CN116087374B - Detection method for trace bisphenol compounds in agricultural products - Google Patents
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Abstract
The invention relates to the field of analytical chemistry, in particular to a detection method for trace bisphenol compounds in agricultural products, which comprises the steps of adding BPA isotopes into a ground and sieved sample, uniformly mixing by vortex, standing, adding a chromatographic pure methanol extraction solvent, performing microwave and vibration extraction, performing centrifugal treatment, extracting supernatant, mixing supernatant obtained by the centrifugal treatment twice to obtain mixed supernatant, diluting the mixed supernatant with pure water, extracting and eluting by a solid-phase extraction column to obtain eluent, drying the eluent by a nitrogen blowing instrument, re-dissolving the eluent by using a mixed solution of methanol and water to obtain a complex solution, passing the complex solution through a microporous filter membrane to obtain filtrate, performing liquid chromatography measurement on the filtrate, and adjusting parameters according to preset conditions to prepare the sample again or determine the content of novel bisphenol compounds in the sample, thereby improving the detection limit and quantitative limit of the trace bisphenol compound detection method in the agricultural products and increasing the detection precision and accuracy.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a detection method for trace bisphenol compounds in agricultural products.
Background
The novel bisphenol compound (BisPhenolcomPounds, BPs) is a chemical substance similar to bisphenol a (bisphenol-based propane, bisPhenolA, BPA) in structure, comprising two phenol groups, bridged together by carbon or different chemical structures in the middle. The novel BPs mainly comprises: bisphenol a, bisphenol C, bisphenol F, bisphenol AF bisphenol Z, bisphenol AP, and the like. BPs are widely applied to industrial production as modifiers, stabilizers and the like of high polymer materials such as epoxy resin, polycarbonate, polyurethane and the like, and are commonly detected in various environmental media such as soil, water, sediment and the like at present.
At present, the detection and analysis of bisphenol compounds are focused on environmental media such as water, soil and the like, but the pretreatment and detection methods of plant samples, especially edible agricultural products, are not perfect. Meanwhile, for detecting trace and ultra-trace bisphenol compounds, the detection limit and the quantitative limit of the existing detection method cannot be fully applied, and further improvement of the detection precision and accuracy of the detection method is needed.
Disclosure of Invention
Therefore, the invention provides a detection method for trace bisphenol compounds in agricultural products, which is used for overcoming the problems that the detection limit and the quantitative limit of the detection method in the prior art cannot be fully applied, and the detection precision and the accuracy of the detection method are required to be further improved.
In order to achieve the above object, the present invention provides a method for detecting trace bisphenol compounds in agricultural products, comprising the steps of:
step S1, freeze-drying a sample to obtain a sample weight R1, and determining a weighing interval duration according to the sample weight R1 and a freeze-drying temperature C1 of a freeze-drying device so as to determine whether the sample is freeze-dried according to the result of each weighing of the sample;
step S2, grinding the freeze-dried sample to obtain the surface area of the freeze-dried sample, determining grinding precision based on the surface area of the freeze-dried sample, obtaining a ground sample after finishing grinding the sample, and sieving the ground sample to obtain a sieved sample;
s3, placing the sieved sample into a centrifuge tube, adding an initial adding amount of BPA isotope into the centrifuge tube to obtain a quality control sample, and carrying out vortex mixing and standing on the sample added with the BPA isotope to obtain a standing sample;
S4, adding an initial addition amount of chromatographic pure methanol extraction solvent into the sample after standing, carrying out vortex mixing, then carrying out microwave extraction to obtain an extracted solution, carrying out vibration and centrifugal treatment on the extracted solution, and extracting supernatant;
step S5, repeating the step S4, and mixing the supernatant extracted by the centrifugal treatment twice to obtain a mixed supernatant;
s6, diluting the mixed clear liquid with pure water to obtain diluted mixed clear liquid, and extracting and eluting the diluted mixed clear liquid through a solid phase extraction column to obtain eluent;
s7, drying the eluent by a nitrogen blower, re-dissolving the eluent by using a mixed solution of methanol and water to obtain a re-solution, and filtering the re-solution by using a 0.22 mu m microporous filter membrane to obtain a filtrate;
step S8, carrying out liquid chromatography measurement on the filtrate by adopting a liquid chromatography measurement method, and judging whether the adding amount of the BPA isotope is required to be optimized, whether the adding amount of the chromatographic pure methanol extraction solvent is required to be optimized and whether the extraction duration of the microwave extraction is required to be optimized under a first preset condition;
and determining the content of the novel bisphenol compound in the sample under a second preset condition;
The sample is maize or wheat in a mature period, the first preset condition is that the recovery rate of the BPA isotope belongs to a first recovery rate interval, the second preset condition is that the recovery rate of the BPA isotope is in a second recovery rate interval, the upper limit of the interval of the first recovery rate interval is smaller than the lower limit of the interval of the second recovery rate interval, and the second recovery rate interval belongs to a standard recovery rate range.
