AU2021102623A4 - Method for rapidly screening substances of very high concern (svhcs) in surface water and soil - Google Patents

Method for rapidly screening substances of very high concern (svhcs) in surface water and soil Download PDF

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AU2021102623A4
AU2021102623A4 AU2021102623A AU2021102623A AU2021102623A4 AU 2021102623 A4 AU2021102623 A4 AU 2021102623A4 AU 2021102623 A AU2021102623 A AU 2021102623A AU 2021102623 A AU2021102623 A AU 2021102623A AU 2021102623 A4 AU2021102623 A4 AU 2021102623A4
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svhcs
soil
acetonitrile
methanol
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Deling FAN
Wen Gu
Min Guo
Mengyuan LIANG
Jining Liu
Mingqing LIU
Lili Shi
Lei Wang
Zhen Wang
Linjun Zhou
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Nanjing Institute of Environmental Sciences MEE
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Abstract

OF THE DISCLOSURE The present disclosure provides a method for rapidly screening substances of very high concern (SVHCs) in surface water and soil. The method includes selection of a list of SVHCs; grouping of the SVHCs; optimization of mass spectrometry (MS) conditions and liquid chromatography (LC) conditions; construction of an MS database of the SVHCs; and rapid screening of SVHCs. The present disclosure rapidly tests samples in surface water and soil by an ultra-high-performance liquid chromatography (UHPLC)-quadrupole/Exactive mass spectrometer, and searches, matches and rapidly identifies SVHCs by the MS database of the SVHCs based on exact mass, retention time, characteristic fragment and isotope ratio. The present disclosure can finish the screening in 70 min, greatly shortening the testing and treatment time of the sample, improving the testing efficiency, and providing technical support for the risk assessment and management of SVHCs. 17691372_1 (GHMatters) P116328.AU 1/3 Screening Production Directories Hazards usages LJ 219 substances of very high concern (SVHCs) I ===============meemmm asanmnmmasmrmaemrmemas m Grouping Functional as omatography Uses Hazards Liquid Chromatography a rou Lqi(GC/LC) Alkylphenols, carcinogens, pharmaceuticals and personal care products (PPCPs), chemicals known to cause reproductive toxicity,'amines, organic phosphates FIG.1 Instrument/method development Optimization of LC conditions Optimizationofmass spectrometry (MS) conditions ml * I.~I~to A tg cain control: Reversed-phase column Sheathgas,auxiiaygas Normal-phase column Spray voltage Ion injection time Mobile phase buffer Capillary temperature Number of cycles salt aa Addition concentration SIM/FullScan/Pe Nonnec ione FIG. 2

Description

1/3
Screening
Production Directories Hazards usages LJ 219 substances of very high concern (SVHCs)
I ===============meemmm Grouping asanmnmmasmrmaemrmemas m
Functional as omatography Uses Hazards Liquid Chromatography a rou Lqi(GC/LC)
Alkylphenols, carcinogens, pharmaceuticals and personal care products (PPCPs), chemicals known to cause reproductive toxicity,'amines, organic phosphates
FIG.1
Instrument/method development
Optimization of LC conditions Optimizationofmass spectrometry (MS) conditions
ml Reversed-phase column * I.~I~to Sheathgas,auxiiaygas A tg cain control:
Normal-phase column Spray voltage Ion injection time
aa Mobile phase buffer Capillary temperature Number of cycles salt
SIM/FullScan/Pe Nonnec ione Addition concentration
FIG. 2
METHOD FOR RAPIDLY SCREENING SUBSTANCES OF VERY HIGH CONCERN (SVHCS) IN SURFACE WATER AND SOIL TECHNICAL FIELD
[01] The present disclosure belongs to the field of environmental protection, and relates to a chemical analysis method, in particular to a method for rapidly screening substances of very high concern (SVHCs) in surface water and soil.
BACKGROUNDART
[02] In 2001, the European Union (EU) proposed an innovative chemical risk management system, namely the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH), in the "White Paper on the Strategy for a Future Chemicals Policy". It defines persistent, bioaccumulative and toxic (PBT) chemicals, including very persistent and very bioaccumulative (vPvB) chemicals, carcinogenic, mutagenic or toxic to reproduction (CMR) chemicals and endocrine-disrupting chemicals (EDCs), as substances of very high concern (SVHCs). Since the REACH regulation was promulgated and implemented in 2007, the SVHCs candidate list has been continuously updated, reaching 191 by 2018.
[03] At present, China is in a critical period of implementing the national strategy of "Integrated Development of the Yangtze River Delta Region". It is urgent to solve the problem of a wide variety of high-risk chemicals used, produced and disposed by chemical plants concentrated in the coastal areas of the Yangtze River Delta. First, it is necessary to test and identify the SVHCs. The testing standards of the EU or other international standards organizations only target single SVHCs, and most of the single-component testing methods are time-consuming, low-efficiency and high-cost. There are many mass spectrometry (MS) databases of chemicals, including the pesticide residue MS database pQSM (including 642 pesticides) and the veterinary drug residue MS database vQSM (including 542 compounds) established by Thermo Fisher Scientific. However, none of them is suitable for the screening and identification of SVHCs. In view of this, the present disclosure establishes a method for rapidly screening SVHCs by an ultra-high-performance liquid chromatography (UHPLC)-quadrupole/Exactive mass spectrometer. The present disclosure provides a convenient and reliable method for the identification of toxic and hazardous substances in the actual environment, and provides technical support for the whole-process risk management
17691372_1 (GHMatters) P116328.AU and control of chemicals in China.
SUMMARY
[04] The present disclosure provides a method for rapidly screening substances of very high concern (SVHCs) in surface water and soil. The present disclosure rapidly tests samples in surface water and soil by an ultra-high-performance liquid chromatography (UHPLC)-quadrupole/Exactive mass spectrometer, and searches, matches and rapidly identifies SVHCs by a mass spectrometry (MS) database of the SVHCs based on exact mass, retention time, characteristic fragment and isotope ratio. This method specifically includes:
[05] step 1: selection of a list of SVHCs
[06] selecting, according to the California Proposition 65, the SVHCs Candidate List, the List of Carcinogens released by the National Toxicology Program (NTP), the Toxics Release Inventory (TRI) and the key control list of the Committee on Community Activities (CCA) of the US, a total of 220 chemicals, including: 46 carcinogens, 22 chemicals known to cause reproductive toxicity, 4 SVHCs listed by the EU, 22 alkylphenols & endocrine-disrupting chemicals (EDCs), 2 persistent, bioaccumulative and toxic (PBT)/very persistent and very bioaccumulative (vPvB) chemicals, 97 pharmaceuticals and personal care products (PPCPs) and 27 others;
[07] step 2: grouping of the SVHCs
[08] dividing the 220 SVHCs into four groups, that is, a, b, c and d, based on uses, structural characteristics and hazards of the SVHCs:
[09] a: carcinogens, chemicals known to cause reproductive toxicity and SVHCs listed by the EU (72): 4,4'-methylenebis(N,N-dimethylaniline), 2-amino-i-methyl-6-phenylimidazo[4,5-b]pyridine, pyridine, bis(2-methoxyethyl)ether, tris(2-chloroethyl)phosphate, 2-aminoanthraquinone, dimethoxyethyl phthalate, diisoamyl phthalate, o-dianisidine, 4,4'-diamino-3,3'-dimethylbiphenyl, 6-methoxy-m-toluidine, diclofenamide, aminoglutethimide, ethoprophos, 1-aminonaphthalene, dipropylpyridine, nitrilotriacetic acid, 2-aminofluorene, 7H-dibenzocarbazole, daminozide, oxadiazon, cyanazine, thiophanate methyl, propyzamide, butylhydroxyanisole, 2-amino-9H-pyrido[2,3-b]indole, toluene diisocyanate, oxydemeton-methyl, mebendazole, -azacytidine, diuron, auranofin, pigment orange 5, procarbazine hydrochloride, ifosfamide,
17691372_1 (GHMatters) P116328.AU triadimefon, auramine 0, 6-propyl-2-thiouracil, N-nitrosodiethylamine, pyrimethamine, colchicine, dicoumarin, thiodicarb, N-nitrosomorpholine, methimazole, N-nitrosodi-n-propylamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone, hydramethylnon, IQ[2-amino-3-methylimidazo(4,5-F)quinoline], quizalofop, hexamethylphosphoric triamide, 2-amino-3,4-dimethyl-3H-imidazo[4,5-f]quinoline, N-methylacetamide, warfarin, dicyclohexyl phthalate, cinnamyl anthranilate, 2,6-dimethylaniline, Sudan I, myclobutanil, 2-methoxyaniline, 4,4'-tetramethyldiaminobenzophenone, 2-naphthylamine, N-nitrosodi-n-butylamine, benzidine, N-nitrosopyrrolidine, 1,2-dimethoxy-4-(2-propenyl)benzene, disperse orange 11, 4-chloro-2-methylaniline, 2,4-diaminotoluene, vinyl sulfide, o-aminoazotoluene, 4-aminobiphenyl and pendimethalin;
[10] b: PPCPs (97): indomethacin, ketoprofen, atenolol, chloramphenicol, azithromycin, nimodipine, ibuprofen, etoposide, ribavirin, cladribine, etretinate, misoprostol, megestrol-17-acetate, sulindac, lovastatin, clarithromycin, cladribine, ganciclovir, aminopterin, ethionamide, misoprostol, sulfachloropyridazine, sulfadiazine, sulfamethazine, amoxapine, melphalan, teniposide, medroxyprogesterone acetate, clobetasol propionate, aspartame, diflunisal, primidone, ganciclovir, thiophanate methyl, isotretinoin, griseofulvin, pimozide, nifedipine, auranofin, dehydroerythromycin A, secbumeton, acesulfame potassium, 2-amino-9H-pyrido[2,3-b]indole, 5-azacytidine, haloperidol, sulfamethazine, azathioprine, ofloxacin, norfloxacin, trimethoprim, roxithromycin, sulfapyridine, sulfadimethoxine, phenytoin, naproxen, florfenicol, sulfametoxydiazine, sulfamonomethoxine, rifaximin, metronidazole, minocycline hydrochloride, sulfamethoxazole, sulfathiazole, sulfisomidine, sulfadimoxine, sulfamethizole sulfabenzamide, demecycline hydrochloride, tonalid, isophorone, ciprofloxacin, triclocarban, halobetasol propionate, reserpine, sulfamethoxypyridazine, gemfibrozil, bezafibrate, fenoprofen, provera, haloperidol, indomethacin, sulfamidine, sulfacetamide, triclosan, clofibric acid, bentazone, salicylic acid, ormetoprim, etodolac, carbamazepine, progesterone, estrone, testosterone, diethylstilbestrol, a-estradiol, p-estradiol, estrone and estriol;
[11] c: alkylphenols and EDCs (22): bisphenol A, bisphenol B, bisphenol AF, bisphenol S, bisphenol AP, bisphenol Z, nonylphenol, 4-(tert-octyl)phenol, methyl eugenol, 4-tert-amylphenol, octylphenol, 3,4-dichlorophenol, 2-amino-4-bromophenol, 4-sec-butyl-2,6-di-tert-butylphenol, 4-heptylphenol, 4-nitrophenol, 4-bromo-2-fluorophenol,
17691372_1 (GHMatters) P116328.AU
4-bromophenol, p-nitrophenol, 2,4-di-tert-amylphenol, o-aminophenol and dichlorophenol/biphenyl-2-phenol;
[12] d: others (28): 8-chlorotheophylline, acesulfame potassium, azobenzene, benzophenone, diphenylamine, p-aminoazobenzene, genistein, anthracene, triphenyl phosphate, tributyl phosphate, isocarbophos, 2,4-dinitroaniline, alachlor, diethyltoluamide, p-phenylenediamine, 3-methylaniline, 3,4-dichloroaniline, spironolactone, furazolidone, p-isopropylaniline, 1,3-dichlorobenzene, 2-chloro-4-nitroaniline, metribuzin, dacarbazine, 2,4-dichlorophenoxyacetic acid, difenoxuron, 2-(diethylamino)ethyl 1-(m-tolyl)cyclopentane-1-carboxylate and ethylene thiourea;
