxy-4-methoxybenzophenone), 2-hydroxy-4-methoxy-5-sulfonic acid Benzophenone (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate), 2'-dihydroxy-4, 4' -dimethoxybenzophenone (2, 2-dihydroxy-4, 4-dimethoxybenzophenone), 2 '-hydroxy-4-methoxybenzophenone (2, 2' -dihydroxy-4-methoxybenzophenone), 4-hydroxybenzophenone (4-hydroxybenzophenone) and 2,3,4-trihydroxybenzophenone (2, 3, 4-trihydroxybenzophenone).

The benzothiazole ultraviolet stabilizers (Benzothiazoles UV stabilizers) include 2-methylbenzothiazole (2-methylbenzothiazole), 2-benzothiazolyl-N-morpholinosulfide (2- (morpholinothio) -benzothiazole), 2-methylthiobenzothiazole (2- (methylthio) benzothiazole), 2-aminobenzothiazole (2-aminobenzothiazole) and 2-hydroxybenzothiazole (2-benzothiazole).

The benzotriazole UV stabilizers include 1-hydroxybenzotriazole (1-hydroxybenzotriazole), 5-methylbenzotriazole (5-methyl-1-hydroxybenzotriazole), 5-chlorobenzotriazole (5-chloro-1-hydroxybenzotriazole), 4-methyl-1-hydroxybenzotriazole (4-methyl-1H-benzotriazole), 2- (2 ' -Hydroxy-5 ' -methylphenyl) benzotriazole (2- (2-Hydroxy-5-methylphenyl) benzotriazole), 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole (2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole) and 2- (2 ' -Hydroxy-3 ',5' -Di-tert-butyl-3 ',5' -Di-tert-butylphenyl) -benzotriazole (2- (5-butyl-2-hydroxyphenyl) benzotriazole, and the like.

Other classes of UV stabilizers (other UV stabilizers) include 4-tert-butyl-4'-methoxydibenzoylmethane (4-tert-butyl-4' -methoxydibenzoylmethane), 4-methylbenzylidene camphor (4-methylbenzylidene camphor), isoamyl methoxycinnamate (isoamyl 4-methoxycinnamate), isooctyl 2-cyano-3, 3-diphenylacrylate (2-ethylhexyl 2-cyanoo-3, 3-diphenyl-2-propenoate (liquid)), isooctyl p-dimethylaminobenzoate (octyl dimethyl-p-aminobenzoic acid), octyl p-methoxycinnamate (Ethylhexyl methoxycinnamate), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol) 2,4-Di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol (2, 4-Di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol) and 2- (2H-benzotriazol-2-yl) -4, 6-Di-tert-amylphenol (2- (2H-benzotriazol-2-yl) -4, 6-Di-tert-amylphenol).

The photoinitiator (photoinitiators) comprises benzophenone (benzophenone), 4-methylbenzophenone (4-methylbenzophenone), 1-hydroxycyclohexyl phenyl ketone (1-hydroxycyclohexyl phenyl ketone), 4-phenyl benzophenone (4-phenyl benzophenone/4-benzoyl biphenyl), 1,2-diphenyl-1,2-ethanedione (1, 2-diphenyl-1, 2-ethane), 2-ethyl anthraquinone (2-ethyl anthraquinone), methyl benzoylbenzoate (methyl-2- (benzoyl) benzoate), 2-dimethoxy-2-phenylacetophenone (2, 2-dimethoxy-2-phenyl acetophenone) p-dimethylaminobenzophenone (4- (dimethylamino) benzophenone), 4'-bis (dimethylamino) benzophenone (4, 4' -bis (dimethylamino) benzophenone), 4'-bis (diethylamino) benzophenone (4, 4' -bis (dimethylamino) benzophenone), ethyl 4-aminobenzoate (ethyl-4-aminobenzoate), ethyl 4-dimethylaminobenzoate (ethyl-4-dimethylaminobenzoate), 2-isopropylthioxanthone (2-isopropylthioxanthone) and 2,4-diethylthioxanthone (2, 4-diethylthioxanthone/2, 4-diethyl-9H-thioxanthone-9-one).

The antioxidants (antioxidants) comprise antioxidants which are detected in a positive ion detection mode and a negative ion detection mode.

<xnotran> 3- -4- (3-tert-butyl-4-hydroxyanisole), 3,5- -4- (3,5-di-tert-butyl-4-hydroxybenzaldehyde), 3,5- -4- (3,5-di-tert-butyl-4-hydroxybenzoic acid), 2,6- -4- ( ) (2,6-di-tert-butyl-4- (hydroxymethyl) phenol), 2,4- (2,4-di-tert-butylphenol), 4,4'- (6- - ) (4,4' -butylidenebis (6-tert-butyl-m-cresol)), 4- (1,1,3,3- ) (4- (1,1,3,3-tetra-methylbutyl) phenol), 2,2'- (4- -6- ) (2,2' -methylenebis (4-ethyl-6-tert-butylphenol)), 2,2'- (6- -4- ) (2,2' -methylenebis (6-tert-butyl-4-methylphenol)), -3,5- -4- (diethyl-3,5-Di-tert-butyl- </xnotran> 4-hydroxybenzyl phosphate), 2'-thiobis (6-tert-butyl-p-cresol) (2, 2' -thiobis (6-tert-butyl-p-cresol)), 1,2-bis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine (1, 2-bis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine) and 4,4'-thiobis (6-tert-butyl-m-cresol) (4, 4' -thiobis (6-tert-butyl-m-cresol)).

The antioxidant for detection in the positive ion detection mode includes 1,3-Di-o-tolylguanidine (1, 3-Di-tolylguanidine), 1,3-diphenyl-2-thiourea (1, 3-diphenyl-2-thiourea), 2' -ethylene-bis (4, 6-Di-tert-butylphenol) (2, 2' -ethylidene-bis (4, 6-Di-tert-butylphenol)), methyl-2-mercaptobenzimidazole (methyl-2-mercaptobenzimidazole), 11-Methyldodecyl3- [4-hydroxy-3,5-bis (2-methyl-2-propyl) phenyl ] propionate (11-Methyldodecyl 3- [4-hydroxy-3,5-bis (2-methyl-2-propyl) phenyl ] propionate) ((2-methyl-2-propyl) phenyl ] propionate) ' dibenzylhydroxylamine (dibenzylhydroxylamine), tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate (Tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate), 1,3,5-trimethyl-2,4,6-Tris (3, 5-Di-tert-butyl-4-hydroxybenzyl) benzene (3, 5-trimethyl-2,4,6-Tris (3, 5-Di-tert-butyl-4-hydroxybenzyl) benzene), 2,6-Di-tert-butyl-4- (dimethylaminomethyl) phenol (2, 6-Di-tert-butyl-4- (dimethylaminomethyl) phenol), tris (2, 4-di-tert-butylphenyl) phosphite (tris (2, 4-di-tert-butylphenyl) phosphate), analixant 1035, 2'-thiobis (6-tert-butyl-p-cresol), analixant 1098, analixant 245, analixant 259, 4- [ [4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl ] amino ] -2, 6-di-tert-butylphenol (4- [ [4,6-bis (octylsulfanyl) -1,3,5-triazin-2-yl ] amino ] -2, 6-di-tert-butylphenol), N-phenyl-1-naphthylamine (N-phenyl-1-naphthylamine), bis [4- (2-phenyl-2-propyl) phenyl ] amine (analtindi [4- (2-phenyl-2-propyl) phenyl ] amine (N-phenyl-1-naphthylamine), N-Diphenyl [4- (2-phenyl-2-propyl) phenyl ] amine (N, 4' -Diphenyl-1-Diphenylguanidine), N-Diphenyl-1-diphenylthiourea (N, 3 '-diphenylthiourea), N-Diphenyl-1-diphenylthiourea and N, 3' -diphenylthiourea).

