CN113484437B - Method for determining ultra-trace halocarban in environmental water sample and application thereof - Google Patents
Method for determining ultra-trace halocarban in environmental water sample and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of detection, and particularly relates to a method for determining ultra-trace halocarban in an environmental water sample and application of the method. The method comprises the following steps: after an environmental water sample is filtered, performing liquid-liquid extraction, concentration and volume fixing, and determining ultra-trace halocarbon in the environmental water sample by adopting an ultra-high performance liquid chromatography-electrospray ionization source quadrupole rod mass spectrometry Multiple Reaction Monitoring (MRM) mode. The method has good linear relation (R) within the range of 0.02-2.00 ng/mL20.9956), the detection limit is 0.01ng/mL, the quantification limit is 0.02ng/mL, the recovery rate of the added standard is 90.39-95.87%, and the relative standard deviation of the results of 6 times of parallel measurement is 3.05-3.93%.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a method for determining ultra-trace halocarbn in an environmental water sample and application thereof.
Background
Halocarban, CAS number: 369-77-7 (also known as fluoromethoxyphenylurea, Halocaban, difluoride, Allen name halocarban, English name Cloflacan, chemical structural formula is shown in figure 1, and molecular formula is C14H9Cl2F3N2O, molecular weight 348.0044, is easily soluble in organic solvents and insoluble in water. Because halocarban has antifungal, disinfectant and antiseptic effects, it is often used as a bacteriostatic for deodorant, soap and medical care personnelA hand sanitizer. In addition, the cationic surfactant is also applied to laundry detergent.
However, due to reproductive toxicity of halocarb, the U.S. Food and Drug Administration (FDA) declared a ban on the continued use of halocarb in antibacterial soaps in 2016. The European Chemicals Agency (ECA) in the list of substances released in 2016 lists halocasan as a suspected carcinogen, suspected of harming aquatic environments, and possibly having persistent and reproductive toxicity in the environment. The argentina-related agency banned the use of halocarb for antimicrobial products (such as personal care products, cosmetics, and/or perfume products) registered with argentina via resolution 13832/2016.
With the acceleration of socialization process in China, the discharge amount of urban domestic sewage and industrial sewage is increased year by year, and the problem of water environment pollution is increasingly serious. Therefore, water environment treatment becomes a major focus problem, and water quality detection is an important link in the water environment treatment process. At present, no complete and rapid method for detecting halocarban in natural waters exists.
Arno H.A. Heyn a et al established a method for determining halocarban in bacteriostatic soaps by gas-liquid chromatography (GLC) in 1982 (International Journal of Environmental Analytical chemistry, 1982,11(2): 131-. The method needs chemical derivatization of target analytes, and has the disadvantages of complex pretreatment, large workload, detection limit of 78ng/mL and low sensitivity.
Therefore, a simple, quick, efficient and sensitive method for determining the content of halocarb is needed to be established at the present stage, and technical support is provided for use monitoring, water quality detection and water environment treatment of halocarb.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to fill the blank of the prior art and provides a method for determining ultra-trace halocarb in an environmental water sample, thereby providing technical support for use monitoring, water quality detection and water environment treatment of halocarb.
In the invention, the term "ultra trace amount" refers to the content of a substance to be measured being less than 1 mug/mL; the method is used for rapidly determining the ultra-trace halocarbn in a complex mixed system, and has the detection limit of 0.01ng/mL and the quantification limit of 0.02 ng/mL.