[13] preparing mixed standard stock solutions separately after grouping:
[14] I. single standard stock solution (20 mg/L): weighing 0.01 g of each of the 220 SVHCs, and dissolving in methanol in a 10 mL volumetric flask to obtain a standard stock solution with a mass concentration of 1,000 mg/L; taking 200 pL (1,000 mg/L) of standard stock solution into a 10 mL volumetric flask, diluting to a mark with methanol to obtain a standard stock solution with a mass concentration of 20 mg/L, and storing in a 4°C refrigerator;
[15] II. mixed standard stock solution (200 g/L): accurately taking 100 L of single standard stock solution (20 mg/L) into a 10 mL volumetric flask, diluting to a mark with methanol to obtain four groups (a, b, c and d) of mixed standard stock solution with a mass concentration of 200 pg/L, and storing at 4°C;
[16] step 3: optimization of mass spectrometry (MS) conditions and liquid chromatography (LC) conditions
[17] optimizing MS conditions, including sheath gas, auxiliary gas, spray voltage, capillary temperature, resolution, automatic gain control (AGC), maximum ion injection time, number of cycles, normalized collision energy (NCE), single ion monitoring (SIM), full scan mode; optimizing LC conditions, including C18/T3 columns, mobile phase buffer salt, addition concentration; analyzing adduct ion modes of different chemical substances to explore a fragmentation behavior of different types of characteristic pollutants under MS;
[18] LC conditions: Poroshell 120, EC-C18, 150 mm x 2.1 x 2.7 pm column, 40°C; positive ion mode: mobile phase A: 0.1% formic acid, and mobile phase D: acetonitrile;
17691372_1 (GHMatters) P116328.AU negative ion mode: mobile phase A: 0.05% ammonium hydroxide, and mobile phase D: acetonitrile; flow rate 0.3 mL/min; injection volume 5 pL; mobile phase gradient: 0 min, 90% A: 10% D; 0-2 min, 90% A: 10% D; 2-3 min, 70% A: 30% D; 3-6 min, 50% A: 50% D; 6-9 min, 40% A: 60% D; 9-15 min, 0% A: 100% D; 15-23 min, 0% A: 100% D; 23-23.5 min, 90% A: 10% D; 23.5-25 min, 90 % A: 10% D;
[19] MS conditions: electrospray ion source, 375°C, 3,500 V; sheath gas 40 arb; auxiliary gas 10 arb; backflush gas 0; S-lens radio frequency (RF): 50; auxiliary gas pressure: 10 arb; spray gas and collision gas: high-purity nitrogen; scan mode: data dependent scan (samples are separately injected in positive ion mode and negative ion mode; this mode includes primary full scan with a resolution of 70,000 and secondary scan with a resolution of 17,500; scan range 100-1,500 m/z; primary scan AGC: 1.0 e6; ion injection time: 100 ms; secondary AGC: 1.0 e5; maximum ion injection time: 100 ms); isolation window: 3.0 m/z; NCE: 30, 40, eV; number of cycles: 3; dynamic exclusion: 10.0 s;
[20] step 4: construction of an MS database of the SVHCs
[21] acquiring secondary information of target compounds, including exact mass, retention time, structural fragment and isotope ratio based on the data dependent scan mode; checking a characteristic fragment, entering the compounds' names, Chemical Abstracts Service registry number (CAS RN) and molecular formulas to form an MS database of the SVHCs covering the data of the compounds such as exact mass of precursor ion, retention time, exact mass of characteristic fragment, isotope ratio, polarity, NCE and charge number;
[22] step 5: rapid screening of SVHCs
[23] establishing non-specific extraction methods for the 220 SVHCs, including 3 targeting surface water and 3 targeting soil:
[24] water sample extraction:
[25] A: adjusting a recovered water sample to pH=2 with hydrochloric acid; activating an Oasis HLB solid-phase extraction (SPE) column by 5 mL of methanol and 5 mL of water respectively; feeding 100 mL of water sample to the SPE column; performing three parallel tests for each group; loading the sample at 3 mL-min'; then rinsing with 5 mL of ultrapure water, vacuum-drying for 30 min under a negative pressure, eluting with 5 mL of methanol twice, and eluting with 5 mL of acetonitrile comprising 0.1% ammonium hydroxide; drying
17691372_1 (GHMatters) P116328.AU an eluate with nitrogen; diluting to 1 mL with methanol, oscillating for 1 min; analyzing with an ultra-high-performance liquid chromatography (UHPLC)-quadrupole/Exactive mass spectrometer;
[26] B: the eluent in method A is changed from methanol: acetonitrile (with 0.1% ammonium hydroxide) (1:1) to dichloromethane, and the other steps are the same as in Method A; Method B may be used as a follow-up supplement to Method A to perform secondary elution extraction of a chemical substance that is not effectively recovered in the water sample;
[27] C: the eluent in Method A is changed from methanol: acetonitrile (with 0.1% ammonium hydroxide) (1:1) to methanol: acetonitrile (1:1), and the other steps are the same as in Method A; Method C may also be used as a follow-up supplement to Method A to perform secondary elution extraction of a chemical substance that is not effectively recovered in the water sample;
[28] soil sample extraction:
[29] A (acetonitrile extraction method): taking 5 g of soil sample into a 50 mL centrifuge tube, adding 25 mL of acetonitrile, oscillating for 20 s, and treating for 15 min in an ultrasonic cleaner to obtain an extract; loading at 3 mL/min to an SPE column (selected according to a substance type and with reference to the water sample extraction method); rinsing with 2 mL of dichloromethane, collecting an eluate, and drying with nitrogen; diluting to 1 mL with acetonitrile, oscillating for 1 min, and passing through a 0.22 m filter membrane for further analysis;
[30] B (methanol extraction method): the eluent in Method A is changed from acetonitrile to methanol (with 1% formic acid), and the other steps are the same as in Method A;
[31] C (QuEChERs): transferring the extract obtained in Method A to a centrifuge tube filled with 150 mg of primary secondary amine (PSA) and 150 mg of C18 in advance for purification; oscillating for 2 min and letting stand for 2 min, where the other steps are the same as in Method A.
[32] The pretreated surface water and soil samples are subjected to a data dependent scan by an UHPLC-quadrupole/Exactive mass spectrometer under the MS and LC conditions according to step 3.
17691372_1 (GHMatters) P116328.AU
[33] After the sample loading and analysis, the compounds are searched and matched in the MS database of the SVHCs based on exact mass, retention time, characteristic fragment and isotope ratio and identified by using a precursor ion search algorithm, an isotope feature extraction algorithm and a structural similarity algorithm (Euclidean distance analysis). The SVHCs are rapidly screened based on a mass accuracy (less than 5 ppm) of a precursor ion in primary MS, a mass accuracy of a fragment in secondary MS (less than 5 ppm) and an isotope ratio error (within 30%).
[34] In the entire analysis process, 1 matrix blank, 1 sample duplicate and 1 matrix spike are prepared for every 10 samples, and a relative error of the parallel samples is less than 30%. In the test, glassware such as conical flasks and heart-shaped flasks are soaked and dried in acetone, and no plastic containers are allowed. The standard curve solution is measured once before and after the testing of each batch of samples to determine a response change of the instrument, and a relative change should not exceed 10%. The 220 SVHCs have good linearity within 5-500 [g/L, with a correlation coefficient greater than 0.9900, a recovery rate reaching 50.5-119.6% and a relative standard deviation (RSD) reaching 6.9-19.8%. A detection limit of the instrument (S/N>3) is 0.008-6.018 g/L, and a limit of quantification ((S/N>10) of the method is 0.027-20.062 [g/L.
[35] The present disclosure has the following beneficial effects. The SVHCs are diverse in types, different in nature and harmful to the environment. The existing environmental testing standards target a certain or a certain type of specific substances, and cannot be applied to the monitoring of the environmental exposure and environmental release of multi-component chemicals. In addition, the pesticide residue MS database pQSM (including 642 pesticides) and the veterinary drug residue MS database vQSM (including 542 compounds) cannot rapidly screen out the SVHCs in unknown samples. The method of the present disclosure is of great significance for risk assessment and management of SVHCs. The laboratory does not need to purchase standard substances of SVHCs. The samples are loaded once in the positive and negative ion modes each (50 min in total), and then matching and identification (20 min) are conducted in the established MS database of the SVHCs. In this way, the SVHCs in unknown samples can be rapidly identified within 70 min. The present disclosure saves time, manpower and material resources, and realizes the accurate qualitative identification of SVHCs (the mass accuracy is within 5 ppm, the retention time deviation is 0.2 s, the mass accuracy of the secondary fragment is less than 5 ppm, and the isotope ratio error is within
17691372_1 (GHMatters) P116328.AU
%). The present disclosure provides a reliable and feasible method for the rapid identification of pollutants in the actual environment.
BRIEF DESCRIPTION OF THE DRAWINGS
[36] FIG. 1 is a flowchart of substance grouping.
[37] FIG. 2 is a flowchart of optimization of mass spectrometry (MS) conditions and chromatographic conditions.
[38] FIG. 3 is a flowchart of construction of an MS database of substances of very high concern (SVHCs).
[39] FIG. 4 is a flowchart of rapid screening of SVHCs.
[40] FIG. 5 shows matching results of isotope ratio and characteristic fragment of tributyl phosphate in the MS database of the SVHCs.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[41] The present disclosure is described in further detail below with reference to the specific examples, but the protection scope of the present disclosure is not limited thereto.
[42] Example 1
[43] Atotal of 17 samples, including water samples (W1-W13) and soil samples (S1-S6), were collected in the Fuling area of Chongqing, China, and substances of very high concern (SVHCs) were rapidly screened by using an ultra-high-performance liquid chromatography (UHPLC)-quadrupole/Exactive mass spectrometer and a mass spectrometry (MS) database of the SVHCs. A rapid screening method includes the following steps:
[44] Step 1: Sample collection
[45] In July 2018, 13 samples were separately collected at 13 points (W1-W13) in Chongqing Rudong Yangkou Chemical Park, Jianfeng Wujiang Bridge, Panjiaba Sewage Outlet, Panjiaba Sewage Outlet, Lizhi Wujiang Bridge, Fuling Wujiang Second Bridge, Shibangou Yangtze River Bridge, Fuling Yangtze River Bridge, Qingcaobei Yangtze River Bridge, Longqiao Sewage Treatment Plant (sewage outlet), Baitao Sewage Treatment Plant (sewage outlet). 1 L of each sample was contained in a brown glass bottle and stored at 4°C
17691372_1 (GHMatters) P116328.AU for testing.
[46] 20 g of soil samples were separately collected at 6 points (S1-S6) in Linshi Town, Xinfu Food Co., Ltd., Miaoyin Village, Taoda Hotel, Jianfeng Haokang Factory and Huafeng Aluminum Factory. After debris was removed, the soil samples were placed in a stainless steel box, freeze-dried, ground through a 60-mesh sieve, and stored at -20°C for testing.