The plasticizers (plasticizers) include diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl azelate, 2,4-trimethyl-1,3-pentanediol diisobutyrate, 2,4-trimethyl-1,3-pentanediol diisobutyrate, dibutyl fumarate, dimethyl sebacate, isopropyl myristate, triethyl citrate, diethylene glycol dibenzoate, dibutyl sebacate, isopropyl palmitate Acetyl Triethyl citrate (Acetyl trietyl citrate), propyl oleate (n-Propyl oleate), di (2-ethylhexyl) maleate (Di (2-ethylhexyl) maleate), dipropylene glycol dibenzoate (Oxydipropyl dicarboxylate), glycerol monooleate (glycomonoleate), dihexyl azelate (Di-n-hexyl acrylate), glycerol stearate (glycomonoleate), tributyl citrate (Tributyl citrate), methyl 2-Tetrahydrofurfuryl (Z) -oleate, butyl 9-ene-octadecanoate (n-Butyl acrylate), isooctyl azelate (diooctyl azelate), acetyl tri-n-butyl citrate (acetyl tri-n-butyl citrate), diisooctyl sebacate (2-Ethylhexyl sebacate), tri-n-hexyl butyryl citrate (n-butyryl tri-n-hexyl citrate), heptylnonyl adipate (di (n-hexyl, n-nonyl) adipate), dibutyl adipate (dibutyl adipate), diisodecyl adipate (diisodecyl adipate), diisononyl cyclohexane 1,2-dicarboxylate (di-isopropyl cyclic hexane-1, 2-dicarboylate) and trioctyl trimellitate (trioctyl trimalate).

The Perfluoro-compound includes Perfluoro-N-octanoic acid (perfluorooctanoic acid), perfluorooctanesulfonic acid (perfluorooctane sulfonic acid), perfluoro-N-butanoic acid (perfluoron-butanoic acid), perfluoro-N-heptanoic acid (perfluorooctanoic acid), perfluoro-N-hexanoic acid (perfluorohexanoic acid), perfluoro-N-decanoic acid (perfluorodecanoic acid), perfluoro-N-dodecanoic acid (perfluorododecanoic acid), perfluoro-N-nonanoic acid (perfluorononanoic acid), perfluoro-N-undecanoic acid (perfluoroundecanoic acid), perfluoro-N-pentanoic acid (perfluoroundecanoic acid), and Perfluoro-N-decanoic acid (tetradecanoic acid) Perfluoro-N-tridecanoic acid (Perfluoro-N-tridecanoic acid), potassium Perfluoro-1-butane sulfonate (Potasium perfluor-1-butanesulfonate), sodium Perfluoro-1-decane sulfonate (Sodium perfluor-1-decane sulfonate), sodium Perfluoro-1-heptane sulfonate (Sodium perfluor-1-heptane sulfonate), sodium Perfluoro-1-hexane sulfonate (Sodium perfluor-1-hexane sulfonate), perfluoro-1-octane sulfonamide (Perfluoro-1-octane sulfonamide), N-methylperfluor-1-octane sulfonamide (N-methylperfluor-1-octane sulfonate), N-ethylperfluor-1-octane sulfonamide (N-ethylperfluor-1-octane sulfonamide), 1H, 2H-Sodium perfluorohexane sulfonate (4H, 1H, 2H-perfluorohexane sulfonate (4.

The organophosphorus pesticides include chlorpyrifos (dursban/chlorpyrifos), diazinon (diazinon), parathion-methyl (parathion-methyl), malathion (malathion), dimethoate (dimethoate), dichlorvos (dichlorvos), 3-methyl-4-Nitrophenol (3-methyl-4-Nitrophenol), coumaphos (coumaphos), dioxazophos (dioxabenzofos), fenamiphos (difenofos), fenamiphos (difenophos), 2-isopropyl-6-methyl-4-pyrimidinol (2-isopropyl-6-methyl-4-pyrimidinol), isofenamiphos (isofenaphos-methyl), mecarbam (mecarbam), pesticides (methocarifos), xanthone (saprophos), pyrazophos (pyrazofos) and Nitrophenol (Nitrophenol).

The pyrethroids include 3-phenoxybenzyl alcohol (3-PBA), 4-fluoro-3-phenoxybenzoic acid (4-fluoro-3-phenoxy benzoic acid), cis-3- (2-chloro-3, 3-trifluoro-1-propenyl) -2, 2-dimethyl-cyclopropanecarboxylic acid (cis-3- (2-chloro-3, 3-trifluoro-1-propynyl) -2, 2-dimethyl-cyclopropanecarboxylic acid) and Lambda-cyhalothrin (Lambda-halothrin).

The neonicotinoid pesticide comprises Acetamiprid (Acetamiprid), dinotefuran (Dinotefuran), imidacloprid (Imidacloprid), thiacloprid (Thiaclprid) and Thiamethoxam (Thiamethoxam).

The carbamate pesticide comprises Carbendazim (Carbendazim), carbofuran (Carbofuran), chlorpromazine (Chlorpropham), fenoxycarb (Fenobucarb), isocarb (Iprovalicarb), methomyl (Methomyl), pirimicarb (Pirimicarb) and anilazine (Propham).

The acidic herbicides include 2, 4-dichlorophenoxybutyric acid (2, 4-DB), 2,4, 5-aldicacid (2, 4,5-TP (Silvex)), 2,4,5-trichlorophenoxyacetic acid (2, 4,5-trichlorophenoxyacetic acid), 2, 4-Dichlorprop-2 (Dichloroprop), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2-methyl-4-chloropentoxypropionic acid (Mecoprop) and 2-methyl-4-chlorophenoxybutyric acid (MCPB).

The azole pesticides include Bitertanol (Bitertanol), cyproconazole (Cyproconazole), difenoconazole (Difenoconazole), epoxiconazole (Epoxiconazole), fenbuconazole (Fenbuconazole), flusilazole (Flusilazole), dichlofluanid (Imazalil), butylaniline (Myclobutanil), pentoconazole (Penconazole), prochloraz (Prochlororaz), tebuconazole (Tebuconazole), tetraconazole (Tetraconazole) and Thiabendazole (Thiabendazole).

The triazolone pesticide comprises clomazone (Chloridazone), hexazinone (Hexazinone), metamitron (Metamitron), metribuzin (Metribzin), aniline (ametryn), attachton (atraton), atrazine (atrazine), prometon (prometon), prometryn (prometryn), promazine (propazine), sec-buteton (secbumeton), simazine (simazine), simetryn (simetryn) and terbutryn (terbutryn/panane).

The urea pesticide comprises chlorsulfuron (Chloroxuron), chlorourone (Chloroloron), 1- (3, 4-dichlorophenyl) -3-methylurea (1- (3, 4-dichlorophenyl) -3-methylurea), 1- (3, 5-dichlorophenyl) urea (DCPU), methabenzthiazuron (Methabenzhiazuron), bromouron (Methobromuron), metoxuron (Methoxyuron), diuron (Diuron), 3-phenyl-1, 1-dimethylurea (Fenuron), isoproturon (Isoproturon) and Linuron (Linuron).

The amide pesticides include Alachlor (Alachlor), dimethachlor (dimethachlorir), N-dimethylamino-N-toluene (DMST) and Fenhexamid (Fenhexamid).