The technical scheme of the invention is as follows: after an environmental water sample is filtered, a method for determining ultra-trace halocarbn in the environmental water sample is established by adopting an ultra-high performance liquid chromatography-electrospray ionization source quadrupole rod mass spectrometry (UPLC-ESI-MS/MS) multi-reaction monitoring (MRM) mode after liquid-liquid extraction, concentration and volume fixing, and specifically comprises the following steps:
step (1), preparing a standard working solution of halocarban series: preparing standard working solutions of halocarbn series with the concentrations of 0.01, 0.02, 0.05, 0.60, 1.20, 1.40, 1.60, 1.80 and 2.00ng/mL by using 80% vol methanol aqueous solution;
step (2), sample pretreatment: filtering m g of environmental water sample to be detected by using a 0.45 mu m microporous filter membrane, extracting the filtrate in a separating funnel for 4 times by using chromatographic pure dichloromethane as an extraction liquid, and combining organic phases; concentrating the combined organic phases by using a rotary evaporator until the combined organic phases are nearly dried to obtain an extraction concentrated solution, performing constant volume on the extraction concentrated solution to obtain a concentrated constant volume sample to be detected by using methanol, transferring the concentrated constant volume sample to a liquid chromatography sample bottle, and performing ultrahigh performance liquid chromatography-electrospray ionization source quadrupole rod mass spectrometry;
step (3), blank experiment: using m g of primary water (see GB/T6682-;
and (4) drawing a standard working curve: measuring the peak area of halocarbn in the series of standard working solutions in the step (1) by adopting ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry, and performing linear regression by taking the concentration of halocarbn as a horizontal coordinate and the corresponding peak area as a vertical coordinate to draw a standard working curve;
step (5), determining the content of halocarban in the sample: measuring the peak area of halocarbn in the concentrated constant volume sample to be measured in the step (2) by adopting ultra-performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry, and obtaining the concentration C of halocarbn in the concentrated constant volume sample according to the standard working curve drawn in the step (4);
and (6) determining the content of halocarban in the blank sample: measuring the peak area of halocarbn in the concentrated constant volume blank sample to be measured in the step (3) by adopting ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry, and obtaining the concentration C of halocarbn in the concentrated constant volume blank sample to be measured according to the standard working curve drawn in the step (4)0；
Step (7), calculating the content of halocarban in the environmental water sample:
calculating the content X of halocarban in the environmental water sample to be detected according to the formula (1),
in the formula (I), the compound is shown in the specification,
x represents the content of halocarban in the environmental water sample to be detected, and the unit is mu g/kg;
c, obtaining the concentration of halocarbn in the concentrated constant volume sample from the standard working curve, wherein the unit is ng/mL;
C0-the concentration of halocarbn in the concentrated constant volume blank obtained from the standard working curve, in ng/mL;
v, concentrating the extract to a constant volume, wherein the unit is mL;
m is the mass of the environmental water sample, and the unit is g; because the density of water is 1g/mL, the mL volume value of the environmental water sample can be directly substituted;
integral multiple-dilution factor; if the concentration of the halocarbn in the sample solution to be tested does not exceed the maximum concentration of the standard working solution, taking 1 as the dilution factor; if the concentration of halocarbn in the sample solution to be tested exceeds the maximum concentration of the standard working solution, adjusting and diluting the solution to be tested by using methanol, and then measuring, if the solution is diluted to 2 times, taking a dilution factor of 2, and so on;
preferably, the arithmetic mean of the results of the multiple replicates is taken as the final measurement, accurate to 0.01. mu.g/kg; the relative mean deviation of multiple parallel measurements should be less than 10%.
Preferably, in the step (4), the step (5) and the step (6), the liquid chromatography conditions of the ultra high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method are as follows: the column was an ACQUITY UPLC HST 3 column (2.1 mm. times.100 mm,1.8 μm, Waters Corp.); the sample injection amount is 5 mu L; the flow rate is 0.3 mL/min; the column temperature is 30 ℃; mobile phase a is 0.1% vol formic acid aqueous solution, mobile phase B is methanol; gradient: 0-1.0 min, wherein the proportion of the mobile phase B is 85-90% vol; 1.0-2.0 min, wherein the proportion of the mobile phase B is 90-100% vol; 2.0-3.0 min, and the mobile phase B accounts for 100-85% vol.
Mass spectrum conditions of the ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method in the step (4), the step (5) and the step (6): the ion source is an electrospray ionization source (ESI); the scanning mode is negative ion scanning (ESI)-) (ii) a The capillary voltage is 3 kV; the extraction taper hole voltage is 5V; the RF mass spectrum voltage is 0.5V; the ion source temperature is 120 ℃; the desolventizing gas is nitrogen, and the purity is not less than 99.99 percent; the temperature of the desolventizing gas is 500 ℃; the flow rate of the desolventizing agent is 600L/hr; the collision gas is argon; the pressure in the collision chamber was 3.80e-3mbar; the voltage of the photomultiplier is 650V; the detection mode is multi-reaction monitoring (MRM); the residence monitoring time of the ion pair was 50 ms.
Preferably, in the step (4), the step (5) and the step (6), the retention time and the multiple reaction monitoring parameters of the halocarbban ultra high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method are shown in the following table:
note: are quantitative ions.