[47] Step 2: Sample pretreatment
[48] Water sample extraction method A: Adjust a recovered water sample to pH=2 with hydrochloric acid; activate an Oasis HLB solid-phase extraction (SPE) column by 5 mL of methanol and 5 mL of water respectively; feed 100 mL of water sample to the SPE column; perform three parallel tests for each group; load the sample at 3 mL-min'; then rinse with 5 mL of ultrapure water, vacuum-dry for 30 min under a negative pressure, elute with 5 mL of methanol twice, and elute with 5 mL of acetonitrile including 0.1% ammonium hydroxide; dry an eluate with nitrogen; dilute to 1 mL with methanol, oscillate for 1 min; analyze with an UHPLC-quadrupole/Exactive mass spectrometer.
[49] Water sample extraction method B: The eluent in method A is changed from methanol: acetonitrile (with 0.1% ammonium hydroxide) (1:1) to dichloromethane, and the other steps are the same as in Method A. Method B may be used as a follow-up supplement to Method A to perform secondary elution extraction of a chemical substance that is not effectively recovered in the water sample.
[50] Water sample extraction method C: The eluent in Method A is changed from methanol: acetonitrile (with 0.1% ammonium hydroxide) (1:1) to methanol: acetonitrile (1:1), and the other steps are the same as in Method A. Method C may also be used as a follow-up supplement to Method A to perform secondary elution extraction of a chemical substance that is not effectively recovered in the water sample.
[51] Soil sample extraction method A (acetonitrile extraction method): Take 5 g of soil sample into a 50 mL centrifuge tube, add 25 mL of acetonitrile, oscillate for 20 s, and treat for min in an ultrasonic cleaner to obtain an extract; load at 3 mL/min to an SPE column (selected according to a substance type and with reference to the water sample extraction method); rinse with 2 mL of dichloromethane, collect an eluate, and dry with nitrogen; dilute to 1ImL with acetonitrile, oscillate for 1 min, and pass through a 0.22 m filter membrane for
17691372_1 (GHMatters) P116328.AU further analysis.
[52] Soil sample extraction method B (methanol extraction method): The eluent in Method A is changed from acetonitrile to (1% formic acid) methanol, and the other steps are the same as in Method A.
[53] Soil sample extraction method C (QuEChERs): Transfer the extract obtained in Method A to a centrifuge tube filled with 150 mg of primary secondary amine (PSA) and 150 mg of C18 in advance for purification; oscillate for 2 min and let stand for 2 min, where the other steps are the same as in Method A.
[54] Step 3: Analysis by ultra-high-performance liquid chromatography-quadrupole/Exactive mass spectrometry (UHPLC-Q-Exactive MS)
[55] LC conditions: Poroshell 120, EC-C18, 150 mm x 2.1 x 2.7 pm column, 40°C; positive ion mode: mobile phase A: 0.1% formic acid, and mobile phase D: acetonitrile; negative ion mode: mobile phase A: 0.05% ammonium hydroxide, and mobile phase D: acetonitrile; flow rate 0.3 mL/min; injection volume 5 pL; mobile phase gradient: 0 min, 90% A: 10% D; 0-2 min, 90% A: 10% D; 2-3 min, 70% A: 30% D; 3-6 min, 50% A: 50% D; 6-9 min, 40% A: 60% D; 9-15 min, 0% A: 100% D; 15-23 min, 0% A: 100% D; 23-23.5 min, 90% A: 10% D; 23.5-25 min, 90 % A: 10% D.
[56] MS conditions: electrospray ion source, 375°C, 3,500 V; sheath gas 40 arb; auxiliary gas 10 arb; backflush gas 0; S-lens radio frequency (RF): 50; auxiliary gas pressure: 10 arb; spray gas and collision gas: high-purity nitrogen; scan mode: data dependent scan (samples are separately injected in positive ion mode and negative ion mode; this mode includes primary full scan with a resolution of 70,000 and secondary scan with a resolution of 17,500; scan range 100-1,500 m/z; primary scan AGC: 1.0 e6; ion injection time: 100 ms; secondary AGC: 1.0 e5; maximum ion injection time: 100 ms); isolation window: 3.0 m/z; NCE: 30, 40, eV; number of cycles: 3; dynamic exclusion: 10.0 s.
[57] Step 4: Rapid screening of SVHCs
[58] Thermo Fisher Scientific's Trance Finder 4.0 software was used for rapid qualitative screening. The chemicals were searched and matched in the MS database of the SVHCs based on exact mass, retention time, fragment ion and isotope ratio by using a precursor ion search algorithm, an isotope feature extraction algorithm and a structural similarity algorithm. A
17691372_1 (GHMatters) P116328.AU mass accuracy of a precursor ion in primary MS was controlled to be less than 5 ppm, a mass accuracy of a fragment in secondary MS was controlled to be less than 5 ppm and an isotope ratio error was controlled to be within 30%. The tributyl phosphate in water samples WI and W9 100% matched with that in the MS database of the SVHCs within the following range: mass accuracy 2 ppm, retention time deviation within 0.1 s, isotope distribution, and characteristic fragments 211.1093, 155.04677 and 98.98417. Therefore, the water samples WI and W9 included the tributyl phosphate compound, as shown in FIG. 5. By searching and matching in the MS database of the SVHCs, 60 SVHCs were rapidly screened in the samples collected in Chongqing, including 52 in the surface water and 38 in the soil.
[59] Then further qualitative identification was conducted. Mixed standard stock solutions (200 g/L) of 86 SVHCs were prepared by accurately taking 100 L of single standard stock solution (20 mg/L) into a 10 mL volumetric flask, diluting to a mark with methanol to obtain mixed standard stock solutions with a mass concentration of 200 pg/L and storing at 4°C.
[60] Methanol was used as a solvent to dilute the mixed standard stock solutions (200 pg/L) in proportion to obtain mixed standard solutions with mass concentrations of 1, 2, 5, 10, , 50 and 100 pg/L. The prepared mixed standard solutions were stored at 44°C.
[61] Further, standard curves were drawn. Methanol was used to prepare mixed standard solutions with mass concentrations of 1, 2, 5, 10, 20, 50 and 100 pg/L, and standard curves with a peak area (y) vs. the mass concentration (x) of target substances were drawn. Then quantitative analysis was conducted by using an external standard method. The results are shown in Table 2.
[62] Example 2
[63] 22 water samples (W1-W22) were collected in the Three Gorges area of China, and SVHCs were rapidly screened by using an (UHPLC)-quadrupole/Exactive mass spectrometer and an MS database of the SVHCs. A rapid screening method includes the following steps:
[64] Step 1: Sample collection
[65] In July 2019, a total of 22 samples were collected at 22 points (W1-W22) in Sanxia Zhuankou, Honghu Xintankou, Honghu Luoshan Town, Chenglingji, Shishou Xiulin Town, Guanyinsi, Chenjiadian, the Gezhou Dam, Taipingxi, Jiuwanxi, Qinggan River, Xiangxi River, Badong Guandukou, Quchitan, Wushan Yangtze River Bridge, Fengjie Yangtze River Bridge,
17691372_1 (GHMatters) P116328.AU
Modao River, Dazhou, Chungzhou Shunxichang, Fengcheng Huangcaoxia, Xiaoxi Tiansheng Bridge and Jialing River. 1 L of each sample was contained in a brown glass bottle and stored at 4°C for testing.
[66] Step 2: Sample pretreatment
[67] Water sample extraction method A: Adjust a recovered water sample to pH=2 with hydrochloric acid; activate an Oasis HLB solid-phase extraction (SPE) column by 5 mL of methanol and 5 mL of water respectively; feed 100 mL of water sample to the SPE column; perform three parallel tests for each group; load the sample at 3 mL-min-1; then rinse with 5 mL of ultrapure water, vacuu for 30 min under a negative pressure to dry, elute with 5 mL of methanol twice, and elute with 5 mL of acetonitrile (with 0.1% ammonium hydroxide); dry an eluent with nitrogen; dilute to 1 mL with methanol, oscillate for 1 min; analyze with an UHPLC-quadrupole/Exactive mass spectrometer.
[68] Water sample extraction method B: The eluent in method A is changed from methanol: acetonitrile (with 0.1% ammonium hydroxide) (1:1) to dichloromethane, and the other steps are the same as in Method A. Method B may be used as a follow-up supplement to Method A to perform secondary elution extraction of a chemical substance that is not effectively recovered in the water sample.
[69] Water sample extraction method C: The eluent in Method A is changed from methanol: acetonitrile (with 0.1% ammonium hydroxide) (1:1) to methanol: acetonitrile (1:1), and the other steps are the same as in Method A. Method C may also be used as a follow-up supplement to Method A to perform secondary elution extraction of a chemical substance that is not effectively recovered in the water sample.
[70] Step 3: Analysis by UHPLC-Q-Exactive MS
[71] LC conditions: Poroshell 120, EC-C18, 150 mm x 2.1 x 2.7 pm column, 40°C; positive ion mode: mobile phase A: 0.1% formic acid, and mobile phase D: acetonitrile; negative ion mode: mobile phase A: 0.05% ammonium hydroxide, and mobile phase D: acetonitrile; flow rate 0.3 mL/min; injection volume 5 pL; mobile phase gradient: 0 min, 90% A: 10% D; 0-2 min, 90% A: 10% D; 2-4 min, 70% A: 30% D; 4-6 min, 50% A: 50% D; 6-9 min, 40% A: 60% D; 9-14 min, O0%A: 100% D; 14-16 min, 90% A: 10% D; 16-17 min, 90% A: 10% D.
17691372_1 (GHMatters) P116328.AU
[72] MS conditions: electrospray ion source, 375°C, 3,500 V; sheath gas 40 arb; auxiliary gas 10 arb; backflush gas 0; S-lens RF: 50; auxiliary gas pressure: 10 arb; spray gas and collision gas: high-purity nitrogen; scan mode: data dependent scan (samples are separately injected in positive ion mode and negative ion mode; this mode includes primary full scan with a resolution of 70,000 and secondary scan with a resolution of 17,500; scan range 100-1,500 m/z; primary scan AGC: 1.0 e6; ion injection time: 100 ms; secondary AGC: 1.0 e5; maximum ion injection time: 100 ms); isolation window: 3.0 m/z; NCE: 30, 40, 50 eV; number of cycles: 3; dynamic exclusion: 10.0 s.
[73] Step 4: Rapid screening of SVHCs
[74] Thermo Fisher Scientific's Trance Finder 4.0 software was used for rapid qualitative screening. The chemicals were searched and matched in the MS database of the SVHCs based on exact mass, retention time, fragment ion and isotope ratio by using a precursor ion search algorithm, an isotope feature extraction algorithm and a structural similarity algorithm. A mass accuracy of a precursor ion in primary MS was controlled to be less than 5 ppm, a mass accuracy of a fragment in secondary MS was controlled to be less than 5 ppm and an isotope ratio error was controlled to be within 30%. In this way, 17 SVHCs were rapidly screened out from the 22 surface water samples collected in the Three Gorges.
[75] Then further qualitative identification was conducted. Mixed standard stock solutions (200 g/L) of 31 SVHCs were prepared by accurately taking 100 L of single standard stock solution (20 mg/L) into a 10 mL volumetric flask, diluting to a mark with methanol to obtain mixed standard stock solutions with a mass concentration of 200 pg/L and storing at 4°C.
[76] Methanol was used as a solvent to dilute the mixed standard stock solutions (200 pg/L) in proportion to obtain mixed standard solutions with mass concentrations of 1, 2, 5, 10, , 50 and 100 pg/L. The prepared mixed standard solutions were stored at 44°C.
[77] Further, standard curves were drawn. Methanol was used to prepare mixed standard solutions with mass concentrations of 1, 2, 5, 10, 20, 50 and 100 pg/L, and standard curves with a peak area (y) vs. the mass concentration (x) of target substances were drawn. Then quantitative analysis was conducted by using an external standard method. The results are shown in Table 3.