The acrylate bactericide comprises Azoxystrobin (Azoxystrobin), fluacrypyr (fluacrypyr), kresoxim-methyl (Kresoxim-methyl), pyraclostrobin (Pyraclostrobin) and Trifloxystrobin (Trifloxystrobin).

Such other insecticides include fluocinolone (Flutolanil), boscalid (Boscalid), famoxadone (Famoxadone), metalaxyl (Metalaxyl), nuarimol (Nuarimol) and Prosulfocarb (Prosulfocarb).

And (4) performing the gas chromatography-tandem mass spectrometry by using a gas chromatography-tandem mass spectrometry combined instrument.

The pollutants quantitatively analyzed for environmental pollutants by gas chromatography-tandem mass spectrometry (GC-MS/MS) in the step (4) comprise at least one of organochlorine pesticides and liquid crystal monomers.

The organochlorine pesticide comprises dichloropropionic acid (Aldrin), ALPHA-hexachloro (ALPHA-HCH), BETA-hexachloro (BETA-HCH), lindane (gamma-HCH (lindane)), delta-hexachloro (delta-HCH), ee-hexachloro (epsilon-HCH), cis-A-chlordane (cis-chlordane), trans-chlordane (trans-chlordane), oxychlorosene (oxy-chlordane), 4-drip (p.p '-DDD), 2-bis (4-chlorophenyl) -1, 1-dichloroethylene (p.p' -DDE), 2-bis (p-chlorophenyl) -1, 1-trichloroethane (p.p '-DDT) 1- (2-chlorophenyl) -1- (4-chlorophenyl) -2, 2-dichloroethane (o.p' -DDD), 3-o-chlorophenyl-2-p-chlorophenyl-1, 1-dichloroethylene solution (o.p '-DDE), 1-trichloro-2- (2-chlorophenyl) -2- (4-chlorophenyl) ethane (o.p' -DDT), dieldrin (Dieldrin), ALPHA-Endosulfan (ALPHA-Endosulfan), BETA-Endosulfan (BETA-Endosulfan), enterin (Endrin), endrin (Endrin ketone), heptachlor (Heptachlor), heptachloro-endo-epoxy (Heptachlor-exo-epoxide), hexachlorobenzene (hexachlorobezene) and Metazachlor (Metazachlor).

The liquid crystal monomer comprises 4-vinyl-4 '-propyl-1, 1' -dicyclohexyl (1- (4-propylcyclohexyl) -4-vinylcyclohexane), 1-methoxy-4- (4-propylcyclohexyl) cyclohexane (1-methoxy-4- (4-propylcyclohexyl 1) cyclohexane), 1- (prop-1-enyl) -4- (4-propylcyclohexyl) cyclohexane (1- (prop-l-enyl) -4- (4-propylcyclohexyl) cyclohexane), 1-ethoxy-2,3-difluoro-4- (4-propylcyclohexyl) benzene (1-ethoxy-2, 3-difluoro-4- (4-propylcyclohexyl) benzene) 4-methyl-4'-pentylbiphenyl (4-methyl-4' -pentyliphenyl), 1-ethoxy-2,3-difluoro-4- (4-propylphenyl) benzene (1-ethoxy-2, 3-difluoroo-4- (4-propylphenyl) bezene), 1- (4-ethylcyclohexyloxy) -4- [4- (trifluoromethylphenyloxy) benzyl ] bezene, 4- (4-methylphenyl) -4'-vinyl-1,1' -bis (cyclohexyl) (4- (4-methylphenenyl) -4'-vinyl-1,1' -bi (cyclohexyloxy)) 4- [ difluoro (3, 4, 5-trifluorophenoxy) methyl ] -3,5-difluoro-4'-propylbiphenyl (4- [ difluoro (3, 4, 5-trifluorophenoxy) methyl ] -3,5-difluoro-4' -propylbiphenyl), 1-methyl-4- (4- (4-propylcyclohexyl) cyclohexyl) benzene (1-methyl-4- (4- (4-propylcyclohexyl) cyclohexyl) cyclohexane), 4- [ difluoro (2-methyl-3, 4, 5-trifluorophenoxy) methyl ] -3,5-difluoro-4'-propylbiphenyl (4- [ difluoro (2-methyl-3, 4, 5-trifluorophenoxy) methyl ] -3,5-difluoro-4' -propylbiphenyl) 2, 3-difluoro-1-methoxy-4- (4- (4-propylcyclohexyl) cyclohexyl) benzene (2, 3-difluoro-l-methoxy-4- (4- (4-propylcyclohexyl) cyclohexyl) bezene), l-ethyl-4- (4- (4-propylcyclohexyl) phenyl) benzene (l-ethyl-4- (4- (4-propylcyclohexyl) phenyl) bezene), 2,3-difluoro-1-ethoxy-4- (4- (4-ethylcyclohexyl) phenyl) benzene (2, 3-difluoro-1-ethoxy-4- (4- (4-ethylcyclohexyl) phenyl) bezene), 4"-ethyl-2'-fluoro-4-propyl-l, l':4',1" -terphenyl (4 "-ethyl-2' -fluoro-4-propyl-l, l ':4',1" -terphenyl), (4-ethoxy-2, 3-difluoro-4'- (4-propylcyclohexyl) biphenyl), 2, 3-difluoro-1-propoxy-4- (4- (4-propylcyclohexyl) cyclohexyl) benzene (2, 3-difluoro-l-propoxy-4- (4- (4-propylcyclohexyl) cyclohexyl) benzene), 1- (4- (4-butylcyclohexyl) cyclohexyl) -4-ethoxy-2,3-difluorobenzene (1- (4- (4-butylcyclohexyl) cyclohexyl) -4-ethoxy-2, 3-difluorobenzene), 4-butyl-4"-ethyl-2' -fluoro-l, 4',1" -cyclohexyl (4-butylcyclohexyl) -4' -difluoro-2 '-biphenyl), 4' -butyl-4 '-ethoxy-2' -biphenyl (4 '-cyclohexyl) biphenyl, 4' -difluoro-cyclohexyl) biphenyl, 4 '-ethoxy-2' -biphenyl, 4 '-ethoxy-2, 3-difluoro-2' -biphenyl ) -4-yl ] biphenol), 3,4-difluoro-4'-propyl-l, l' -Biphenyl (3, 4-difluoro-4'-propyl-l, l' -biphenol), 4 '-ethylbiphenyl-4-carbonitrile (4' -ethylbishydroxybenzyl-4-carbonitrile), 4 '-propoxy-4-biphenol-4-carbonitrile, 4-propyl 1-4' - [4- (trifluoromethoxy) phenyl ] -1,1 '-dicyclohexyl (4-propyl 1-4' - [4- (trifluoromethylphenoxy) phenyl ] -1,1 '-bicyclohexyl), 4"-ethyl-2',3,4,5-tetrafluoro-1,1':4',1" -terphenyl (4 "-ethyl-2',3,4,5-tetrafluoro-1,1' -cyano-4 '-biphenylyl), 4' -cyano-4 '-carbonyloxy-4' - (4-carbonyloxy) Biphenyl (4 '-methoxy-4-biphenylyl), 4' -methoxy-4 '-Biphenyl (4' -carbonyloxy) -4'- (4-carbonyloxy) Biphenyl (4-carbonyloxy) and 4' -carbonyloxy-4-biphenylyl).