Further, in the step S1, the weighing interval parameter M is calculated according to the formula (1),
in the formula (1), R10 represents the weight of a preset standard sample, and C10 represents the preset standard freeze-drying temperature;
and comparing the weighing interval parameter M with a preset first weighing interval parameter standard M1 and a second weighing interval parameter standard M2, and determining the weighing interval duration according to the comparison result, wherein M1 is smaller than M2,
if M is less than M1, setting the weighing interval duration to be T1;
if M1 is less than or equal to M2, setting the weighing interval duration to be T2;
if M2 is less than or equal to M, setting the weighing interval duration to be T3;
wherein T1 is less than T2 and less than T3.
Further, in the step S1, the weights of two adjacent times are determined to calculate a weight difference DeltaW, the weight difference DeltaW is compared with a preset first weight difference standard parameter DeltaW 1 and a second weight difference standard parameter DeltaW 2, whether the sample is freeze-dried or not is determined according to the comparison result,
If DeltaW < DeltaW1, determining that freeze drying of the sample is complete;
if DeltaW 1 is less than or equal to DeltaW < DeltaW2, determining to adjust the weighing interval time by adopting a first weighing interval adjustment mode;
if delta W2 is less than or equal to delta W1, determining to adjust the weighing interval time length by adopting a second weighing interval adjustment mode;
the first weighing interval adjustment mode is to increase the weighing interval time by adopting a first interval time adjustment coefficient, the second weighing interval adjustment mode is to increase the weighing interval time by adopting a second interval time adjustment coefficient, and the first interval time adjustment coefficient is set to be smaller than the second interval time adjustment coefficient.
Further, in the step S2, the surface area of the freeze-dried sample is compared with a preset standard parameter Δva1 of the difference of the surface area of the first freeze-dried sample and a preset standard parameter Δva2 of the difference of the surface area of the second freeze-dried sample, and grinding precision is determined according to the comparison result,
setting the polishing accuracy to J1 if Δva < Δva1;
setting the grinding precision to J2 if DeltaVa1 is less than or equal to DeltaVa < DeltaVa2;
setting the grinding precision to J3 if DeltaVa2 is less than or equal to DeltaVa;
Wherein J1 is less than J2 and less than J3.
Further, in the step S3, the BPA isotope is 13 C 12 Isotopes of BPA.
Further, in the step S8, the liquid chromatography determination method is ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for detecting the concentration of each novel bisphenol compound in the agricultural product sample, and controlling the working parameters of the ultra-high performance liquid chromatograph includes:
liquid chromatography parameters, adopting an ACQUITYUPLCBEHShieldRP18 chromatographic column with a length of 150mm, an inner diameter of 2.1mm, a particle diameter of 1.7 μm, a sample injection amount of 5 μl, and a chromatographic column temperature of 55deg.C;
the mobile phase parameters, the inorganic phase A of the mobile phase is an aqueous solution containing 0.1% ammonia water, the organic phase B is chromatographic grade pure methanol, and the ultrasonic treatment is carried out for 20 minutes before the mobile phase is put on the machine, so that the gas interference in the solution is removed, the influence on the detection of an instrument is reduced or avoided, and the flow rate of the mobile phase is set to be 0.3mL/min;
the gradient of the mobile phase was such that the initial phase was 70% a and 30% b, the organic phase was raised to 80% b for 1.5min, held for 1.5min, then raised to 950% b, held for 0.5min, lowered to 30% b at 3.5min, and returned to the initial mobile phase state;
mass spectrum parameters, adopting an ESI source negative ion mode, wherein the gas curtain gas is 30.0Psi, the ion source temperature is 500 ℃, the spray gas is 50Psi, the auxiliary heating gas is 50Psi, the ionization voltage is-4500 v, and the collision gas Medium is sprayed.