17691372_1 (GHMatters) P116328.AU
[78] Table 1 MS database of 220 SVHCs CAS RN Molecular Precursor Exact LOD LOQ Retention Characteristic fragment formula ion mass (pg/L) (pg/L) time 0060-09-3 C12HllN3 [M+H]* 198.1023 0.1128 0.3760 3.605 93.05768/77.0391/95.04948 97-56-3 C14H15N3 |[M+H] 226.1335 0.0509 0.1697 4.829 91.05464/106.0654 101-61-1 C17H22N2 |[M+H] 255.1851 0.0225 0.0752 1.056 239.1539/240.1609/196.112 842-07-9 C16H12N20 |[M+H] 249.102 0.0563 0.1879 6.145 93.05769/128.0495/231.0914 43121-43-3 C14H16ClN302 [M+H] 294.0998 0.0617 0.2058 3.956 57.07068/141.01 13194-48-4 C8H1902PS2 [M+H] 243.0634 0.1458 0.4860 3.813 130.9384/142.1589 82410-32-0 C9H13N504 [M+H] 256.1036 0.0092 0.0308 0.452 152.0564/153.0405/135.0299 4291-63-8 C1OH12ClN503 [M+H] 286.0697 0.0189 0.0632 0.619 170.0225/134.0459/244.9483 04243-04-3 C6H1ON60 [M+H] 183.0996 0.2471 0.8239 1.337 56.94299/72.93773/113.9638 75330-75-5 C24H3605 [M+H] 405.2628 0.0243 0.0812 5.349 100.1124/72.08136/199.1478 81103-11-9 C38H69NO13 [M+H] 748.4832 0.0253 0.0845 2.996 158.1174/83.04964/116.1071 536-33-4 C8H1ON2S [M+H] 215.0322 0.0556 0.1856 3.828 90.90368/98.98445 29885-18-5 C7H7ClN402 [M+H] 167.0636 0.0091 0.0305 0.625 140.0526/125.0293 54-62-6 C19H20N805 [M+H] 441.1627 0.0350 0.1169 4.197 441.2178/330.8538/325.176 120-71-8 C8HlINO [M+H] 138.0912 0.0546 0.1821 0.821 122.06/78.04694/123.0681 320-67-2 C8H12N405 [M+H] 245.0878 0.0532 0.1775 0.484 180.9598/113.0459 64091-91-4 C1OH13N302 [M+H] 208.1079 0.2181 0.7271 0.659 122.06/84.96017/79.04219 38194-50-2 C20H17FO3S [M+H] 357.0947 0.0266 0.0888 2.639 248.0991/295.0951 148-82-3 C13H18Cl2N202 [M+H] 485.1898 0.0177 0.0590 4.390 276.1501/261.1273 14028-44-5 C17H16ClN30 [M+H] 314.1049 0.0141 1 0.0472 2.194 271.0627/70.06576/297.078 621-64-7 C6H14N20 [M+H] 131.1179 0.0089 0.0296 16.966 74.09702/72.04504 492-80-8 C17H21N3 [M+H] 268.1804 0.0175 0.0583 2.244 268.1805/122.0965 924-16-3 C8H18N20 [M+H] 159.149 0.0604 0.2016 3.594 72.93775/76.93346 26471-62-5 C9H6N202 [M+H] 175.0501 0.0138 0.0462 1.120 97.00793/60.98721 59-89-2 C4H8N202 [M+H] 117.066 0.0942 0.2313 0.631 56.9656/58.0659 680-31-9 C6H18N30P | [M+H]* | 180.1258 | 0.0259 | 0.0866 0.991 | 92.02633/110.0368 125-84-8 C13H16N202 | [M+H]* | 233.1282 | 0.0080 | 0.0269 0.690 | 146.0961/131.0728/160.1117 110-86-1 C5H5N | [M+H]* | 80.05 | 0.0179 | 0.0599 10.545 | 53.03941/53.00301/51.02373 4759-48-2 C20H2802 | [M+H]* | 301.2159 | 0.0445 | 0.1486 7.749 | 57.07068/81.07024 153-78-6 C13HIlN | [M+H]* | 182.0963 | 0.0672 | 0.2240 1.441 | 165.0696/72.93774 80474-14-2 C25H31F305S [M+H] 501.1909 0.0173 0.0579 4.557 275.1423/293.1532/205.0656 82-28-0 C15HIlN02 [M+H] 238.086 0.0425 0.1417 3.916 238.0858/223.0624/165.0696 -56-0 C4H6N2S [M+H] 115.0326 0.0419 0.1397 0.591 57.05809/56.05027/59.52189 68-35-9 C10H1ON402S [M+H] 251.0575 0.9173 3.0578 0.643 108.0438/92.04918/96.05524 121163-60-8 C8H7N305 [M+H] 226.0436 0.8266 2.7554 1 0.866 67.04181/122.0102/211.0064 2447-57-6 C12H14N404S [M+H] 311.078 0.0781 0.2604 1.258 156.0753/108.0438/92.0492 127-79-7 CllH12N402S [M+H] 265.0731 0.9474 3.1583 0.679 108.0438/110.0706/92.04918 80621-81-4 C43H51N3011 [M+H] 786.3528 0.3911 1.3039 3.685 754.3253/151.0738/755.3253 -35-3 CllH12N403S [M+H] 281.0675 0.1850 0.6166 0.667 108.0437/266.9963/92.04914 57-68-1 C12H14N402S [M+H] 279.0884 0.1334 0.4448 0.694 124.0859/108.0437/92.04913 33419-42-0 C29H32013 [M-H]- 587.1749 0.0445 0.1483 6.555 113.0225/337.1074/339.1207 40925-68-6 C6H6BrNO [M-H]- 185.9543 0.0235 0.0784 5.232 169.064/170.0674 57-41-0 C15H12N202 [M-H]- 251.0815 0.1481 0.4939 5.236 214.925/103.0363 140-66-9 C14H220 [M-H]- 205.1584 0.0499 0.1666 13.431 133.0639/59.98347/56.994 25154-52-3 C15H240 [M-H]- 219.174 0.0237 0.0791 14.589 133.0638/147.0795/134.0669 -77-2 C6H4Cl20 [M-H]- 160.9549 0.0504 0.681 5.036 89.00135/124.978/61.00658 144-83-2 CIlHIlN302S [M-H]- 248.0489 0.0286 0.0955 1.089 93.04386/138.0178/91.02822 25812-30-0 C15H2203 [M-H]- 249.1485 0.1129 0.3764 5.811 121.0639/122.0672/61.98644 56-75-7 CllH12Cl2N205 [M-H]- 321.0038 0.0442 0.1235 6.544 121.0277/151.0257 31879-05-7 C15H1403 [M-H]- 241.0858 0.0228 0.0762 | 5.377 93.03265/154.9455/79.95544 120-95-6 C16H260 [M-H]- 233.1897 0.0247 0.0823 15.316 233.1896/203.1425/214.9124 -27-1 C18H2403 [M-H]- 287.1643 0.0442 0.1800 6.147 288.1675/188.9377 25013-16-5 C11H1602 [M-H]- 179.1062 0.0974 0.3247 10.159 164.0824/108.0197 69-72-7 C7H603 [M-H]- 137.0226 0.0952 0.3175 1.086 65.03782/94.03594 1220-83-3 CllH12N403S [M-H]- 279.0547 0.5597 1.8654 1.051 159.0658/200.0687 106-41-2 C6H5BrO [M-H]- 170.9434 0.1496 0.4567 6.541 170.943/84.94925 0097-02-9 C6H5N304 [M-H]- 182.019 537750 0.2792 7.489 135.0182/89.01262
17691372_1 (GHMatters) P116328.AU
CAS RN Molecular Precursor Exact LOD LOQ Retention Characteristic fragment formula ion mass (pg/L) (pg/L) time 17540-75-9 C18H300 [M-H]- 261.2214 0.1313 0.4377 16.6882 261.2212/111.9355/262.2249 194-59-2 C20H13N [M-H]- 266.0965 0.0481 0.1604 13.899 267.0997/264.0809 80-46-6 C11H160 [M-H]- 163.111 0.0463 0.1544 10.780 133.0639/56.99401/59.98335 139-13-9 C6H9NO6 [M-H]- 190.0341 0.0282 0.0940 0.883 87.00684/168.9469/78.95714 94-75-7 C8H6Cl203 [M-H]- 218.9608 0.1504 0.5014 5.038 160.9549/124.9781/219.1739 24353-61-5 CllH16NO4PS [M-H]- 288.0454 0.0748 0.2494 9.542 94.93426/125.9765/188.9374 29767-20-2 C32H32013S [M-H]- 655.1469 0.0164 0.0549 8.064 113.0226/99.00685/337.1067 22494-42-4 C13H8F203 [M-H]- 249.0356 0.0549 0.1832 5.642 205.0454/206.0489/185.0391 097-02-9 C6H5N304 [M-H]- 182.019 0.0884 0.2948 7.49 122.02287/135.0182/89.01262 59122-46-2 C22H3805 [M-H]- 381.2635 0.0275 0.0918 10.285 231.1377/263.1641 120-97-8 C6H6Cl2N204S2 [M-H]- 302.9063 0.0977 0.3257 1.090 187.9562/159.9709 27193-28-8 C14H220 [M-H]- 205.1582 0.0528 0.1762 13.533 133.064/205.1584/134.0671 1571-75-1 C20H1802 [M-H]- 289.1224 0.0167 0.0559 9.491 274.0987/156.9413/211.075 122-11-2 C12H14N404S [M-H]- 309.0653 0.0528 0.1761 1.092 66.00792/309.0652/154.0604 77-40-7 C16H1802 [M-H]- 241.1223 0.0726 0.2420 8.862 211.0749/74.9889/212.0792 1987-50-4 C13H200 [M-H]- 191.1426 0.0431 0.1439 13.942 106.0404/107.0438/98.12817 100-02-7 C11H160 [M-H]- 163.1111 0.0372 0.1242 10.784 133.0639/56.994/59.98325 446-86-6 C9H7N702S [M-H]- 276.0298 0.0770 0.2567 1.091 158.001/117.0186/134.0213 57-63-6 C20H2402 [M-H]- 295.1692 0.0427 0.1424 9.003 296.1725/267.1379 22071-15-4 C16H1403 [M-H]- 253.0859 0.0974 0.3249 5.222 215.9248/214.9259 2062-78-4 C28H29F2N30 [M-H]- 460.2195 0.0091 0.0304 13.049 460.219/133.039/461.2223 2105-94-4 C6H4BrFO [M-H]- 188.9344 0.0327 0.1090 3.802 188.9343/56.99396 080-05-7 C15H1602 [M-H]- 227.1065 0.0366 0.1221 8.152 133.064/211.0751/212.0814 301-12-2 C6H1504PS2 [M+H]* 247.0214 0.0255 0.0851 1.102 142.9921/124.9818 51-52-5 C7H1ON2OS [M+H]* 171.0579 0.1704 0.5680 1.12 130.93228/112.0755/59.99078