The detection conditions of the liquid chromatography-tandem mass spectrometry in the step (4) are as follows:

(1) diesters of phthalic acid (phthalates esters)

The chromatographic conditions include:

a mobile phase A: 0.1% by volume of aqueous formic acid;

mobile phase B: methanol;

and (3) chromatographic column: c18 column (preferably: luna 2.5 μm C18 (2) -HST)

100×2.0mm)；

Flow rate: 0.2mL/min;

column temperature: at 40 ℃;

elution procedure: the volume percentage content of the initial mobile phase B is 40%; the volume percentage of the mobile phase B is increased from 40 percent to 70 percent within 0-2 min; 2-8 min, the volume percentage of the mobile phase B is increased to 100%; keeping the volume percent of the mobile phase B unchanged at 100% for 8-13 min, and reducing the volume percent of the mobile phase B to 40% for 13-13.1 min; 13.1-17 min, keeping constant at 40%;

the mass spectrometry conditions include: an electrospray ion source, wherein the temperature of the ion source is 550 ℃; the detection mode is a positive ion detection mode; atomization air pressure: nitrogen at 55psi;

(2) monoesters of phthalic acid (Phthalate monoesters), benzophenone-based UV stabilizers (Benzophenone UV stabilizers), bisphenol analogs (biphenol analogs), and Personal Care Products (Personal Care Products)

The chromatographic conditions include:

mobile phase A:0.2mmol/L aqueous ammonium acetate solution;

mobile phase B: methanol;

and (3) chromatographic column: c18 column (preferably: ZORBAX Extended-C18.5 μm)

100×2.1mm)；

Flow rate: 0.2mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping the 10 percent constant in 0-0.5 min; the volume percentage of the mobile phase B is increased from 10 percent to 50 percent within 0.5-1 min; 1-7 min, the volume fraction of the mobile phase B is increased from 50% to 99%; keeping the temperature constant at 99 percent for 7-10 min; 10-10.1 min, from 99% to 10%, 10.1-12 min, keeping the volume fraction of the mobile phase B unchanged at 10%;

the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a negative ion detection mode; atomization air pressure: nitrogen at 55psi;

(3) plasticizers (plasticizers), benzothiazoles (Benzothiazoles UV stabilizers), benzotriazoles (benzotriazoles UV stabilizers) and other classes of UV stabilizers, photoinitiators (photoinitiator Additives) and antioxidants for testing in positive ion testing mode

The chromatographic conditions include:

a mobile phase A: 0.1% by volume of aqueous formic acid;

and (3) mobile phase B: methanol;

a chromatographic column: c18 column (preferably: luna 2.5 μm C18 (2) -HST)

100×2.0mm)；

Flow rate: 0.3mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B is 40 percent, and the initial mobile phase B is kept unchanged at 40 percent within 0-2 min; 2-4 min, the volume percentage of the mobile phase B is increased from 40% to 80%; 4-14 min, the volume percentage of the mobile phase B is increased from 80% to 100%; 14-17 min, keeping the volume percentage of the mobile phase B constant at 100%; the volume percentage of the mobile phase B is reduced to 40 percent within 17-20 min, and the volume percentage of the mobile phase B is kept unchanged within 20-24 min;

the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a positive ion detection mode; atomization air pressure: nitrogen at a pressure of 55psi;

(4) organic phosphoric acid triesters (Organophosphate triesters)

The chromatographic conditions include:

mobile phase A: formic acid aqueous solution with volume fraction of 0.1 percent;

mobile phase B: methanol;

a chromatographic column: an RP18 column (preferably: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm);

flow rate: 0.3mL/min;

column temperature: at 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B is 5 percent, and the initial mobile phase B is kept at 5 percent in 0-1 min; the volume fraction of the mobile phase B is increased from 5 percent to 40 percent within 1-3 min; 3-12 min from 40% to 100%; keeping 100 percent unchanged for 12-15 min; 15-15.1 min, the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent; the volume fraction of the mobile phase B is kept unchanged at 5 percent for 15.1 to 18 min;

the mass spectrometry conditions include: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a negative ion detection mode; atomization air pressure: nitrogen at a pressure of 55psi;

(5) organophosphate diesters (Organophosphate diesters)

The chromatographic conditions include:

mobile phase A:0.2mmol/L aqueous ammonium acetate solution;

mobile phase B: methanol;

a chromatographic column: an RP18 column (preferably: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1 mm);

flow rate: 0.3mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B is 5 percent, and the initial mobile phase B is increased from 5 percent to 35 percent in 0-4 min; 4-7min, the volume fraction of the phase B is increased from 35% to 80%; rising from 80% to 100% in 7-12 min; keeping 100 percent unchanged for 12-14 min; 14-15 min, reducing the volume percentage of the mobile phase B from 100% to 5%; the volume percentage of the mobile phase B is kept unchanged at 5 percent for 15-20 min;

the mass spectrometry conditions include: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a negative ion detection mode; atomization air pressure: nitrogen at 55psi;

(6) antioxidant for detection in negative ion detection mode

The chromatographic conditions include:

mobile phase A:4mmol/L ammonium acetate aqueous solution;

mobile phase B: methanol;

a chromatographic column: c18 column (preferably: luna 2.5 μm C18 (2) -HST)

100×2.0mm)；

Flow rate: 0.2mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping 10% unchanged for 0-0.5 min; the volume percentage of the mobile phase B is increased from 10 percent to 50 percent in 0.5-1 min, and is increased to 99 percent in 1-7 min; keeping the temperature constant at 99 percent for 7-10 min; the volume percentage of the mobile phase B is rapidly reduced to 10 percent within 10 to 10.1 min; keeping the volume fraction of the mobile phase B unchanged at 10.1-12 min;

the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen at a pressure of 55psi;

(7) a perfluoro compound:

the chromatographic conditions include:

a mobile phase A:0.2mmol/L ammonium formate (pH = 4);

mobile phase B: methanol;

a chromatographic column: RP18 column (preferably: ACQUITY UPLC BEH Shield RP18,1.7 μm; 100X 2.1 mm);

flow rate: 0.3mL/min;

column temperature: at 40 ℃;

elution procedure: the initial mobile phase B volume percentage was 40%; keeping the content of the mobile phase B unchanged within 0-2 min, and increasing the volume percentage of the mobile phase B to 66% within 2-3 min; rising to 70 percent in 3-12 min; the volume fraction of the mobile phase B is increased from 70% to 100% in 12-14 min, and is kept constant at 100% in 14-16 min; quickly reducing the temperature to 40 percent within 16 to 16.1 min; the volume fraction of the mobile phase B is kept constant at 40% from 16.1 to 22;

the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a negative ion detection mode; atomization air pressure: nitrogen at 55psi;

(8) organophosphorus Pesticides (organophosphorous Pesticides), pyrethroids (pyrethioles), neonicotinoids (Neonicotinoids), carbamates (Carbamates), acid herbicides (Acid herbicides), azole Pesticides (Azoles), triazolones (triazenes/triazones), ureas (Urea), amides (Amide Pesticides), strobilurins (Strobilurins), other insecticides (Other Pesticides)

The chromatographic conditions include:

mobile phase A:5mmol/L ammonium acetate solution;

mobile phase B: acetonitrile;

and (3) chromatographic column: c18 chromatographic column (preferably: kinetex 2.6 μm C18)

100*2.1mm；00D4462-AN)；

Flow rate: 0.4mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B was 2%; the volume percentage of the mobile phase B rises from 2 percent macroscopically to 30 percent in 0-4 min; the volume percentage of the mobile phase rises from 30 percent to 68 percent in 4-22 min; the mobile phase B rises from 68% to 99% in 22-22.1 min; for 22.1-23 min, keeping the temperature unchanged at 99%; 23-23.1 min, reducing the volume percentage of the mobile phase B from 99% to 2%; keeping 2 percent unchanged for 23.1-26 min;

mass spectrum conditions: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen, at a pressure of 55psi.