Further, in the step S8, the method comprises the steps of 13 C 12 -BPA isotope recovery, calculated as 13 C 12 -BPA isotope recovery and presetting 13 C 12 A recovery difference DeltaP of standard recovery of BPA isotopes, and comparing the recovery difference DeltaP with a first BPA isotope recovery difference standard parameter DeltaP 1 and a second BPA isotope recovery difference standard parameter DeltaP 2, and judging whether the adding amount of the BPA isotopes needs to be optimized, whether the adding amount of the chromatographic pure methanol extraction solvent needs to be optimized and whether the extraction duration of the microwave extraction needs to be optimized according to comparison results, wherein,
if the delta P is less than the delta P1, judging that the extraction duration of the microwave extraction needs to be optimized;
if delta P1 is less than or equal to delta P < deltaP 2, judging that the adding amount of the chromatographic pure methanol extraction solvent needs to be optimized;
if delta P2 is less than or equal to delta P, judging that the adding amount of the BPA isotope needs to be optimized.
Further, in the step S8, if it is determined that the extraction duration of the microwave extraction needs to be optimized, according to the following steps 13 C 12 Recovery of BPA isotope 13 C 12 Determining a mode of optimizing the extraction duration of the microwave extraction by comparing the percentage ΔPa of the standard recovery rate of the BPA isotope with a first extraction duration adjustment percentage standard parameter ΔPa1 and a second extraction duration adjustment percentage standard parameter ΔPa2, wherein ΔPa2 > - ΔPa1,
If delta Pa < [ delta ] Pa1, determining to adjust the extraction time length by adopting a first extraction time length adjustment mode;
if delta Pa1 is less than or equal to delta Pa2 and less than or equal to delta Pa2, determining to adjust the extraction time by adopting a second extraction time adjustment mode;
if delta Pa2 is less than or equal to delta Pa, determining to adjust the extraction time by adopting a third extraction time adjustment mode;
the first extraction time length adjusting mode is to increase the extraction time length by adopting a first extraction time length adjusting coefficient, the second extraction time length adjusting mode is to increase the extraction time length by adopting a second extraction time length adjusting coefficient, the third extraction time length adjusting mode is to increase the extraction time length by adopting a third extraction time length adjusting coefficient, and the first extraction time length adjusting coefficient is smaller than the second extraction time length adjusting coefficient and is smaller than the third extraction time length adjusting coefficient, and the first extraction time length adjusting coefficient and the second extraction time length adjusting coefficient are all in a range of [5%,15% ].
Further, in the step S8, if it is determined that the addition amount of the chromatographic pure methanol extraction solvent needs to be optimized, the method is performed according to the following steps 13 C 12 Determining a mode when optimizing the addition of the chromatographic pure methanol extraction solvent by comparing the percentage DeltaPb of the BPA isotope recovery accounting for the standard parameter DeltaP 1 of the difference value of the first BPA isotope recovery with the standard percentage DeltaPb 1 of the adjustment of the addition of the first chromatographic pure methanol extraction solvent and the standard percentage DeltaPb 2 of the addition of the second chromatographic pure methanol extraction solvent, wherein DeltaPb 2 > DeltaPb1,
If DeltaPb < DeltaPb1, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a first chromatographic pure methanol extraction solvent adding amount adjusting mode;
if delta Pb1 is less than or equal to delta Pb2, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a second chromatographic pure methanol extraction solvent adding amount adjusting mode;
if delta Pb2 is less than or equal to delta Pb, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a third chromatographic pure methanol extraction solvent adding amount adjusting mode;
the first chromatographic pure methanol extraction solvent addition amount adjustment mode is to increase the chromatographic pure methanol extraction solvent addition amount by adopting a first chromatographic pure methanol extraction solvent addition amount adjustment coefficient, the second chromatographic pure methanol extraction solvent addition amount adjustment mode is to increase the chromatographic pure methanol extraction solvent addition amount by adopting a second chromatographic pure methanol extraction solvent addition amount adjustment coefficient, the third chromatographic pure methanol extraction solvent addition amount adjustment mode is to increase the chromatographic pure methanol extraction solvent addition amount by adopting a third chromatographic pure methanol extraction solvent addition amount adjustment coefficient, and the first chromatographic pure methanol extraction solvent addition amount adjustment coefficient is smaller than the second chromatographic pure methanol extraction solvent addition amount adjustment coefficient and is smaller than the third chromatographic pure methanol extraction solvent addition amount adjustment coefficient, and all belong to the interval [5%,15% ].