126-07-8 C17H17C106 [M+H]* 353.0775 0.1330 0.4433 1.170 69.03398/165.054/215.0097 55-18-5 C4H1ON20 [M+H]* 103.0866 0.0951 0.3171 4.9 97.00764/78.99734/56.96539 66085-59-4 C21H26N207 [M+H]* 419.1797 0.1119 0.3732 1.236 301.0808/257.091/302.0841 64-73-3 C21H22Cl2N208 [M+H]* 501.0897 0.2098 0.6995 1.124 169.0489/92.98292 76180-96-6 C11H1ON4 [M+H]* 199.0972 0.0507 0.1690 1.142 199.0971/131.06 34031-32-8 C20H34ApO9PS [M+H]* 679.1467 0.0853 0.2844 1.086 402.0464/679.1422 080-09-1 C12H1004S [M-H]- 239.0492 0.2118 0.74 0.74 239.0492/223.02769/132.0316 26148-68-5 CllH9N3 [M+H]P 184.0864 168811 0.1105 1.176 140.0489/167.0598 105650-23-5 C13H12N4 [M+H]P 225.1129 0.0996 0.3323 1.159 210.0893/225.1126/226.1159 144-80-9 C8H1ON2O3S [M+H]P 215.0479 0.0300 0.1002 1.074 92.04966/108.0443/65.03913 57-83-0 C21H3002 [M+H]P 315.2306 0.1531 0.5105 1.376 109.0648/315.1339 82419-36-1 C18H20FN304 [M+H]P 362.1497 0.0316 0.1053 5.951 261.1022/318.1599/262.1056 53-86-1 C19H16ClNO4 [M+H]P 358.0831 0.0957 0.3190 1.080 138.994/233.0752/248.0983 80214-83-1 C41H76N2015 [M+H]P 837.5284 0.1047 0.3492 1.574 158.117/116.1068/679.435 99-88-7 C9H13N [M+H]P 136.1116 0.0569 0.1897 1.214 91.05438/77.0389/65.0391 106-50-3 C6H8N2 [M+H]P 109.076 0.0664 0.2213 1.113 65.03918/80.04987/107.0604 67485-29-4 C25H24F6N4 [M+H]P 495.196 0.0594 0.1982 1.596 323.1464/496.1989 1 117-79-3 C14H9NO2 [M+H]P 224.0673 0.5913 1.9711 2.842 209.011/225.0421/73.04729 2 19666-30-9 C15H18Cl2N203 [M+H]P 345.0752 0.0940 0.3133 1.404 184.9868/219.9555 3 930-55-2 C4H8N20 [M+H]P 101.0711 0.0730 0.2435 1.153 55.05491/58.02938/53.03928 4 330-54-1 C9H1OCl2N20 [M+H]P 233.0235 0.1776 0.5922 1.230 159.9709/73.04815 23950-58-5 C12HllCl2NO [M+H]P 256.0281 0.0969 0.3233 2.632 225.042/227.0213 6 23564-05-8 C10H18N404S2 [M+H]P 355.0549 0.1267 0.4225 1.187 165.054/88.02177 7 59669-26-0 C12H14N404S2 [M+H]P 343.0518 0.0753 0.2510 1.136 85.9698/74.00634 8 76578-14-8 C19H17ClN204 [M+H]P 391.2828 0.0777 0.2591 2.394 84.95992/232.9281 9 134-32-7 C10H9N [M+H]P 144.0803 0.0388 0.1294 1.182 155.0597/127.0539/143.0724 40487-42-1 C13H19N304 [M+H]P 282.1438 0.1427 0.4758 1.562 267.1031/282.1139/266.0952 738-70-5 C14H18N403 [M+H]* 291.1438 0.0479 0.1598 5.126 230.115/123.0661/261.0971 2 1912-24-9 C8H14ClN5 [M+H]* 216.1004 0.0508 0.1695 8.430 104.001/96.05569/79.00605 3 58-14-0 C12H13ClN4 [M+H]* 249.0891 0.2325 0.7750 6.143 177.0206/249.0889/233.0578 4 81-81-2 C19H1604 [M+H]* 309.1107 0.1742 0.5809 9.694 251.069/191.0329 052-01-7 C24H3204S [M+H]* 417.2056 0.0787 0.2624 9.361 417.206/248.8995 6 119-90-4 C14H16N202 [M+H]* 245.1276 0.0953 0.3178 4.720 187.0857/186.0779
17691372_1 (GHMatters) P116328.AU
CAS RN Molecular Precursor Exact LOD LOQ Retention Characteristic fragment formula ion mass (pg/L) (pg/L) time 90-04-0 C7H9NO [M+H]* 124.0754 0.0625 0.2084 2.192 109.0521/80.04977/65.03906 21829-25-4 C17H18N206 |[M+H] 347.1224 0.0668 0.2228 8.917 254.1036/195.0907/84.96004 31431-39-7 C16H13N303 |[M+H] 296.1017 0.5150 1.7169 7.176 264.0755/158.9271/84.95991 6981-18-6 C14H18N402 |[M+H] 275.1492 0.1599 0.5332 5.194 123.0662/259.1179/81.04503 605-50-5 C18H2604 |[M+H] 307.1895 0.4756 1.5851 15.162 71.08599/150.0262 64-86-8 C22H25NO6 |[M+H] 400.1738 0.1656 0.5522 6.351 310.1184/358.1631/282.1238 67-45-8 C8H7N305 [M+H] 226.0451 0.0524 0.1748 5.706 67.04212/122.0107/83.03677 92-87-5 C12H12N2 [M+H] 185.1065 0.1150 0.3835 1.699 184.0986/183.091 70458-96-7 C16H18FN303 |[M+H] 320.1389 0.1688 0.5628 5.220 233.1075/320.1385/277.1198 52-86-8 C21H23ClFNO2 |[M+H] 376.1459 0.2762 0.9209 7.422 165.0703/123.0237/166.0736 95-76-1 C6H5Cl2N [M+H] 161.9866 0.2010 0.6712 8.674 127.0179/108.9838 111-96-6 C6H1403 |[M+H] 135.1011 0.0742 0.2475 3.32 136.0209/109.01044/65.0391 333-41-5 C4H6N2S |[M+H] 305.1071 0.1068 0.3560 12.99 169.07863/153.10149/96.9508 125-33-7 C12H14N202 |[M+H] 219.1119 0.0135 0.0395 5.482 117.0696/106.065 95-80-7 C7H1ON2 |[M+H] 123.0914 0,0089 0.0268 3.459 108.0681/81.05759 3380-34-5 C12H7C1302 |[M+H] 289.2151 0.3247 289.21 8.814 109.0647/84.95992 1596-84-5 C6H12N203 |[M+H] 161.0914 0.3798 161.09 0.869 55.01843/61.07654 41340-25-4 C38H69NO13 |[M+H] 288.1582 0.1215 0.4052 10.43 210.12669/172.11128/144.08032 54350-48-0 C23H3003 |[M+H] 355.2253 0.7526 2.5087 5.513 356.35123/159.07994/131.08507 84-61-7 C20H2604 |[M+H] 331.1891 0.3633 1.2111 15.545 91.05438/150.0261 115-86-6 C18H1504P |[M+H] 327.0768 0.2343 0.7812 12.568 233.0352/153.0693 71-58-9 C24H3404 |[M+H] 387.2514 0.4072 1.3575 12.095 123.0801/97.06491/214.9166 93-15-2 C11H1402 [M-H]- 179.1064 0.0693 0.2310 0.545 164.08282/165.08615/179.05534 88671-89-0 C15H17ClN4 [M+H] 289.1212 0.0766 0.2553 3.956 70.040771/125.01550/289.12124 96-45-7 C3H6N2S [M+H] 103.0329 0.0935 0.3118 0.451 103.03292/102.12823/56.96569 92-67-1 C12HIlN | [M+H]* | 170.0965 | 0.0150 | 0.0500 1.667 | 170.09651/171.0998/153.06977 91-59-8 C10H9N | [M+H]* | 144.0809 | 0.0260 | 0.0866 1.296 | 144.08088/145.08438/155.06015 25122-46-7 C25H32ClFO5 | [M+H]* | 467.1992 | 0.0518 | 0.1726 4.455 | 278.16625/263.14285/147.08045 595-33-5 C24H3204 | [M+H]* | 385.2372 | 0.0830 | 0.2765 4.617 | 267.17431/224.15596/282.19793 79-16-3 C3H7NO | [M+H]* | 74.0608 | 0.0152 | 0.0507 0.735 | 74.060806/74.097167/55.055160 651-06-9 CllH12N403S [M+H] 281.0702 0.0090 0.0302 0.872 156.01136/281.07031/126.06639 95-69-2 C7H8ClN [M+H] 142.0419 0.0319 0.1063 1.641 142.04191/107.07340/113.96402 645-05-6 C9H18N6 [M+H] 211.166 0.0150 0.0500 1.48 211.16586/96.05579/71.06089 87-62-7 C8HllN [M+H] 122.0967 0.0243 0.0810 1.007 122.09671/105.07033/107.07341 121-87-9 C6H5ClN202 [M+H] 173.0116 0.0342 0.1138 2.212 148.97711/130.96661/174.12776 499-75-2 C10H140 [M+H] 151.1119 0.0231 0.0769 0.883 150.11254/132.10203/88.076293 541-73-1 C6H4Cl2 [M+H] 146.9759 0.0932 0.3215 6.612 123.96461/64.928085/147.11466 120-12-7 C14H1O [M+H] | 179.1432 0.0271 0.0673 2.841 113.9640/179.06355/131.97436 22204-53-1 C15H17ClN4 [M+H] 231.1013 0.2858 0.9528 7.478 149.0234/150.0267487/174.1276398 6 73231-34-2 C12H14Cl2FNO4S [M-H]- 355.9951 0.0413 0.1376 4.862 119.0492706/78.984642/185.02778 7 41859-67-0 C19H20ClNO4 [M-H]- 360.1026 0.1977 0.6590 6.597 274.06518/154.00590/85.028335 8 15687-27-1 C13H1802 [M-H]- 205.1235 3.4033 11.3444 9.572 78.957855/99.92465/61.986949 9 57-67-0 C7H1ON402S [M+H] 215.0607 1.0899 3.6329 0.510 65.039688/80.050528/92.05046 723-46-6 C10HIlN303S [M+H] 254.0605 0.0556 0.1853 4.494 65.03973/108.04537/92.05055 1 72-14-0 C9H9N302S2 [M+H] 256.022 1.0899 3.6329 1.522 65.03970/108.04531/92.05043 2 36791-04-5 C8H12N405 [M+H] 245.087 0.0348 0.1160 1.09 114.02964/113.04561/96.01932 3 29122-68-7 C14H22N203 [M+H] 267.1715 0.0382 0.1275 3.127 145.06550/56.05064/107.05019 4 144-82-1 C9H10N402S2 [M+H] 271.033 0.1190 0.3967 1.836 65.03971/108.04532/92.05043 127-71-9 C13H12N203S [M+H] 277.0654 0.0188 0.0626 1.743 65.03973/108.04534/92.050453 6 515-64-0 C12H14N402S [M+H] 279.0923 0.0281 0.0937 1.152 124.08769/65.03972/108.04538 7 80-32-0 C1OH9ClN402S [M+H] 285.0221 0.0216 0.0719 3.350 65.03972/108.04531/92.05051 8 59-40-5 C14H12N402S [M+H] 301.0768 0.3115 1.0385 6.075 65.03970/108.04528/92.05045 9 526-08-9 C15H14N402S [M+H] 315.0924 0.0642 0.2139 6.013 158.07209/131.06112/92.05049 50-55-5 C33H40N209 [M+H] 609.2834 0.0563 0.1878 11.632 609.28375/195.06611/174.09223 1 23893-13-2 C37H65NO12 [M+H] 716.461 0.1025 0.3416 11.633 158.11840/83.05020/558.36621 2 62-73-7 C4H7Cl204P [M+H] 220.9528 0.0708 0.2361 6.670 127.01549/220.95280/78.99495 3 139-40-2 C9H16ClN5 [M+H] 230.1163 0.5272 1.7574 8.383 146.02258/230.11630/188.06947 4 122-39-4 C12HIlN [M+H] 170.0965 0.0295 0.0985 9.721 170.09655/93.057929/92.050135 119-61-9 C13H100 [M+H] 183.0806 0.0620 0.2068 9.148 105.03407/105.04453/183.08012 6 134-62-3 C12H17NO [M+H] 192.1384 6.0187 20.062 7.692 119.04955/192.13836/119.06047
17691372_1 (GHMatters) P116328.AU