The detection conditions of the gas chromatography-tandem mass spectrometry in the step (4) are as follows:

(9) organic chlorine pesticide:

the chromatographic conditions include:

a chromatographic column: agilent HP-5MS column 19091S-433 (Agilent 19091S-433, HP-5MS,30m 0.250mm 0.25 μm);

sample inlet temperature: 260 ℃;

temperature rising procedure: the initial temperature is 60 ℃, and the temperature is kept for 1min; heating to 300 deg.C at a speed of 5 deg.C/min, and maintaining for 9min;

mass spectrum conditions: electron bombardment ion source, ion source temperature is 230 ℃, quadrupole rod temperature is 150 ℃, solvent delay time is 3min;

liquid crystal monomer r:

the chromatographic conditions include:

a chromatographic column: agilent HP-5MS column 19091S-433 (Agilent 19091S-433, HP-5MS,30m 0.250mm 0.25 μm);

sample inlet temperature: 260 ℃;

temperature rising procedure: the initial temperature is 80 ℃, and the temperature is kept for 2.5min; then heating to 200 ℃ at the speed of 25 ℃/min and keeping for 1min; then the temperature is increased to 250 ℃ at the speed of 10 ℃/min, and then the temperature is increased to 285 ℃ at the speed of 5 ℃/min, and the temperature is kept for 5min; finally, the temperature is increased to 300 ℃ at the speed of 30 ℃/min, and the temperature is kept for 1min;

mass spectrum conditions: the electron bombards the ion source, the temperature of the ion source is 230 ℃, the temperature of the quadrupole rod is 150 ℃, and the solvent is delayed for 6min.

The method for analyzing the environmental pollutants in the blood plasma in the targeted exposure group is applied to analyzing the environmental pollutants in the blood plasma for the purpose of non-disease diagnosis and treatment.

Compared with the prior art, the invention has the following advantages and effects:

(1) The invention provides a high-throughput and convenient method for analyzing the targeted exposure group of the environmental pollutants in the human plasma, which can realize the simultaneous detection of various types of environmental pollutants in the plasma, has convenient pretreatment, short analysis time and low cost, can improve the analysis efficiency to the maximum extent, and can provide technical support for the subsequent observation and detection of the influence of the mixed effect of the environmental pollutants on the human health.

(2) The method can simultaneously analyze hundreds of different types of environmental pollutants in the plasma, and has the advantages of simple and convenient treatment method, short time consumption and high efficiency.

(3) When the plasma sample is pretreated, the extract liquor is blown to be nearly dry and is redissolved by methanol, then the extract liquor is frozen to separate out lipid, and then the low temperature is kept in a freezing centrifuge for freezing centrifugation to ensure that the lipid precipitation is beneficial to the transfer of supernatant, thereby achieving the aim of removing the lipid, reducing the matrix effect and further improving the recovery rate of the added standard.

Drawings

FIG. 1 is a graph showing the results of comparing the recovery of the spiked samples in the process of the present invention with that in comparative example 1.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Test methods without specifying specific experimental conditions in the following examples are generally performed according to conventional experimental conditions or according to the experimental conditions recommended by the manufacturer. Unless otherwise specified, reagents and starting materials for use in the invention are commercially available.

The extraction solvent involved in the examples, namely the mixed solvent of ethyl acetate and n-hexane containing 0.6% formic acid, the volume ratio of ethyl acetate to n-hexane is at least LC-MS grade, 2, and the pH value is adjusted by formic acid (the formic acid content is 0.6%); for example, 500mL of extracting agent is prepared, the dosage of ethyl acetate is 298.2mL, the dosage of n-hexane is 198.8mL, and the dosage of formic acid is 3mL.

Example 1: targeted exposure group analysis of environmental pollutants in human plasma

(1) Reagents and materials

A total of 377 compound standards, 74 isotopically labeled Chemicals as recovery indicators or internal standards, were purchased from AccuStandard, usa, sigma-Aldrich, hulington, canada, and Toronto Research Chemicals, canada; these include 39 Organophosphates (OPs) (including organophosphate diesters and organophosphate triesters), 36 Phthalates (PAEs) (including phthalate monoesters and phthalate diesters), 7 Personal Care Products (PCPs), 14 phenolic compounds (bisphenol analogs), 29 UV stabilizers (UV) (including benzophenones, benzothiazoles, benzotriazoles, and other classes of UV stabilizers), 15 photoinitiators, 34 Antioxidants (AO) (including positive and negative ion detection modes), 31 plasticizers, 25 perfluorinated compounds (PFCs), 18 Organophosphorus Pesticides (OPs), 24 organochlorine pesticides (OCPs), 4 pyrethroids, 5 neonicotinoids, 8 carbamates, 7 acid herbicides, 13 azole pesticides, 14 triazolones, 11 urea pesticides, 4 amide pesticides (amide insecticides), 5 methoxyacrylate fungicides, 6 other classes of pesticides (other insecticides), 28 Liquid Crystal Monomers (LCMs). Details of specific compounds are shown in table 1.

The target analyte is measured by a 5500Q Trap triple-chromatography-tandem mass spectrometer (7890B-5970A) and a gas chromatography tandem mass spectrometer (DURP-HPLC tandem mass spectrometer) which is purchased from Toronto AB Sciex company of Canada; gas chromatography tandem mass spectrometry is available from Agilent, USA; the nitrogen blower (12N-Evap. TM.) used for the experiments was purchased from Oganomation; the centrifuge is purchased from Hunan instrument company of Hunan province; cryocentrifuges were purchased from Sammer Feishel Scientific Inc. (Thermo Fisher Scientific); shaker Purchase and Kylin-Bell; the reagents used in the experiments were all of LC-MS grade, purchased from Thermo Fisher Scientific, inc.

TABLE 1 quantitative determination of the Compounds

(2) Sample collection

Plasma samples were collected at the third subsidiary hospital of the university of Zhongshan (Guangzhou, china) using blood collection tubes (BD Co., USA). The collected plasma was centrifuged at 3000rpm for three minutes to separate the plasma from the blood cells, and the supernatant was transferred to a glass vial and stored at-80 ℃ prior to analysis. Plasma samples were collected from a total of 10 volunteers in this experiment.