Further, in the step S8, if it is determined that the amount of the BPA isotope to be added needs to be optimized, the method is performed according to the following steps 13 C 12 -comparing the percentage ΔPc of the recovery of the BPA isotope to the standard parameter ΔP2 of the difference in recovery of the second BPA isotope with the standard parameter ΔP1 of the adjustment of the initial addition amount of the first BPA isotope and the standard parameter ΔPc2 of the adjustment of the initial addition amount of the second BPA isotope to determine the manner in which the addition amount of the BPA isotope is optimized, wherein ΔPc1 < ΔPc2 < ΔPc1 < ΔPc2)
If ΔPc < ΔP1, then the first is determined to be employed 13 C 12 -means for adjusting the amount of added BPA isotope;
if ΔPc1 is less than or equal to ΔPc2, then determining to use a second 13 C 12 -means for adjusting the amount of added BPA isotope;
if ΔPc2 is less than or equal to ΔPc, then determining to use a third 13 C 12 -means for adjusting the amount of added BPA isotope;
the first mentioned 13 C 12 The mode of adding the BPA isotope is that a first mode is adopted 3 C 12 -increasing the BPA isotope addition quantity adjustment coefficient 3 C 12 -an added amount of BPA isotope, said second 13 C 12 The mode of adding the BPA isotope is to adopt a second mode 3 C 12 -increasing the BPA isotope addition quantity adjustment coefficient 3 C 12 -the amount of added BPA isotope, said third 13 C 12 The mode of adjusting the adding amount of the BPA isotope adopts a third mode 3 C 12 -increasing the BPA isotope addition quantity adjustment coefficient 3 C 12 -the amount of added BPA isotope, said first 3 C 12 -BPA isotope addition level adjustment coefficient is less than said second 3 C 12 -BPA parityThe element addition amount adjustment coefficient is smaller than the third 3 C 12 BPA isotope addition amount adjustment coefficient, and all belong to the interval [5%,15%]。
Compared with the prior art, the method has the beneficial effects that BPA isotopes are added into a ground and sieved sample, then vortex mixing is carried out, standing is carried out, then a chromatographic pure methanol extraction solvent is added for carrying out microwave and vibration extraction, centrifugal treatment is carried out, supernatant is extracted, supernatant obtained by centrifugal treatment is mixed to obtain mixed supernatant, the mixed supernatant is diluted by pure water and then passes through a solid phase extraction column for extraction and elution to obtain eluent, the eluent is dried by a nitrogen blowing instrument and then is redissolved by a mixed solution of methanol and water to obtain a complex solution, the complex solution is filtered by a microporous filter membrane to obtain filtrate, the filtrate is subjected to liquid chromatography measurement by a liquid chromatography measurement method, and the content of novel bisphenol compounds in the sample is prepared again or is determined according to a preset condition, so that the detection limit and the quantitative limit of a trace bisphenol compound detection method in agricultural products are improved, and the detection precision and the accuracy of the detection method are improved.
Further, in step S1, a weighing interval parameter is determined according to the sample weight and the freeze-drying temperature, and the standard sample weight and the standard freeze-drying temperature, and a weighing interval duration is determined according to the weighing interval parameter and the weighing interval parameter standard, so that the accuracy of the whole drying treatment of the sample in the sample pretreatment is improved.
Further, in step S2, the sample is weighed at intervals, and the adjustment mode of the weighing interval length and whether the freeze drying of the sample is completed are determined according to the comparison result of the freeze drying weight difference value between the freeze drying weight of the current sample and the freeze drying weight of the previous interval weighing and the standard parameter of the freeze drying weight difference value, so that the accuracy of the whole drying treatment of the sample in the sample pretreatment is further improved.