CAS RN Molecular Precursor Exact LOD LOQ Retention Characteristic fragment formula ion mass (pg/L) (pg/L) time 103-33-3 C12H10N2 [M+H]* 183.0918 0.1985 0.6617 8.529 105.04524/183.09196/77.03932 21087-64-9 C8H14N4OS |[M+H] 215.0962 0.0640 0.2132 6.388 215.09629/187.101397/58.04093 26259-45-0 C10H19N50 |[M+H] 226.1662 0.1019 0.3397 7.944 170.10385/226.16638/100.0511 298-46-4 C15H12N20 |[M+H] 237.1014 0.0456 0.1519 7.34 194.09554/192.07983/193.0874 66852-54-8 C25H31ClF205 |[M+H] 485.1889 0.2079 0.6930 11.44 250.93761/232.92714/182.90167 15972-60-8 C14H20ClN02 |[M+H] 270.1255 0.1090 0.3634 9.840 162.12797/238.09954/147.10444 115-96-8 C6H12Cl304P [M+H] 284.9611 0.1458 0.4860 7.372 63.00053/98.98479/125.00024 14214-32-5 C16H18N203 |[M+H] 287.1387 0.0585 0.1949 7.987 72.04521/123.04438/287.13894 33665-90-6 C4H5NO4S [M-H]- 161.9854 1.1956 3.9853 0.334 82.02835/162.8923/161.98542 90-43-7 C12H100 [M-H]- 169.0647 0.0896 0.2987 8.623 169.06471/170.0681/134.86401 882-09-7 C1OHI1C103 [M-H]- 213.0316 0.0449 0.1496 3.329 126.99401/85.0278015/127.99751 25057-89-0 C1OH12N2O3S [M-H]- 239.0491 0.4641 1.5470 0.513 239.04928/132.03160/223.027664 0080-09-1 C12H1004S [M-H]- 239.0492 0.0923 0.3564 0.739 239.04924/132.03160/223.027694 97-23-4 C13H10C1202 [M-H]- 266.9984 0.0597 0.1992 9.604 126.99417/266.99853/127.99761 101-20-2 C13H9Cl3N20 [M-H]- 312.9706 0.1349 0.4496 10.806 159.97142/126.01010/160.97462 108-43-0 C6H5CO [M-H]- 126.9942 0.2577 0.8590 6.8087 126.9941/126.9036/61.98671 1478-61-1 C15H1OF602 [M-H]- 335.0511 0.2461 0.8204 9.2134 265.0481/335.0513/68.994 1221230-59-6 CllH12N403S [M+H] 281.0685 0.2874 0.7698 0.758 108.04409/299.05981/156.01045 1136506-12-1 C18H20FN304 [M+H] 362.15106 0.1249 0.4696 1.162 223.06245/113.96339/297.08071 53-16-7 C18H2202 [M+H] 271.16926 0.2589 0.7658 3.341 223.06221/100.07549/297.08041 66-76-2 C19H1206 [M+H] 337.069 0.2678 0.7869 12.4 175.0382/163.03822/84.95988 21145-77-7 C18H260 [M+H] 259.2049 0.0879 0.2156 15.47 176.11441/175.11099 /147.07968 83905-01-5 C38H72N2012 [M+H] 749.5189 5.8495 19.498 18.891 83.05020/158.11840/116.10790 148-79-8 C10H7N3S [M+H] 202.0426 0.5163 1.5163 4.61 202.04247/175.03171/131.05986 78-59-1 C9H140 [M+H] 139.1111 0.7896 2.7896 7.71 69.03391/56.94281 3778-73-2 C7H15Cl2N202P | [M+H]P | 261.0312 | 0.7834 | 2.2756 6.36 | 142.01793/140.0022/56.05011 7287-19-6 C10H19N5S | [M+H]P | 242.1424 | 0.8156 | 2.5317 10.57 | 158.04880/116.02747/68.02477 1113-02-6 C5H12NO4PS | [M+H]P | 214.0289 | 1.0635 | 3.2015 2.13 | 142.99200/127.01500/124.98164 85721-33-1 C17H18FN303 | [M+H]P | 332.1393 | 0.6879 | 1.9023 5.25 | 332.13937/ 245.10735/ 98.98419 443-48-1 C17H18FN303 | [M+H]P | 172.071 | 0.1637 | 0.3978 2.97 | 128.04494/ 82.05281/ 56.03753 57837-19-1 C15H21NO4 [M+H] 280.15310 0.5126 1.6021 8.43 160.11139/148.11139/84.95995 366-70-1 C12H20ClN30 [M+H] 258.1331 0.7021 2.2015 6.66 175.04945/147.05457/84.95992 58-22-0 C19H2802 [M+H] 289.2151 0.1876 0.5012 8.81 109.06466/97.06485/84.95992 90-94-8 C17H20N20 [M+H] 269.16360 0.5016 1.5323 11.11 210.09019/149.07854/148.07497 13614-98-7 C23H28ClN307 [M+H] 494.1711 0.6015 1.8302 17.08 359.02658/237.07831/91.05758 21725-46-2 C9H13ClN6 [M+H] 241.09530 0.4112 1.2347 7.35 158.92697/104.00095/84.95992 834-12-8 C9H17N5S [M+H] 228.127 0.5012 1.5390 9.4 186.07993/96.05569/68.02478 87-29-6 C16H15NO2 [M+H] 254.1165 0.15987 0.5012 12.73 117.06958/115.05387/98.9842 117-82-8 C14H1806 [M+H] 283.1165 0.1897 0.4567 7.76 143.88118/84.95997/59.04978 6 22839-47-0 C14H18N205 [M+H] 295.1277 0.5326 1.6231 1.09 120.08047/91.05434/88.03950 7 3468-63-1 C16H1ON405 [M+H] 339.0713 0.6321 1.8852 13.28 156.04375/128.04906/84.95992 8 136-45-8 C13H17N04 [M+H] 252.1221 0.5122 1.5023 10.49 182.08041/140.03351/122.02332 9 108-44-1 C7H9N [M+H] 108.08060 0.1568 0.5012 6.7 93.05739/91.05434/65.03908 126-73-8 C12H2704P [M+H] 267.1721 0.6122 1.9023 10.56 211.10937/155.04677/98.98417
17691372_1 (GHMatters) P116328.AU
[79] Table 2 Detected concentrations of chemical substances in water and soil samples collected in Chongqing (water unit: ng/L; soil unit: ng/g) W W W W W W W W W W W W W S S S S S S6 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 4 5 8. 8. 8. 8. 8.2 8. N 8. 8. 8. 11 8. 0. 0. 0. 0. 0. 0. Bisphenol B 7.9 1 0 2 2 2 D 3 2 1 .0 1 8 8 8 8 8 8 . N N N N N N N N N N N N N N N 0. N N 0. N-nitrosodiphenylamme D D D D D D D D D D D D D D D 5 D D 1 25 25 2525252525 25 2 2 3 2 2 N 25 25 N Pendimethalin D D 8. 7.0 D 7. 7. 7. 7. 7. 8. 5. 8. 0. 5. 5. 25 3 3 9 6 0 0 0 0 5 7 6 9 8 7 .7
N N 34 N N N N N N N N N N-nitrosodiethylamine D D .3 D D D D D D D D D 3. N N N N N N 6 D D D D D D Etoposide 65 6. 7. 6. 6. N 6. 6. 6. N 6. N N 0. 0. 0. N 0. N Etoposde 6. 6 6 3 7 D 3 3 3 D 3 D D 6 6 6 D 6 D 4-sec-butyl-2,6-di-tert-bu 16. 16 16 16 16 N N N N 16 N 16 16 1. 1. 1. N 1. 1. tylphenol 3 .1 .1 .2 .4 D D D D .7 D .2 .1 6 6 6 D 6 6 11 11 11 11 11 11 11 14 11 1 11I N 11 12 Cladribine 6.6 D 6. 0. 8. 6.8 7. 7. 7. 8. 6. 7. 6. N 1. N N N N 4 3 8 5 3 2 5 9 5 6 D 6 D D D D N 2. 1. 2. 1.5 1. 1. 1. 1. 1. 1. 1. 0. 0. 0. 0. 0. 0. Diclofenamide N D D 0 4 0 4 5 5 4 4 4 4 1 1 1 1 1 1 N 24 N 24 24 N 24 N 24 24 24 N 40 N 2. N 2. 2. 2. 4-heptyiphenol D .7 D .7 .7 D .7 D .7 .7 .7 D .7 D 5 D 5 5 5 N 3. N 3. N N N N N N N 3. 0. 0. 0. 0. 0. 0. Ketoprofen N D D 6 D 5 D D D D D D D 7 3 3 3 3 3 3 5. 5. 5. 5. 5.4 5. 5. 5. 5. 5. 17 N N N 0. N N N Estrone N D 2 2 3 3 2 3 3 3 2 .7 D D D 5 D D D N 31 31 N 29. 29 N 30 N 29 N 41 N N 2. N N 2. Colchicine N D D .4 .7 D 4 .3 D .2 D .5 D .0 D D 9 D D 9 31 37 33 N N N 44 38 18 N N 1. N N N N 1. Estriol 32. 34 0 .7 .3 .1 .0 D D D .1 .4 .1 D D 5 D D D D 5
39. 84 36 44 51 45. 75 62 72 N 49 15 46 Spironolactone 9 7 9 7 3 1 8 0 D .8 3. N N N N N N 9 .5 5 .9 .7 3 1 8 0 3 0 D D D D D D . 15. 15 15 15 15 15. 15 15 15 15 15 18 16 N N N N N N Nimodipme 1 .3 .1 .4 .2 2 .2 .6 .3 .2 .2 .0 .2 D D D D D D 13 N N 14 14 N N N 14 1 N 13 14 13 p-aminoazobenzene D 9. 3. 9. 9. D D 2. 1. D D D 7. N N 4. N N N 7 3 2 9 5 3 1 D D 0 D D D N N N N N N N N N N N N N 0. 0. 0. 0. 0. 0. Progesterone D D D D D D D D D D D D D 4 4 4 4 4 4 N 17 N N 17. N N N 17 N 17 N 1. N 1. 1. 1. N Nitrilotriacetic acid 17. 8 D .8 D D 8 D D D .8 D .8 D 8 D 8 8 8 D
N N 18 N N N N N N 34 N N N N N Etodolac D D 2. D D D D D D 8 D D D D D N N N N 6 D D D D 6.7 N N 6. N N N N N 6. N N N 0. 0. N 0. N 0. Quizalofop D D 7 D D D D D 7 D D D 7 7 D 7 D 7 N N N N 0.4 N N N N N N 1. -0 N 1. N N N Mebendazole N D D D D D D D D D D D 6 .1 D 2 D D D N N N N 25 N N N N N 25 25 25 2. 2. N 2. 2. 2. 7H-dibenzocarbazole D D D D .4 D D D D D .5 .5 .9 5 5 D 5 6 6 N 29 N N N N N N N N N N N 2. 2. N 2. 2. 2. Naproxen D .1 D D D D D D D D D D D 9 9 D 9 9 9
15. 16 N N N N N 19 19 N 14 49 Butylhydroxyanisole 7 .0 D D D D D .9 .2 D .3 D 0. N N N N N N 8 D D D D D D N N N N N N N I 1 I N N N N Primidone D D D D D D D D D 8. 8. D D 1. N N 1. 1. N 6 7 9 D D 9 9 D N 40 N N N N N 39 39 39 39 83 3. N N N 3. N Atrazine 39. 4 D .2 D D D D D .4 .3 .8 .5 .0 9 D D D 9 D N 20 N 20 20. 20 20 20 N 20 N N N N N N N N Ethinylestradiol N D D .6 D .6 5 .5 .6 .6 D .6 D D D D D D D D N N N N 28 28. N N N N N N 28 N 2. 2. N N N Ofloxacin D D D D .3 3 D D D D D D .4 D 8 8 D D D