(3) Sample pretreatment and instrumental analysis

(1) Putting 200 mul sample into a 15mL glass centrifuge tube, adding recovery rate indicators (the addition amount of each recovery rate indicator in 200 mul plasma is 0.5-20 ng, the specific addition amount of the recovery rate indicators in the experiment is as follows, namely 5ng of an organophosphate recovery rate indicator, 2ng of a phthalate monoester recovery rate indicator, 1ng of a phthalate diester recovery rate indicator, 2ng of a personal care product recovery rate indicator, 2ng of a bisphenol analogue recovery rate indicator, 5ng of a benzophenone ultraviolet stabilizer recovery rate indicator, 5ng of a benzothiazole ultraviolet stabilizer recovery rate indicator, 5ng of a benzotriazole ultraviolet stabilizer fungicide, 5ng of other ultraviolet stabilizers, 5ng of a photoinitiator recovery rate indicator, 5ng of an antioxidant recovery rate indicator, 5ng of a plasticizer indicator, 0.5ng of a perfluoro compound organophosphate indicator, 5ng of a pesticide recovery rate indicator, 20ng of an organochlorine pesticide recovery rate indicator, 5ng of a pyrethroid recovery rate indicator, 5ng of a neonicotinate indicator, 5ng of an amino formate indicator, 5ng of an amide indicator, 5ng of an acrylic acid pesticide recovery rate indicator, 5ng of an amide, and 5mL of an acid pesticide extraction solvent after being added into the centrifuge tube, and the centrifugal separation of an acid pesticide recovery rate indicator, then the mixture is rotated and shaken for 5min and then centrifuged for 3min at 3000rpm, the supernatant is taken and transferred to another glass centrifuge tube, and the steps are repeated for two times; wherein, the first two extraction solvents are mixed solvent of ethyl acetate and n-hexane containing 0.6% (v/v) formic acid (ethyl acetate: n-hexane =3, volume ratio: 2), and the third extraction solvent is ethyl acetate (3 mL);

(2) the combined extracted liquid nitrogen is blown to be nearly dry, then 50 mu L of methanol is added for redissolution, then the mixed extracted liquid nitrogen is transferred to a 1.5mL centrifuge tube, the mixed liquid nitrogen is frozen for one night at the temperature of minus 40 ℃, then the mixed liquid nitrogen is centrifuged for 5min at the temperature of 15000rpm of a refrigerated centrifuge, supernatant is transferred to a 1.5mL sample feeding bottle, and internal standards (the dosage of each internal standard is 1-20 ng, in the experiment, the dosage of the internal standards is 1ng for normal mode internal standard coumaphos-d10, 5ng for negative mode internal standard bisphenol A-d16 (BPA-d 16), 1ng for perfluorinated compound internal standard Perfluoro-n- [13C8] caprylic acid (Perfluoro-n- [13C8] octoic acid (M8 PFOA)), and 20ng for internal standard decachloro diphenyl ether (Decalopylene ether (DCDE)) are added to be analyzed, wherein the dosage of the internal standards is shown in Table 1.

The target compound is subjected to quantitative analysis on a sample on an ultra performance liquid chromatography-tandem mass spectrometer (UPLC-MS/MS) and a gas chromatography-tandem mass spectrometer (GC-MS/MS), and the total number of the analysis methods is 8, and the specific information is shown in tables 2 and 3. Wherein:

mass spectrometry conditions in LC-MS/MS include: the electrospray ion source has an ion temperature of 550 ℃ and detection modes shown in Table 2; atomization pressure: nitrogen at 55psi;

mass spectrometry conditions in GC-MS/MS include: and (3) electron bombardment ion source, wherein the temperature of the ion source is 230 ℃, the temperature of a quadrupole rod is 150 ℃, and the solvent is delayed for 3min (organic chlorine pesticide) or 6min (liquid crystal monomer).

TABLE 2 LC-MS/MS information of the compound (column temperature: 40 ℃ C.)

TABLE 3 GC-MS/MS information for the compounds (inlet temperature: 260 ℃ C.)

(4) Quality assurance and quality control

The quality assurance and quality control procedures examined procedure blanks and recovery rates of recovery indicators, while the matrix spiked samples were analyzed. Two laboratory procedure blanks were simultaneously processed each time 10 different plasma samples were processed, and procedure blanks were prepared by replacing actual samples with 200 μ L of ultrapure water, the processing procedure being the same as that of the actual samples, and repeated three times. Isotopic recovery of all samples was calculated to be 50-110% by integration using AB Sciex 5500Q Trap triple quatrup-linear ion Trap mass spectrometer analysis software Analyst 1.6.3 software.

The standard substance is added into five parts of sheep blood plasma (Guangzhou future biotechnology limited, china), the addition amount of each standard substance is 1-10 ng, and the specific addition amount of the standard substance in the experiment is as follows: organic phosphoric acid diester 5ng, organic phosphoric acid triester 2ng, phthalic acid monoester 2ng, phthalic acid diester 1ng, personal care product 2ng, bisphenol analogue 2.5ng, benzophenone ultraviolet stabilizer 5ng, benzothiazole ultraviolet stabilizer 5ng, benzotriazole ultraviolet stabilizer 5ng, other ultraviolet stabilizer 2ng, photoinitiator 5ng, antioxidant 5ng, plasticizer 5ng, perfluoro compound 2ng, organophosphorus pesticide 2ng, organochlorine pesticide 3.5ng, pyrethroid 2ng, neonicotinoid 2ng, carbamate pesticide 2ng, acid herbicide 2ng, azole pesticide 2ng, triazolone pesticide 2ng, urea pesticide 2ng, amide pesticide 2ng, strobilurin pesticide 2ng, other pesticide 2ng, liquid crystal monomer 10ng, treated with the same pretreatment method as the above step (3) (triple repetition), treated with sciab 5500Q Trap three primer-linear Trap trace analysis software to obtain average recovery of compounds 1.6. The target effect calculation software 1.6. The average recovery of compounds and the target effect calculation software: the average recovery rate of all target compounds ranged from 71 to 98%, and the matrix effect ranged from 96 to 120%.

Each class of compounds was quantified using a standard curve at more than five concentration levels, with the correlation coefficient for the standard curve being greater than 0.995. The method limit of quantitation (LOQ), i.e., the detection limit, is defined as the concentration of the compound corresponding to a response that is 3 or 10 times the noise standard deviation, and if the LOQ is calculated to be lower than the background contamination value in the blank, the highest blank concentration is used as the LOQ. The LOQ of all specific compounds are shown in Table 1.

(5) Analysis results

The total number of tested compounds is 377, the detection rate of 40 compounds is more than 50 percent, and the detection rate of 32 compounds is more than 70 percent; the perfluorinated compounds are detected in the most variety, and 13 detection rates among 25 perfluorinated compounds are more than 70%, wherein the detection rates of perfluorooctanoic acid (PFOA), perfluoro-1-heptanesulfonic acid (L-PFHxS), perfluoro-1-hexanesulfonic acid (L-PFHpS), perfluoro-n-nonanoic acid (PFNA), perfluorooctanesulfonic acid (PFOS), perfluoro-n-decanoic acid (PFDA), perfluoro-n-undecanoic acid (PFUdA), 9-chlorodecahexafluoro-3-oxacyclohexane-1-potassium sulfonate (9 Cl-PF3 ONS) and 11-chloroeicosafluoro-3-oxacyclobutane-1-potassium sulfonate (11 Cl-PF3 OUdS) are 100%; the plastic additive detects the phthalate with the most variety, but detects Glycerol Monooleate (GMO) with the highest concentration in the plasticizer, and the concentration range is 127 to 10914ng/mL; the pesticide category only detects organochlorine pesticides, wherein the detection rate of alpha-hexachlorocyclohexane (alpha-HCH) and 4, 4'-dichlorodiphenyl trichloroethane (p, p' -DDE) is 100%. The detection information of the specific compounds is shown in table 4.