The second aspect of the invention provides the use of the method for determining the ultra-trace halocarbn in the environmental water sample, which is used for rapidly determining the ultra-trace halocarbn in a complex mixed system, wherein the detection limit is 0.01ng/mL, and the quantification limit is 0.02 ng/mL.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for determining the ultra-trace amount of halocarbn in the environmental water sample, which is established by adopting ultra-high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS) for the first time, has higher specificity and anti-interference capability, can accurately determine the content of the halocarbn in a complex mixed system even if the environmental water sample is seriously polluted and contains more interference substances, and is favorable for determining the ultra-trace amount of halocarbn in the complex mixed system;
2. the invention adopts the ultra-high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS) to establish the quantitative analysis method of halocarbn in the environmental water sample for the first time, and unexpectedly discovers that: the ultra-trace halocarbn in a complex mixed system can be quickly and sensitively detected only by simple pretreatment (such as filtration, liquid-liquid extraction, concentration and constant volume) and without chemical derivatization; the detection limit is as low as 0.01ng/mL, and the quantification limit is as low as 0.02 ng/mL;
3. the method for determining the ultra-trace amount of halocarbn in the environmental water sample, which is established by adopting ultra-high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS) for the first time, has a good linear relation (R) within the range of 0.02-2.00 ng/mL20.9956), the recovery rate of the added standard is 90.39-95.87%, the relative standard deviation of the results of 6 times of parallel measurement is 3.05-3.93%, and the reliability of the measurement results is ensured by better recovery rate and repeatability;
4. the method for determining the ultra-trace halocarbn in the environmental water sample is established by adopting ultra-high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS) for the first time, and can provide technical support for use monitoring, water quality detection and water environment treatment of the halocarbn.
Drawings
FIG. 1 shows the structural formula of halocarban according to the present invention;
FIG. 2 is a halogen Carban UPLC-ESI-MS/MS total ion flow chromatogram (TIC) of a standard working solution of concentration 1.00ng/mL according to an embodiment of the present invention;
FIG. 3 is a halogen Carban UPLC-ESI-MS/MS quantitative ion chromatogram (MRM) of a standard working solution of concentration 1.00ng/mL according to an embodiment of the present invention;
FIG. 4 shows a halogen Carban UPLC-ESI-MS/MS qualitative ion chromatogram (MRM) of a standard working solution of concentration 1.00ng/mL according to an embodiment of the present invention;
FIG. 5 is a halogen Carban UPLC-ESI-MS/MS quantitative ion chromatogram (MRM) of a standard working solution of concentration 0.01ng/mL (detection limit) according to an embodiment of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to these examples. In the examples, the experimental methods in which specific conditions are not specified are generally commercially available under the conditions described in general and handbooks, or under the conditions recommended by the manufacturers using general-purpose equipment, materials, reagents and the like, unless otherwise specified. The starting materials required in the following examples and comparative examples are all commercially available.
Example 1
A method for determining ultra-trace halocarban in an environmental water sample comprises the following steps:
1 Instrument, reagent and Material selection
The instrument comprises: WatersACQUITYTM UPLC ultra high performance liquid chromatograph tandem UPLC QUATTRO PREMI XE mass spectrometer (Waters corporation, USA); an ACQUITY UPLC HSS T3 column (2.1 mm. times.100 mm,1.8 μm, Waters Corp.); P300H ultrasonic cleaner (Elma, switzerland); HYQ-2110 vortex mixer (Crystal Co., USA); METTLER TOLODO XP 504 electronic analytical balance (METTLER TOLODO, Switzerland, sensory was 0.1 mg); BCD-620WDBF refrigerator (Qingdao Haier Ltd.); r-2155244 rotary evaporator (BUCHI, Switzerland); CA-1111 Coolant circulation apparatus (BUCHI, Switzerland); b-491 Water bath (BUCHI, Switzerland); v-700 + V-85 diaphragm vacuum pump (BUCHI, Switzerland); DIRET UV3 water purifier (Millipore, USA); a vortex oscillator with the use rotating speed of 500 r/min; a centrifuge with the use speed of 5000 r/min; pipettes of various specifications, pipette guns, volumetric flasks, triangular flasks with stoppers and centrifuge tubes.