17691372_1 (GHMatters) P116328.AU w w w w w w w w w w w w w S S S S S6 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 4 5 10. 10 N N N N 10 N N 10 N N N 1. N 1. N N N Diethylstilbestrol 2 .2 D D D D .2 D D .2 D D D 0 D 0 D D D 21 N N N 23. N N N 24 N 22 24 N N N 2. N 2. Isotretinoin N D .6 D D D 5 D D D .0 D .3 .3 D D D 1 D 1 N N N 77 77 N N N 77 N N N 77 N N N 7. N N Fenoprofen D D D .2 .1 D D D .1 D D D .1 D D D 7 D D
15 N N 20 N 16 N N 16 N N N N Triforine 155 2 N 168 4 D D N N N N N 15 8 0 D D D D D .0 .. N N N N N N N N N N N 11 N N 1. N N N N Toluenedisocyanate D D D D D D D D D D D .5 D D 1 D D D D . 54. N N N N N N N 61 N N N N N N 5. N N N Temposide 2 D D D D D D D .5 D D D D D D 4 D D D N N N N N N N N N N 27 N N N 2-phenylphenol D D D D D D D D D D D D D N N N N N 9. D D D D D 3
N N N N N N N N N N N N 22 2-aminoanthraquinone D D D D D D D D D D D D 3. N N N N N N 8 D D D D D D N N N 80 N N N N N N N N N N 80. N N N N Tributylphosphate 9 D D D D D D D .1 D D D D D D D D D D N N N N N N N N 19 19 N N N N 1. N N N N 3,4-dichlorophenol D D D D D D D D .3 .3 D D D D 9 D D D D 19 N N N N 17 N N 95 N N N N Misoprostol 64. D D D D 489. D D D D N N N N N N 3 1 4 D D D D D D
N N N N N N N N N N 2 -azacytidine D D D 4 N N N N N 21 9 3 D D D D D .4 4,4'-(1-phenylethyl)bisph N N N N N N N 38 N N N N N N N 3. N N N enol D D D D D D D .9 D D D D D D D 9 D D D
N N N N N N N N N N N N N 1 SudanI D D D D D D D D D D D D D N N 2. N N N D D 7 D D D N N N N N N N N N N N N N N N 0. N N N Diflunisal D D D D D D D D D D D D D D D 9 D D D N N N N N N N N N N 22 N N N N N N N N 4-bromo-2-fluorophenol D D D D D D D D D D .0 D D D D D D D D N N N N N N N N N N N N N N N N 1. L. Triadimefon N D D D D D D D D D D D D D D D D D 3 3
N N N N N N N N N 42 N N N Methyl eugenol 7. D N N N N N N 5 D D D D D D N N N N N N N N N N N N N N N N N N 5. Hydramethylnon D D D D D D D D D D D D D D D D D D 6
N NN N N N N N N N N 1 Pigment orange 5 6. D D 6. N N N N N N 6 7 D D D D D D N N 4. 3. N N N 3. 3. 3. 3. 65 N N N N N N 6-propyl-2-thiouracil D D 0 9 D D D 9 9 9 9 .6 D D D D D D . 15. 16 N 15 15 15. 15 15 15 N 15 15 19 N N N N N N N,N'-diacetylbenzidme 5 .3 D .5 .6 5 .5 .7 .6 D .5 .6 .3 D D D D D D N N N N N N N N 0. N N N N N N N N N N 2-amino-4-bromophenol D D D D D D D D 9 D D D D D D D D D D N N 54 53 N N N N N 56 N N 54 N N N N N N Dicoumarin D D .7 .9 D D D D D .8 D D .8 D D D D D D N N N N 51 N N N N N N N N N N N N N N aminoazotoluene D D D D .6 D D D D D D D D D D D D D D N N N N N N 61 N N N N N N N N N N N N 2,4-dibromophenol D D D D D D .2 D D D D D D D D D D D D N N N N N N N N N N N 36 36 N N N N N N Melphalan D D D D D D D D D D D .5 .6 D D D D D D 2-amino-I-methyl-6-phe 10. N N N N N N N N N N N N nylimidazo[4,5-b]pyridin 9 D D D D D D D D D D D D N L. L. L 1. L. e D 2 3 0 1 3 N 0. N N 0. N N N N N N 0. 0. N N N N 0. N Phenytoin D 3 D D 5 D D D D D D 2 2 D D D D 0 D 1. N N 7. 2.7 N N N N N N N N N N N N N 4-sec-butylphenol 1.3 9 D D 7 D D D D D D D D D D D D D Pimozide N N N N N N N N N N N N N N N N 0. 0. N
17691372_1 (GHMatters) P116328.AU w w w w w w w w w w w w w S S S S S5 S6 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 4 D D D D D D D D D D D D D D D D 3 3 D N N N N N N 25 N N N N N N N N N N N Tonalid N D D D D D D D .4 D D D D D D D D D D D
17691372_1 (GHMatters) P116328.AU
[80] Table 3 Detected concentrations of chemical substances in water samples collected in the Three Gorges (water unit: ng/L) S S S S S S S S S S S S S S S S S S S S S S x xx x x x x x x x x x x x x x x x x x x x W W W W W W W W W W W W W W W W W W W W W W 0 0 0 0 0 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 1 2 3 4 5 4-isopropyl 1 1 1 1 1 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 aniline 5. 5. 5. 5. 5. .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 6 5 5 5 5 1 1 1 1 2 1 1 2 2 2 1 1 1 1 0 0 1 2 3 4 4 1 2,6-diethyl 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. 0. aniline 4 3 3 3 3 38 39 38 38 38 38 38 38 38 38 38 38 38 38 38 38 38 0 8 8 8 8 2,4-diamin 1 1 1 1 2 97 59 19 24 18 31 32 14 14 78 12 12 16 11 14 13 20 otoluene 6. 3. 4. 4. 0. .4 .4 .7 .4 .3 .5 .9 .0 .1 .2 .4 .1 .5 .6 .0 .3 .8 9 9 4 7 0 7 7 8 4 0 0 7 4 1 8 9 2 4 1 1 9 2 8 6 5 3 2 2,6-dim eth 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. 1. ylaniline 1 1 2 2 1 17 14 18 12 26 09 44 07 07 13 10 11 08 03 06 04 03 4 8 2 0 3 Diphenyla 5 5 5 5 5 58 58 59 59 58 58 58 58 59 58 58 58 58 58 58 58 58 mine 8. 9. 8. 8. 8. .9 .9 .0 .0 .8 .8 .9 .9 .0 .8 .8 .8 .8 .8 .8 .8 .8 9 1 8 9 8 2 3 6 6 8 9 2 3 7 4 9 3 5 6 4 3 6 6 3 9 2 7 Tris(2-chlo 1 1 1 1 1 15 20 14 8. 16 11 13 13 14 12 16 19 16 18 16 15 21 roethyl)ph 4. 6. 5. 1. 6. .0 .2 .6 36 .0 .7 .9 .7 .6 .6 .4 .3 .1 .2 .9 .8 .4 osphate 4 3 0 1 0 9 5 9 2 9 2 9 0 5 7 6 9 0 0 9 8 9 3 6 7 1 Isophorone 1 1 1 1 1 12 12 20 14 16 14 12 12 13 12 12 14 11 10 14 11 10 5. 3. 3. 6. 6. .9 .4 .4 .2 .2 .7 .1 .7 .8 .5 .7 .2 .9 .5 .9 .6 .2 7 8 2 0 8 4 5 7 7 2 2 2 4 6 4 0 7 8 7 4 6 6 2 2 7 8 5
Ofloxacin 1 1 1 N N N N 15 N N N N 15 N N 15 15 N 16 16 N N 5. 6. 5. D D D D .9 D D D D .8 D D .7 .8 D .5 .3 D D 8 0 9 1 6 7 7 0 3 3 3 2 Atenolol 2 3 1 8. 7. 5. 6. 9. 3. 4. 6. 22 5. 4. 3. 10 4. 12 3. 5. 5. 7. 7. 8. 4. 4 5 92 48 64 11 73 44 .5 01 79 37 .5 23 .8 79 34 22 23 9 8 8 9 8 8 2 8 9 9 9 Benzophen 3 1 1 8 2 22 37 42 44 21 48 36 15 10 12 25 23 12 10 30 21 25 one 3. 4. 4. 4. 0. .7 .5 .2 .3 .5 .7 .7 .1 .1 .1 .0 .6 .0 .7 .7 .6 .9 0 3 9 0 0 2 6 5 2 0 9 9 9 1 5 4 7 5 0 4 5 1 4 0 9 4 6 Roxithrom N N N N N N N 32 N N N N N N N N N 32 N N N N ycin D D D D D D D .2 D D D D D D D D D .2 D D D D 3 3
Tris(2,3-di 1 N N 7 N N N N N N N N N N N N N N N N N N bromoprop 1. D D 7. D D D D D D D D D D D D D D D D D D yl)phospha 5 8 te 8 0 Progestone 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 5. 6. 4. 4. 4. 5. 4. 8 3 0 2 7 84 70 60 71 53 63 76 32 86 36 11 25 69 63 90 17 95 3 2 9 7 3
1-naphthol 1 2 1 2 2 16 16 13 17 16 15 21 16 17 27 18 15 20 13 18 15 16 5. 4. 6. 5. 0. .8 .7 .5 .9 .2 .0 .0 .3 .1 .7 .2 .9 .2 .2 .2 .5 .1 5 9 9 0 4 0 8 1 9 1 2 2 7 5 1 7 1 7 6 4 6 1 3 0 0 7 9 2,4-di-tert- 3 4 3 4 4 39 40 39 40 39 41 39 40 39 39 39 42 40 41 39 40 39 amylpheno 9. 0. 9. 3. 0. .5 .2 .9 .3 .4 .0 .6 .4 .5 .5 .9 .7 .0 .2 .7 .0 .3 1 6 8 4 1 2 8 1 8 8 0 4 5 2 6 7 4 3 5 4 5 4 1 1 1 9 0 7
17691372_1 (GHMatters) P116328.AU s s s s s s s s s s s s s s s s s s s s s s x xx x x x x x x x x x x x x x x x x x x x W W W W W W W W W W W W W W W W W W W W W W 0 0 0 0 0 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 1 2 3 4 5 Ketoprofen 1 8 6 9 1 90 58 67 63 37 51 61 54 78 26 36 32 44 18 10 38 37 1 5. 4. 0. 0 .6 .1 .8 .2 0. .1 .1 .6 .2 2. .3 .0 .9 .8 4. .7 .9 2. 0 9 3 0. 0 3 0 3 72 5 3 0 9 81 4 3 9 6 28 0 0 6 3 7 5 0 5 6 Aspartame 3. 3. 4. 3. 2. 1. 2. 2. 2. 3. 2. 2. 3. 3. 2. 2. 2. 3. 2. 2. 2. 2. 3 8 1 8 2 86 35 49 18 30 70 17 39 58 69 52 07 53 57 86 40 39 0 7 5 8 2
[81] It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
[82] In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
17691372_1 (GHMatters) P116328.AU

Claims (5)

WHAT IS CLAIMED IS:
1. A method for rapidly screening substances of very high concern (SVHCs) in surface water and soil, wherein the method comprises the following steps: step 1: selection of a list of SVHCs; step 2: grouping of the SVHCs; step 3: optimization of mass spectrometry (MS) conditions and liquid chromatography (LC) conditions; step 4: construction of an MS database of the SVHCs; and step 5: rapid screening of SVHCs in surface water and soil.