Further, in step S2, the grinding precision is determined according to the comparison result of the standard surface area difference value of the freeze-dried sample and the standard surface area of the freeze-dried sample and the standard parameter of the standard surface area difference value of the freeze-dried sample, so that the precision of the grinding treatment in the sample pretreatment process is improved.
Further, working parameters of the ultra-high performance liquid chromatograph are set, and analysis accuracy of the ultra-high performance liquid chromatograph tandem mass spectrometry is improved, so that process parameters of sample pretreatment can be conveniently adjusted according to analysis results, and accuracy of chromatographic analysis is further guaranteed.
Further, in step S8, the following is obtained 13 C 12 Recovery of BPA isotope according to 13 C 12 Standard recovery of BPA isotopes and the process 13 C 12 -comparing the BPA isotope recovery difference Δp of BPA isotope recovery with a BPA isotope recovery difference standard parameter to determine whether to optimize the amount of added BPA isotope, whether to optimize the amount of added chromatographically pure methanol extraction solvent and whether to optimize the extraction duration of the microwave extraction, thereby ensuring the accuracy of sample pretreatment process parameter setting.
Further, if it is determined that the extraction duration of the microwave extraction needs to be optimized, according to the following steps 13 C 12 Recovery of BPA isotope 13 C 12 The comparison result of the percentage of the standard recovery rate of the BPA isotope and the standard parameter of the extraction time length adjustment percentage determines the mode when optimizing the extraction time length of the microwave extraction, thereby ensuring the accuracy of the parameter determination of the extraction time length in the pretreatment process parameters and further improving the accuracy of the parameter setting of the sample pretreatment process.
Further, according to the following 13 C 12 And determining an optimization mode when optimizing the adding amount of the chromatographic pure methanol extraction solvent according to the comparison result of the percentage of the BPA isotope recovery ratio to the first BPA isotope recovery ratio difference standard and the chromatographic pure methanol extraction solvent adding amount adjustment percentage standard parameter, thereby ensuring the accuracy of the adding amount of the methanol extraction solvent in the pretreatment process parameter and further improving the accuracy of the sample pretreatment process parameter setting.
Further, if it is determined that the BPA isotope is to be targetedIs optimized according to the addition amount of 13 C 12 -percentage ΔPc and BPA isotope recovery from second BPA isotope recovery difference criterion 13 C 12 -comparing the initial addition amount adjustment percentage standard parameters of the BPA isotope to determine the manner in which the addition amount of the BPA isotope is optimized, thereby ensuring that during the pretreatment process 13 C 12 The accuracy of the amount of added BPA isotope further improves the accuracy of the parameter settings of the sample pretreatment process.
Drawings
FIG. 1 is a flow chart of steps of the method for detecting trace bisphenol compounds in agricultural products according to the present invention.
Detailed Description
In order that the objects and advantages of the invention will become more apparent, the invention will be further described with reference to the following examples; it should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are merely for explaining the technical principles of the present invention, and are not intended to limit the scope of the present invention.