Reagent: analytical grade or more reagents should be used, except for special requirements. Halocarban (Halocarban, CAS number 369-77-7; Alfaaesar Standard, UK, purity 99.7%); methanol (HPLC grade, Merck, germany); dichloromethane (HPLC grade, TEDIA corporation, usa); formic acid (LC-MS grade, bailing technologies ltd, china); water, GB/T6682, first order.
Materials: the detected 3 environmental water samples were collected from Panlongjiang (midstream), Dian chi (sea ridge park) and grand river (downstream) in Kunming city, respectively.
2 method of experiment
2.1 preparation of Halocarban Standard solution
2.1.1 preparation of Primary Standard stock solution
Accurately weighing 10mg halocasin (accurate to 0.1mg) in a 100mL volumetric flask, and diluting to constant volume with 80% vol methanol water solution to prepare a halocasin standard stock solution with the concentration of 0.1 mg/mL. Sealed and lightproof at 0-4 ℃ for storage, and the effective period is 6 months.
2.1.2 preparation of Secondary Standard stock solutions
Taking 50 mu L of halocarbn standard stock solution with the concentration of 0.1mg/mL into a 100mL volumetric flask, and using 80% vol methanol water solution for constant volume to prepare 50ng/mL halocarbn secondary standard stock solution. Sealed and lightproof at 0-4 ℃ for 3 months of effective period.
Preparation of 2.1.3 series standard working solution
Accurately transferring 2 mu L, 4 mu L, 10 mu L, 120 mu L, 240 mu L, 280 mu L, 320 mu L, 360 mu L and 400 mu L of halogen-carban secondary standard stock solution with the concentration of 50ng/mL into different 10mL volumetric flasks, and carrying out constant volume by using 80% vol methanol water solution to obtain halogen-carban series standard working solution which is ready for use. The concentration of halocarban in the prepared series of standard working solutions is 0.01, 0.02, 0.05, 0.60, 1.20, 1.40, 1.60, 1.80 and 2.00ng/mL respectively.
2.2 sample pretreatment
Filtering the water sample to be detected with 0.45 μm microporous membrane, extracting 100mL of filtrate from each sample in 250mL separating funnel with chromatographically pure dichloromethane (200mL) as extraction liquid for 4 times (50 mL each time, 200mL for 4 times), and combining the organic phases. And (3) concentrating the combined organic phase to be nearly dry by using a rotary evaporator, then diluting the mixed organic phase to 1mL by using methanol, transferring the mixed organic phase to a liquid chromatography sample bottle, and detecting by using ultra-high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS/MS).
2.3 blank experiment
Replacing the water sample to be detected with primary water (see GB/T6682-.
2.4 apparatus conditions
2.4.1 conditions of liquid chromatography
And (3) chromatographic column: ACQUITY UPLC HST 3 column (2.1 mm. times.100 mm,1.8 μm, Waters, USA); sample introduction amount: 5 mu L of the solution; flow rate: 0.3 mL/min; column temperature: 30 ℃; mobile phase a is 0.1% vol formic acid aqueous solution, mobile phase B is methanol; gradient: 0-1.0 min, wherein the proportion of the mobile phase B is 85-90% vol; 1.0-2.0 min, wherein the proportion of the mobile phase B is 90-100% vol; 2.0-3.0 min, and the proportion of the mobile phase B is 100-85% vol (the specific gradient elution condition is shown in Table 1).