2. The method for rapidly screening SVHCs in surface water and soil according to claim 1, wherein step 1 comprises: selecting a total of 220 chemicals, comprising 46 carcinogens, 22 chemicals known to cause reproductive toxicity, 4 SVHCs listed by the European Union (EU), 22 alkylphenols and endocrine-disrupting chemicals (EDCs), 2 persistent, bioaccumulative and toxic (PBT)/very persistent and very bioaccumulative (vPvB) chemicals, 97 pharmaceuticals and personal care products (PPCPs) and 27 others.
3. The method for rapidly screening SVHCs in surface water and soil according to claim 2, wherein step 2 comprises grouping the SVHCs selected in step 1 based on uses, structural characteristics and hazards of the SVHCs: a: carcinogens and chemicals known to cause reproductive toxicity (72): 4,4'-methylenebis(N,N-dimethylaniline), 2-amino--methyl-6-phenylimidazo[4,5-b]pyridine, pyridine, bis(2-methoxyethyl)ether, tris(2-chloroethyl)phosphate, 2-aminoanthraquinone, dimethoxyethyl phthalate, diisoamyl phthalate, o-dianisidine, 4,4'-diamino-3,3'-dimethylbiphenyl, 6-methoxy-m-toluidine, diclofenamide, aminoglutethimide, ethoprophos, 1-aminonaphthalene, dipropylpyridine, nitrilotriacetic acid, 2-aminofluorene, 7H-dibenzocarbazole, daminozide, oxadiazon, cyanazine, thiophanate methyl, propyzamide, butylhydroxyanisole, 2-amino-9H-pyrido[2,3-b]indole, toluene diisocyanate, oxydemeton-methyl, mebendazole, 5-azacytidine, diuron, auranofin, pigment orange 5, procarbazine hydrochloride, ifosfamide, triadimefon, auramine 0, 6-propyl-2-thiouracil, N-nitrosodiethylamine, pyrimethamine, colchicine, dicoumarin, thiodicarb, N-nitrosomorpholine, methimazole, N-nitrosodi-n-propylamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone, hydramethylnon, IQ[2-amino-3-methylimidazo(4,5-F)quinoline], quizalofop, hexamethylphosphoric triamide,
17691372_1 (GHMatters) P116328.AU
2-amino-3,4-dimethyl-3H-imidazo[4,5-f]quinoline, N-methylacetamide, warfarin, dicyclohexyl phthalate, cinnamyl anthranilate, 2,6-dimethylaniline, Sudan I, myclobutanil, 2-methoxyaniline, 4,4'-tetramethyldiaminobenzophenone, 2-naphthylamine, N-nitrosodi-n-butylamine, benzidine, N-nitrosopyrrolidine, 1,2-dimethoxy-4-(2-propenyl)benzene, disperse orange 11, 4-chloro-2-methylaniline, 2,4-diaminotoluene, vinyl sulfide, o-aminoazotoluene, 4-aminobiphenyl and pendimethalin; b: PPCPs (97): indomethacin, ketoprofen, atenolol, chloramphenicol, azithromycin, nimodipine, ibuprofen, etoposide, ribavirin, cladribine, etretinate, misoprostol, megestrol-17-acetate, sulindac, lovastatin, clarithromycin, cladribine, ganciclovir, aminopterin, ethionamide, misoprostol, sulfachloropyridazine, sulfadiazine, sulfamethazine, amoxapine, melphalan, teniposide, medroxyprogesterone acetate, clobetasol propionate, aspartame, diflunisal, primidone, ganciclovir, thiophanate methyl, isotretinoin, griseofulvin, pimozide, nifedipine, auranofin, dehydroerythromycin A, secbumeton, acesulfame potassium, 2-amino-9H-pyrido[2,3-b]indole, 5-azacytidine, haloperidol, sulfamethazine, azathioprine, ofloxacin, norfloxacin, trimethoprim, roxithromycin, sulfapyridine, sulfadimethoxine, phenytoin, naproxen, florfenicol, sulfametoxydiazine, sulfamonomethoxine, rifaximin, metronidazole, minocycline hydrochloride, sulfamethoxazole, sulfathiazole, sulfisomidine, sulfadimoxine, sulfamethizole sulfabenzamide, demecycline hydrochloride, tonalid, isophorone, ciprofloxacin, triclocarban, halobetasol propionate, reserpine, sulfamethoxypyridazine, gemfibrozil, bezafibrate, fenoprofen, provera, haloperidol, indomethacin, sulfamidine, sulfacetamide, triclosan, clofibric acid, bentazone, salicylic acid, ormetoprim, etodolac, carbamazepine, progesterone, estrone, testosterone, diethylstilbestrol, a-estradiol, p-estradiol, estrone and estriol; c: alkylphenols (22): bisphenol A, bisphenol B, bisphenol AF, bisphenol S, bisphenol AP, bisphenol Z, nonylphenol, 4-(tert-octyl)phenol, methyl eugenol, 4-tert-amylphenol, octylphenol, 3,4-dichlorophenol, 2-amino-4-bromophenol, 4-sec-butyl-2,6-di-tert-butylphenol, 4-heptylphenol, 4-nitrophenol, 4-bromo-2-fluorophenol, 4-bromophenol, p-nitrophenol, 2,4-di-tert-amylphenol, o-aminophenol and dichlorophenol/biphenyl-2-phenol; and d: others (29): 8-chlorotheophylline, acesulfame potassium, azobenzene, benzophenone, diphenylamine, p-aminoazobenzene, genistein, anthracene, triphenyl phosphate, tributyl phosphate, isocarbophos, 2,4-dinitroaniline, alachlor, diethyltoluamide, p-phenylenediamine, 3-methylaniline, 3,4-dichloroaniline, spironolactone, furazolidone, p-isopropylaniline, 1,3-dichlorobenzene, 2-chloro-4-nitroaniline, metribuzin, dacarbazine,
17691372_1 (GHMatters) P116328.AU
2,4-dichlorophenoxyacetic acid, difenoxuron, 2-(diethylamino)ethyl 1-(m-tolyl)cyclopentane-1-carboxylate and ethylene thiourea;
4. The method for rapidly screening SVHCs in surface water and soil according to claim 1, wherein in step 3, the MS conditions comprise sheath gas, auxiliary gas, spray voltage, capillary temperature, resolution, automatic gain control (AGC), maximum ion injection time, number of cycles, normalized collision energy (NCE), single ion monitoring (SIM), full scan mode; the LC conditions comprise C18/Hillic/T3 columns, mobile phase buffer salt and addition concentration; wherein after the optimization, the LC conditions comprise Poroshell 120, EC-C18, 150 mm x 2.1 x 2.7 pm column, 40°C; positive ion mode: mobile phase A: 0.1% formic acid, and mobile phase D: acetonitrile; negative ion mode: mobile phase A: 0.05% ammonium hydroxide, and mobile phase D: acetonitrile; flow rate 0.3 mL/min; injection volume 5 pL; mobile phase gradient: 0 min, 90% A: 10% D; 0-2 min, 90% A: 10% D; 2-3 min, 70% A: 30% D; 3-6 min, 50% A: 50% D; 6-9 min, 40% A: 60% D; 9-15 min, 0% A: 100% D; 15-23 min, 0% A: 100% D; 23-23.5 min, 90% A: 10% D; 23.5-25 min, 90 % A: 10% D; wherein after the optimization, the MS conditions comprise: electrospray ion source, 375°C, 3,500 V; sheath gas 40 arb; auxiliary gas 10 arb; backflush gas 0; S-lens radio frequency (RF): 50; auxiliary gas pressure: 10 arb; spray gas and collision gas: high-purity nitrogen; scan mode: data dependent scan (samples are separately injected in positive ion mode and negative ion mode; this mode comprises primary full scan with a resolution of ,000 and secondary scan with a resolution of 17,500; scan range 100-1,500 m/z; primary scan AGC: 1.0 e6; ion injection time: 100 ms; secondary AGC: 1.0 e5; maximum ion injection time: 100 ms); isolation window: 3.0 m/z; NCE: 30, 40, 50 eV; number of cycles: 3; dynamic exclusion: 10.0 s.
5. The method for rapidly screening SVHCs in surface water and soil according to claim 1, wherein step 4 comprises acquiring secondary information of target compounds based on a data dependent scan, comprising exact mass, retention time, structural fragment and isotope ratio; checking a characteristic fragment, entering the compounds' names, Chemical Abstracts Service registry number (CAS RN) and molecular formulas to form an MS database of the SVHCs covering the data of the compounds such as exact mass of precursor ion, retention time, exact mass of characteristic fragment, isotope ratio, polarity, NCE and charge number; wherein step 5 specifically comprises: rapidly screening different groups of SVHCs in
17691372_1 (GHMatters) P116328.AU surface water and soil samples: first, pretreating the water and soil samples by 6 extraction methods as follows: water sample extraction method A: adjusting a recovered water sample to pH=2 with hydrochloric acid; activating a solid-phase extraction (SPE) column by 5 mL of methanol and mL of water respectively; feeding 100 mL of water sample to the SPE column; performing three parallel tests for each group; loading the sample at 3 mL-min-1; then rinsing with 5 mL of ultrapure water, vacuum-drying for 30 min under a negative pressure, eluting with 5 mL of methanol twice, and eluting with 5 mL of acetonitrile comprising 0.1% ammonium hydroxide; drying an eluate with nitrogen; diluting to 1 mL with methanol, oscillating for 1 min; analyzing with an ultra-high-performance liquid chromatography (UHPLC)-quadrupole/Exactive mass spectrometer; water sample extraction method B: the eluent in method A is changed from the methanol: acetonitrile to dichloromethane, and the other steps are the same as in Method A; water sample extraction method C: the eluent in Method A is changed from the methanol: acetonitrile to methanol: pure acetonitrile, and the other steps are the same as in Method A; soil sample extraction method A: taking 5 g of soil sample into a 50 mL centrifuge tube, adding 25 mL of acetonitrile, oscillating for 20 s, and treating for 15 min in an ultrasonic cleaner to obtain an extract; loading at 3 mL/min to an SPE column; rinsing with 2 mL of dichloromethane, collecting an eluate, and drying with nitrogen; diluting to 1 mL with acetonitrile, oscillating for 1 min, and passing through a 0.22 m filter membrane for further analysis; soil sample extraction method B: the eluent in the soil sample extraction method A is changed from the acetonitrile to a methanol solution with 1% of formic acid, and the other steps are the same as in the soil sample extraction method A; soil sample extraction method C: transferring the extract obtained in the soil sample extraction method A to a centrifuge tube filled with 150 mg of primary secondary amine (PSA) and 150 mg of Cis in advance for purification; oscillating for 2 min and letting stand for 2 min, wherein the other steps are the same as in the soil sample extraction method A; then, conducting sample loading and analysis according to the MS and LC conditions in step 3; matching in the MS database of the SVHCs based on the exact mass, retention time, characteristic fragment and isotope ratio by using a precursor ion search algorithm, an isotope feature extraction algorithm and a structural similarity algorithm (Euclidean distance analysis);
17691372_1 (GHMatters) P116328.AU screening out SVHCs based on a mass accuracy (less than 5 ppm) of a precursor ion in primary MS, a mass accuracy (less than 5 ppm) of a fragment in secondary MS and an isotope ratio error (within 30%).
17691372_1 (GHMatters) P116328.AU
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CN115201382A (en) * 2022-09-08 2022-10-18 沧州大化股份有限公司 Method for detecting sample containing diaminotoluene

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