TABLE 4 Compound detection information

Comparative example 1

A sample was collected according to the method in step (2) of example 1, and then examined as follows:

(1) Putting 200 mu L of plasma into a 15mL glass centrifuge tube, adding the recovery rate indicator, and uniformly mixing;

(2) Adding 3mL of an extraction solvent (containing 0.6% (v/v) formic acid) of ethyl acetate and n-hexane in a volume ratio of 3 to a centrifuge tube, rotating and shaking for 5min, centrifuging at 3000rpm for 3min, and transferring the supernatant into another glass centrifuge tube;

(3) Repeating the step (2) for the second extraction, changing the extraction solvent into ethyl acetate for the third extraction, and combining the three extraction solutions;

(4) Blowing the extractive solution to 1mL under slow nitrogen flow, adding 3mL of 0.6% formic acid aqueous solution for dilution, then nitrogen-blowing and concentrating to 3mL, passing through HLB column (

PRiME HLB 3cc (60 mg) Extraction Cartridges) was placed on the SPE Extraction apparatus, and then the HLB column was pre-washed with 3mL methanol, 3mL water in sequence;

(5) Transferring the diluent to an HLB column, removing interference by using 3mL of formic acid aqueous solution with the volume fraction of 2%, adding 3mL of methanol water for elution after the solvent flows out, connecting elution liquid nitrogen by a glass tube, blowing to 50 mu L, transferring to a sample injection bottle, and adding an internal standard to be subjected to sample loading;

(6) The samples were quantitatively analyzed by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS) as in example 1, step (3) (table 2, table 3).

The recovery indicator and the internal standard added in the above process were the same as those used in example 1, except for the pretreatment process.

Performing matrix labeling experiment by using the pretreatment method, putting 6 parts of sheep blood plasma (China Guangzhou future biotechnology limited) into a 15mL glass centrifuge tube, wherein 5 parts of the sheep blood plasma are added with 2-10 ng of each target compound, and the specific addition is as follows: 5ng of organic phosphoric acid diester, 2ng of organic phosphate triester, 2ng of phthalic acid monoester, 1ng of phthalic acid diester, 2ng of personal care product, 2.5ng of bisphenol analog, 5ng of benzophenone ultraviolet stabilizer, 5ng of benzothiazole ultraviolet stabilizer, 5ng of benzotriazole ultraviolet stabilizer, 2ng of other ultraviolet stabilizer, 5ng of photoinitiator, 5ng of antioxidant, 5ng of plasticizer, 2ng of perfluoride, 2ng of organophosphorus pesticide, 3.5ng of organochlorine pesticide, 2ng of pyrethroid, 2ng of neonicotinoid pesticide, 2ng of carbamate pesticide, 2ng of acid herbicide, 2ng of azole pesticide, 2ng of triazolone pesticide, 2ng of urea pesticide, 2ng of amide pesticide, 2ng of strobilurin pesticide, 2ng of other pesticide and 10ng of liquid crystal monomer, and the other part is used as blank control, then all the indicators are added and mixed, and then the pretreatment and analysis are carried out according to the steps (repeated for three times).

The results are shown in FIG. 1: method one was the method used in example 1 and method two was the method used in comparative example 1. As shown in the figure, the recovery rate of the standard addition in the method I is mostly about 70-100%, is relatively stable and meets the standard, the recovery rate of the standard addition in the method II is relatively dispersive and unstable, the recovery rate is relatively low compared with the method I, and even the recovery rate of the standard addition of some compounds is 0%. The results show that the matrix interference of the second method is stronger, and the first method is obviously better than the second method in combination.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A method for analyzing targeted exposure of environmental pollutants in blood plasma for non-disease diagnostic and therapeutic purposes, comprising the steps of:

(1) Adding the recovery rate indicator into the plasma, and uniformly mixing to obtain a mixture of the plasma and the recovery rate indicator;

(2) Adding an extraction solvent I into the mixture of the plasma and the recovery rate indicator obtained in the step (1) for extraction, centrifuging, taking the supernatant, and repeating the step for more than 1 time; adding an extraction solvent II for extraction to obtain an extract liquid; wherein the extraction solvent I is a mixed solvent of ethyl acetate containing formic acid and n-hexane; the extraction solvent II is ethyl acetate;

(3) Drying the extract obtained in the step (2) by using nitrogen, adding methanol for redissolution, freezing at the temperature of minus 40 +/-5 ℃, freezing and centrifuging, and taking supernatant to obtain a pretreated sample;

(4) Adding an internal standard into the pretreated sample obtained in the step (2), and then carrying out quantitative analysis on the environmental pollutants by utilizing a liquid chromatography-tandem mass spectrometry and a gas chromatography-tandem mass spectrometry;

the contaminants described in step (4) are as follows:

the detection conditions of the liquid chromatography-tandem mass spectrometry in the step (4) are as follows:

(1) phthalic acid diesters

The chromatographic conditions include:

mobile phase A: 0.1% by volume of aqueous formic acid;

mobile phase B: methanol;

and (3) chromatographic column: luna 2.5 μm C18 (2) -HST

100×2.0mm；

Flow rate: 0.2mL/min;

column temperature: at 40 ℃;

elution procedure: the volume percentage content of the initial mobile phase B is 40%; the volume percentage of the mobile phase B is increased from 40 percent to 70 percent within 0-2 min; 2-8 min, the volume percentage of the mobile phase B is increased to 100%; keeping the volume percent of the mobile phase B unchanged at 100% for 8-13 min, and reducing the volume percent of the mobile phase B to 40% for 13-13.1 min; 13.1-17 min, keeping constant at 40%;

the mass spectrometry conditions included: an electrospray ion source, wherein the temperature of the ion source is 550 ℃; the detection mode is a positive ion detection mode; atomization pressure: nitrogen at 55psi;

(2) monoesters of phthalic acid, UV stabilizers of the benzophenone class, bisphenol analogs and personal care products

The chromatographic conditions include:

mobile phase A:0.2mmol/L ammonium acetate aqueous solution;

mobile phase B: methanol;

a chromatographic column: ZORBAX Extended-C18.5 μm

100×2.1mm；

Flow rate: 0.2mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping the 10 percent constant within 0-0.5 min; the volume percentage of the mobile phase B is increased from 10 percent to 50 percent within 0.5-1 min; 1-7 min, the volume fraction of the mobile phase B is increased from 50% to 99%; keeping the temperature constant at 99 percent for 7-10 min; 10-10.1 min, from 99% to 10%, 10.1-12 min, keeping the volume fraction of the mobile phase B unchanged at 10%;

the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization pressure: nitrogen at 55psi;

(3) plasticizers, benzothiazoles, benzotriazoles and other classes of UV stabilizers, photoinitiators and antioxidants for detection in positive ion detection mode

The chromatographic conditions include:

mobile phase A: 0.1% by volume of aqueous formic acid;

mobile phase B: methanol;

a chromatographic column: luna 2.5 μm C18 (2) -HST

100×2.0mm；

Flow rate: 0.3mL/min;

column temperature: at 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B is 40 percent, and the initial mobile phase B is kept unchanged at 40 percent in 0-2 min; 2-4 min, the volume percentage of the mobile phase B is increased from 40% to 80%; 4-14 min, the volume percentage of the mobile phase B is increased from 80% to 100%; the volume percentage of the mobile phase B is kept constant at 100 percent for 14-17 min; the volume percentage of the mobile phase B is reduced to 40 percent within 17-20 min, and the volume percentage of the mobile phase B is kept unchanged at 40 percent within 20-24 min;

the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a positive ion detection mode; atomization air pressure: nitrogen at 55psi;

(4) organic phosphoric acid triesters

The chromatographic conditions include:

mobile phase A: formic acid aqueous solution with volume fraction of 0.1 percent;

mobile phase B: methanol;

and (3) chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1mm;

flow rate: 0.3mL/min;

column temperature: at 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B is 5 percent, and the initial mobile phase B is kept at 5 percent in 0-1 min; the volume fraction of the mobile phase B rises from 5 percent to 40 percent within 1-3 min; 3-12 min from 40% to 100%; keeping 100 percent unchanged for 12-15 min; 15-15.1 min, the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent; the volume fraction of the mobile phase B is kept unchanged at 5 percent for 15.1 to 18 min;

the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen at 55psi;