TABLE 1 gradient elution procedure
2.4.2 Mass Spectrometry conditions
An ion source: electrospray ionization source (ESI); the scanning mode is as follows: anion scanning (ESI)-) (ii) a Capillary voltage: 3 kV; extraction taper hole voltage: 5V, and (5); RF radio frequency mass spectrum voltage: 0.5V; ion source temperature: 120 ℃; removing the solvent gas: nitrogen with the purity not less than 99.99%; desolventizing gas temperature: 500 ℃; desolventizing agent gas flow: 600L/hr; collision gas: argon gas; collision chamber pressure: 3.80e- 3mbar; photomultiplier tube voltage: 650V; the detection mode comprises the following steps: multiple Reaction Monitoring (MRM); residence monitoring time of ion pair: 50 ms;
in the Multiple Reaction Monitoring (MRM), since there is no mass spectrometry method reported for halocarbn at present, mass spectrometry conditions thereof need to be intensively and thoroughly optimized. Considering the reactivity of two C-N bonds on the urea group in halocarban molecule, halocarban reacts with Ar in a mass spectrometer collision cell2Ion-molecule collision reactionThen, the two C — N bonds are easily broken, and in different fragments containing a benzene ring, a lone pair of electrons on the N atom connected to the benzene ring easily forms a conjugated structure with the benzene ring, and it is presumed that the different ion fragments formed are easily negatively charged. From this, the negative ion mode (ESI) was calculated-) Relative accurate mass of parent ion and daughter ion which can appear in the next time, thereby predicting negative ion scanning mode (ESI)-) The lower halocarban should present m/z 347/194 and m/z 347/126 ion pairs. The results show that, in negative ion scan mode (ESI)-) A parent ion Scan (MS Scan) was performed on halocarbn, and indeed an m/z 346.75 ion peak (fig. 2) appeared; successively in negative ion mode (ESI)-) Subsequently, a daughter ion Scan (Dauhter Scan) was performed, and two daughter ion peaks of m/z 193.94 and m/z 126.03 did appear, and the ion peaks were stable (see FIG. 3). Positive ion mode (ESI)+) Scanning, no expected ion pairs were present, and the other fragment ions present were unstable. Therefore, mass spectrometry of halocarban can be performed in electrospray negative ion mode (ESI)-) Multiple Reaction Monitoring (MRM) was performed.
After optimization, the retention time and the multi-reaction monitoring (MRM) key parameter results of the halocarbn ultra-performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method are detailed in Table 2.
UPLC-ESI-MS/MS retention time and Multiple Reaction Monitoring (MRM) parameters of Table 2 Halocarban
Note: are quantitative ions.
FIGS. 2 to 4 are UPLC-ESI-MS/MS total ion flow chromatogram (TIC), quantitative ion chromatogram (MRM) and qualitative ion chromatogram (MRM) of halocasan, respectively; FIG. 5 is a UPLC-ESI-MS/MS quantitative ion chromatogram (MRM) of the detection limit of halocarban (0.01 ng/mL).
2.5 Standard working Curve drawing, detection Limit and quantification Limit
Performing ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS) on the conditions of the optimized liquid chromatography method and mass spectrometry method to the conditions of the ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry (UPLC-ESI-MS/MS) 2.1.3Analyzing and measuring standard working solution of halocarbn series with concentration of 0.01, 0.02, 0.05, 0.60, 1.20, 1.40, 1.60, 1.80 and 2.00ng/mL respectively to obtain peak area of halocarbn, performing linear regression with concentration of halocarbn standard working solution as abscissa and corresponding peak area as ordinate to draw standard working curve, and square R of correlation coefficient2≥0.99。
Taking the halocarbn concentration corresponding to the signal-to-noise ratio of 3 (S/N-3) as the detection Limit (LOD) of the method; the concentration of halocarbn corresponding to a signal-to-noise ratio of 10 (S/N-10) was taken as the limit of quantitation (LOQ) of the method. Regression equation, linear range, square of correlation coefficient (R) for halocasan2) The detection limits and the quantification limits are shown in table 3.
The result shows that the halocarban has good linear relation (R) in the range of 0.02-2.00 ng/mL20.9956), limit of detection (LOD) was 0.01ng/mL, and limit of quantitation (LOQ) was 0.02 ng/mL.
Adding a mixed standard working solution with medium concentration after each sample injection for 20 times, and if the relative deviation of the measured value and the original value exceeds 10%, then making a standard working curve again.
TABLE 3 regression equation, Linear Range, Square of correlation coefficient (R) for Halocarban2) Limit of detection (LOD) and limit of quantification (LOQ)
2.6 measurement of Halocarban content in the sample
And (3) sequentially carrying out sample injection analysis on the 2.2 concentrated constant volume sample and the 2.3 blank sample, quantifying by adopting an external standard method, and calculating the content of the component to be measured in the sample according to a working curve. Each concentrated volumetric sample (2.2 as described) was run in duplicate and a set of blanks were run for each batch according to the procedure described in 2.3.
And calculating the content of the halocarban in the sample according to the peak area of the halocarban quantitative ion in the sample. Under the same experimental conditions, the deviation of the relative retention time of the halocarban in the sample and the corresponding retention time of the halocarban in the standard working solution is within +/-2.5 percent; comparing the relative abundance of the halocarb characteristic ions in the sample spectrogram with the relative abundance of the halocarb corresponding characteristic ions in the standard working solution with the adjacent concentration, wherein the relative abundance is allowed to deviate +/-20% when the relative abundance is more than 50%, is allowed to deviate +/-25% when the relative abundance is between 20% and 50%, is allowed to deviate +/-30% when the relative abundance is between 10% and 20%, and is allowed to deviate +/-50% when the relative abundance is less than 10%.
And if the concentration of the halocarbn in the sample solution to be detected exceeds the maximum concentration of the halocarbn in the standard working solution, adjusting the dilution factor of the solution to be detected by using methanol and then detecting.
2.7 calculation of Halocarban content in environmental Water sample
The content X of halocarban in the environmental water sample is calculated according to the formula (1):
in the formula (I), the compound is shown in the specification,
x represents the content of halocarban in the environmental water sample, and the unit is mu g/kg;
c, obtaining the concentration of halocarbn in the concentrated constant volume sample from the standard working curve, wherein the unit is ng/mL;
C0-the concentration of halocarbn in the concentrated constant volume blank obtained from the standard working curve, in ng/mL;
v, concentrating the extract to a constant volume, and taking 1 in milliliter (mL);
m is the mass of the environmental water sample, and the unit is g; because the density of water is 1g/mL, the volume (mL) value of the environmental water sample can be directly substituted;
integral factor, this example takes 1.
The arithmetic mean of the two replicates was used as the final assay to the nearest 0.01. mu.g/kg.
The relative mean deviation of the two parallel measurements should be less than 10%.
Example 2 Bidding recovery experiment-method accuracy and precision verification
10mL of standard working solutions of halocarbn were prepared at concentrations of 0.05ng/mL (low concentration), 1.20ng/mL (medium concentration), and 2.00ng/mL (high concentration). Transferring 6 parts of each concentration solution according to the amount of 1mL of each part, respectively, placing the solutions in a triangular flask with a plug containing 100mL of ultrapure water, and pretreating according to a 2.2 method (namely, the standard adding recovery test is divided into three groups of low-concentration, medium-concentration and high-concentration according to the concentration of the standard working solution, each group is provided with 6 parallel tests, and the scheme is shown in Table 3).
After each concentrate was processed, sample measurement and result calculation were performed according to the methods 2.6 and 2.7 of example 1. Calculating the low, medium and high concentration standard recovery rates and relative standard deviations (RSD, percent) according to the detection results, wherein the calculation results are shown in table 3, the standard recovery rates of the three concentrations are between 90.39 and 95.87 percent, the RSD of the standard recovery data of the three concentrations is between 3.05 and 3.93 percent, and the RSD is less than 5 percent, which indicates that the method has good repeatability.
TABLE 3 Halecarban recovery on scale, relative standard deviation (n ═ 6)
EXAMPLE 3 determination of actual samples
In this example, 3 environmental water samples were collected from the kongjiang (midstream), the yunnan pond (sea bank park) and the grand river (downstream) in Kunming, and the ultra-trace halocasan in the environmental water samples was determined by the method for determining the ultra-trace halocasan in the environmental water samples described in example 1, and the content of halocasan in the collected 3 environmental water samples was determined.
TABLE 4 determination results of halocarban in real environmental water samples
The results show that no halocarban was detected in any of the 3 environmental water samples. Therefore, water bodies of the Kunming city Panlongjiang (midstream), Dian chi (sea ridge park) and grand river (downstream) are not polluted by halocarbon.