(5) organic phosphoric acid diesters

The chromatographic conditions include:

mobile phase A:0.2mmol/L aqueous ammonium acetate solution;

mobile phase B: methanol;

a chromatographic column: ACQUITY UPLC BEH Shield RP18,1.7 μm, 100X 2.1mm;

flow rate: 0.3mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B is 5 percent, and the initial mobile phase B is increased from 5 percent to 35 percent in 0-4 min; 4-7min, wherein the volume fraction of the phase B is increased from 35% to 80%; increasing the temperature from 80% to 100% in 7-12 min; keeping 100 percent unchanged for 12-14 min; the volume percentage of the mobile phase B is reduced from 100 percent to 5 percent within 14-15 min; the volume percentage of the mobile phase B is kept unchanged at 5 percent for 15-20 min;

the mass spectrometry conditions included: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a negative ion detection mode; atomization air pressure: nitrogen at 55psi;

(6) antioxidant for detection in negative ion detection mode

The chromatographic conditions include:

mobile phase A:4mmol/L ammonium acetate aqueous solution;

mobile phase B: methanol;

a chromatographic column: luna 2.5 μm C18 (2) -HST

100×2.0mm；

Flow rate: 0.2mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B was 10%; keeping 10% unchanged for 0-0.5 min; the volume percentage of the mobile phase B is increased from 10 percent to 50 percent in 0.5-1 min, and is increased to 99 percent in 1-7 min; keeping the temperature constant at 99 percent for 7-10 min; the volume percentage of the mobile phase B is rapidly reduced to 10 percent within 10-10.1 min; keeping the volume fraction of the mobile phase B unchanged at 10.1-12 min;

the mass spectrometry conditions include: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization air pressure: nitrogen at 55psi;

(7) perfluorinated compounds:

the chromatographic conditions include:

mobile phase A:0.2mmol/L ammonium formate;

mobile phase B: methanol;

a chromatographic column: ACQUITY UPLC BEH Shield RP 18.7 μm; 100X 2.1mm;

flow rate: 0.3mL/min;

column temperature: 40 ℃;

elution procedure: the initial mobile phase B volume percentage was 40%; keeping the content of the mobile phase B unchanged within 0-2 min, and increasing the volume percentage of the mobile phase B to 66% within 2-3 min; rising to 70% in 3-12 min; the volume fraction of the mobile phase B is increased from 70% to 100% in 12-14 min, and is kept constant at 100% in 14-16 min; quickly reducing the temperature to 40 percent within 16 to 16.1 min; the volume fraction of the mobile phase B is kept constant at 40% from 16.1 to 22;

the mass spectrometry conditions included: the electrospray ion source has an ion temperature of 550 ℃ and a detection mode of a negative ion detection mode; atomization pressure: nitrogen at 55psi;

(8) organophosphorus pesticides, pyrethroids, neonicotinoids, carbamates, acid herbicides, azoles, triazoles, ureas, amides, strobilurins, other insecticides

The chromatographic conditions include:

mobile phase A:5mmol/L ammonium acetate solution;

mobile phase B: acetonitrile;

and (3) chromatographic column: kinetex 2.6 mu m C18

100*2.1mm；00D4462-AN；

Flow rate: 0.4mL/min;

column temperature: 40 ℃;

elution procedure: the volume percentage of the initial mobile phase B was 2%; the volume percentage of the mobile phase B rises from 2 percent macroscopically to 30 percent in 0-4 min; the volume percentage of the mobile phase rises from 30 percent to 68 percent in 4-22 min; the mobile phase B rises from 68% to 99% in 22-22.1 min; 22.1-23 min, keeping the temperature at 99%; 23-23.1 min, reducing the volume percentage of the mobile phase B from 99% to 2%; keeping 2 percent unchanged for 23.1-26 min;

mass spectrum conditions: an electrospray ion source, wherein the ion temperature is 550 ℃, and the detection mode is a negative ion detection mode; atomization pressure: nitrogen at a pressure of 55psi;

the detection conditions of the gas chromatography-tandem mass spectrometry described in the step (4) are as follows:

(9) organic chlorine pesticide:

the chromatographic conditions include:

and (3) chromatographic column: agilent HP-5MS column 19091S-433;

sample inlet temperature: 260 ℃;

temperature rising procedure: the initial temperature is 60 ℃, and the temperature is kept for 1min; heating to 300 deg.C at a speed of 5 deg.C/min, and maintaining for 9min

Mass spectrum conditions: electron bombardment ion source with ion source temperature of 230 deg.C, quadrupole rod temperature of 150 deg.C, solvent delay time of 3min

Liquid crystal monomer r:

the chromatographic conditions include:

and (3) chromatographic column: agilent HP-5MS chromatographic column 19091S-433;

sample inlet temperature: 260 ℃;

temperature rising procedure: the initial temperature is 80 ℃, and the temperature is kept for 2.5min; then heating to 200 ℃ at the speed of 25 ℃/min and keeping for 1min; then the temperature is increased to 250 ℃ at the speed of 10 ℃/min, and then the temperature is increased to 285 ℃ at the speed of 5 ℃/min, and the temperature is kept for 5min; finally, the temperature is increased to 300 ℃ at the speed of 30 ℃/min, and the temperature is kept for 1min

Mass spectrum conditions: the electron bombardment ion source has the ion source temperature of 230 ℃, the quadrupole rod temperature of 150 ℃ and the solvent delay time of 6min.

2. The method of claim 1, wherein:

the dosage of the recovery rate indicator in the step (1) is calculated according to 0.5-20 ng of each recovery rate indicator added into every 200 mu L of blood plasma;

the formula of the extraction solvent I in the step (2) is as follows: 298.2mL ethyl acetate, 198.8mL n-hexane, and 3mL formic acid;

the dosage of the internal standard in the step (4) is calculated according to 1-20 ng of each internal standard added into each 50 mu L of the pretreated sample.

3. The method of claim 1, wherein:

the freezing time in the step (3) is more than 12 hours;

the conditions of the freezing and centrifuging in the step (3) are as follows: centrifuging at-10 deg.C and 15000rpm for more than 5 min.

4. The method of claim 1, wherein:

the internal standard in the step (4) comprises an internal standard of a perfluorinated compound, a plasticizer, an organochlorine pesticide, an organophosphorus pesticide and a liquid crystal monomer;

the internal standard of the perfluoro compound is perfluoro-n- [13C8] caprylic acid;

the internal standard of the positive mode of the plasticizer is coumaphos-d10, and the internal standard of the negative mode of the plasticizer is bisphenol A-d16;

the internal standard of the organochlorine pesticide is decachlorodiphenyl ether;

the positive mode internal standard of the organophosphorus pesticide is coumaphos-d10, and the negative mode internal standard is p-hydroxybenzoic acid tert-butyl ester-d 9;

the internal standard of the liquid crystal monomer is decachlorodiphenyl ether.

5. The method of claim 1, wherein:

the plasma in the step (1) is human or animal plasma;

the plasma in the step (1) is obtained by the following method: centrifuging the collected blood, and taking supernatant to obtain required blood plasma;

the centrifugation conditions are as follows: centrifuging at 3000rpm for 3min;

the repetition frequency in the step (2) is more than 2 times;

the centrifugation conditions in the step (2) are as follows: centrifuging at 3000-4000 rpm for more than 3 min.

6. Use of the method of any one of claims 1 to 5 for the analysis of environmental contaminants in plasma for non-disease diagnostic and therapeutic purposes.

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