Claims (1)
1. A method for determining ultra-trace halocarban in an environmental water sample is characterized by comprising the following steps:
step (1), preparing a standard working solution of halocarban series: preparing standard working solutions of halocarbn series with the concentrations of 0.01, 0.02, 0.05, 0.60, 1.20, 1.40, 1.60, 1.80 and 2.00ng/mL by using 80% vol methanol aqueous solution;
step (2), sample pretreatment: filtering m g of environmental water sample to be detected with a 0.45 μm microporous membrane, extracting the filtrate in a separating funnel for 4 times with chromatographically pure dichloromethane as an extraction liquid, and combining organic phases; concentrating the combined organic phases by using a rotary evaporator until the combined organic phases are nearly dried to obtain an extraction concentrated solution, performing constant volume on the extraction concentrated solution to obtain a concentrated constant volume sample to be detected by using methanol, transferring the concentrated constant volume sample to a liquid chromatography sample bottle, and performing ultrahigh performance liquid chromatography-electrospray ionization source quadrupole rod mass spectrometry;
step (3), blank experiment: m g of primary water is used as a blank sample to replace an environmental water sample to be detected, the step (2) is carried out to obtain a concentrated constant volume blank sample to be detected, the blank sample is transferred to a liquid chromatography sample bottle, and ultra performance liquid chromatography-electrospray ionization source quadrupole rod mass spectrometry detection is carried out;
and (4) drawing a standard working curve: measuring the peak area of halocarbn in the series of standard working solutions in the step (1) by adopting ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry, and performing linear regression by taking the concentration of halocarbn as a horizontal coordinate and the corresponding peak area as a vertical coordinate to draw a standard working curve;
step (5), determining the content of halocarban in the sample: measuring the peak area of halocarban in the to-be-measured concentrated constant volume sample in the step (2) by adopting ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry, and obtaining the concentration C of halocarban in the concentrated constant volume sample according to the standard working curve drawn in the step (4);
step (6), emptyDetermining the content of halocarban in the white sample: measuring the peak area of halocarbn in the concentrated constant volume blank sample to be measured in the step (3) by adopting ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry, and obtaining the concentration C of halocarbn in the concentrated constant volume blank sample to be measured according to the standard working curve drawn in the step (4)0；
Step (7), calculating the content of halocarban in the environmental water sample:
calculating the content X of halocarban in the environmental water sample to be detected according to the formula (1),
in the formula (I), the compound is shown in the specification,
x represents the content of halocarban in the water sample of the environment to be detected, and the unit is mu g/kg;
c, obtaining the concentration of halocarbn in the concentrated constant volume sample from the standard working curve, wherein the unit is ng/mL;
C0-the concentration of halocarbn in the concentrated constant volume blank obtained from the standard working curve, in ng/mL;
v, concentrating the extract to a constant volume, wherein the unit is mL;
m is the mass of the environmental water sample, and the unit is g; because the density of water is 1g/mL, the mL volume value of the environmental water sample can be directly substituted;
integral multiple-dilution factor; if the concentration of halocarban in the sample solution to be detected does not exceed the maximum concentration of the standard working solution, taking 1 as the dilution factor; if the concentration of halocarbn in the sample solution to be tested exceeds the maximum concentration of the standard working solution, adjusting and diluting the solution to be tested by using methanol, and then measuring, if the solution is diluted to 2 times, taking a dilution factor of 2, and so on;
taking the arithmetic mean value of the multiple parallel measurement results as a final measurement result, and accurately measuring the result to 0.01 mu g/kg;
the relative average deviation of the results of multiple parallel measurements should be less than 10%;
in the step (4), the step (5) and the step (6), the liquid chromatography conditions of the ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method are as follows: the chromatographic column is ACQUITYUPLC HSS T3 chromatographic column of Waters corporation, 2.1mm × 100mm,1.8 μm; the sample injection amount is 5 mu L; the flow rate is 0.3 mL/min; the column temperature is 30 ℃; mobile phase a is 0.1% vol formic acid aqueous solution, mobile phase B is methanol; gradient: 0-1.0 min, wherein the proportion of the mobile phase B is 85-90% vol; 1.0-2.0 min, wherein the proportion of the mobile phase B is 90-100% vol; 2.0-3.0 min, wherein the mobile phase B accounts for 100-85% vol;
mass spectrum conditions of the ultra performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method in the step (4), the step (5) and the step (6): the ion source is an electrospray ionization source; the scanning mode is negative ion scanning; the capillary voltage is 3 kV; the extraction taper hole voltage is 5V; the RF mass spectrum voltage is 0.5V; the ion source temperature is 120 ℃; the desolventizing gas is nitrogen, and the purity is not less than 99.99 percent; the temperature of the desolventizing gas is 500 ℃; the flow rate of the desolventizing agent is 600L/hr; the collision gas is argon; the pressure in the collision chamber is 3.80e-3mbar; the voltage of the photomultiplier is 650V; the detection mode is multi-reaction monitoring; the residence monitoring time of the ion pair is 50 ms;
in the step (4), the step (5) and the step (6), the retention time and the multiple reaction monitoring parameters of the halocarbn ultra-high performance liquid chromatography-electrospray ionization source quadrupole mass spectrometry method are shown in the following table:
note: are quantitative ions.
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