It should be noted that, in the description of the present invention, terms such as "upper," "lower," "left," "right," "inner," "outer," and the like indicate directions or positional relationships based on the directions or positional relationships shown in the drawings, which are merely for convenience of description, but do not indicate or imply that the apparatus or element must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Referring to fig. 1, fig. 1 is a flowchart illustrating steps of a method for detecting trace bisphenol compounds in agricultural products according to an embodiment of the present invention. The detection method for trace bisphenol compounds in agricultural products comprises the following steps:
step S1, freeze-drying a sample to obtain a sample weight R1, and determining a weighing interval duration according to the sample weight R1 and a freeze-drying temperature C1 of a freeze-drying device so as to determine whether the sample is freeze-dried according to the result of each weighing of the sample;
step S2, grinding the freeze-dried sample to obtain the surface area of the freeze-dried sample, determining grinding precision based on the surface area of the freeze-dried sample, obtaining a ground sample after finishing grinding the sample, and sieving the ground sample to obtain a sieved sample;
s3, placing the sieved sample into a centrifuge tube, adding an initial adding amount of BPA isotope into the centrifuge tube to obtain a quality control sample, and carrying out vortex mixing and standing on the sample added with the BPA isotope to obtain a standing sample;
s4, adding an initial addition amount of chromatographic pure methanol extraction solvent into the sample after standing, carrying out vortex mixing, then carrying out microwave extraction to obtain an extracted solution, carrying out vibration and centrifugal treatment on the extracted solution, and extracting supernatant;
Step S5, repeating the step S4, and mixing the supernatant extracted by the centrifugal treatment twice to obtain a mixed supernatant;
s6, diluting the mixed clear liquid with pure water to obtain diluted mixed clear liquid, and extracting and eluting the diluted mixed clear liquid through a solid phase extraction column to obtain eluent;
s7, drying the eluent by a nitrogen blower, re-dissolving the eluent by using a mixed solution of methanol and water to obtain a re-solution, and filtering the re-solution by using a 0.22 mu m microporous filter membrane to obtain a filtrate;
step S8, carrying out liquid chromatography measurement on the filtrate by adopting a liquid chromatography measurement method, and judging whether the adding amount of the BPA isotope is required to be optimized, whether the adding amount of the chromatographic pure methanol extraction solvent is required to be optimized and whether the extraction duration of the microwave extraction is required to be optimized under a first preset condition;
and determining the content of the novel bisphenol compound in the sample under a second preset condition;
the sample is maize or wheat in a mature period, the first preset condition is that the recovery rate of the BPA isotope belongs to a first recovery rate interval, the second preset condition is that the recovery rate of the BPA isotope is in a second recovery rate interval, the upper limit of the interval of the first recovery rate interval is smaller than the lower limit of the interval of the second recovery rate interval, and the second recovery rate interval belongs to a standard recovery rate range.
Specifically, in the embodiment of the present invention, in performing the operation of step S1, the drying and freezing device is selected as a vacuum freeze dryer, the weight of the sample for each freeze drying is 500Kg, the selected freeze drying temperature is-80 ℃, and the freeze drying temperature is determined by the weight of the sample to be common knowledge of a person skilled in the art, so details of the method for determining the freeze drying temperature of the freeze drying device according to the weight of the sample are not described in detail herein.
Specifically, in step S1, the freeze-dried sample mass analysis strategy includes determining a weighing interval parameter M based on a comparison of the sample weight R1 and the standard sample weight R10 and a comparison of the freeze-drying temperature C1 and the standard sample weight R10, determining a weighing interval duration based on the weighing interval parameter M and a weighing interval parameter standard including a first weighing interval parameter standard M1 and a second weighing interval parameter standard M2, and setting
，M1＜M2，
If M is less than M1, setting the weighing interval duration to be T1;
if M1 is less than or equal to M2, setting the weighing interval duration to be T2;
if M2 is less than or equal to M, setting the weighing interval duration to be T3;
wherein T1 is less than T2 and less than T3.
Specifically, in the step S1, the weighing interval parameter M is calculated according to the formula (1),
In the formula (1), R10 represents the weight of a preset standard sample, and C10 represents the preset standard freeze-drying temperature;
and comparing the weighing interval parameter M with a preset first weighing interval parameter standard M1 and a second weighing interval parameter standard M2, and determining the weighing interval duration according to the comparison result, wherein M1 is smaller than M2,
if M is less than M1, setting the weighing interval duration to be T1;
if M1 is less than or equal to M2, setting the weighing interval duration to be T2;
if M2 is less than or equal to M, setting the weighing interval duration to be T3;
wherein T1 is less than T2 and less than T3.
Specifically, in the step S1, the weights of two adjacent times are determined to calculate a weight difference DeltaW, the weight difference DeltaW is compared with a preset first weight difference standard parameter DeltaW 1 and a second weight difference standard parameter DeltaW 2, and whether the sample is freeze-dried or not is determined according to the comparison result,
if DeltaW < DeltaW1, determining that freeze drying of the sample is complete;
if DeltaW 1 is less than or equal to DeltaW < DeltaW2, determining to adjust the weighing interval time by adopting a first weighing interval adjustment mode;
if delta W2 is less than or equal to delta W1, determining to adjust the weighing interval time length by adopting a second weighing interval adjustment mode;
In this embodiment, the first weighing interval adjustment manner is to increase the weighing interval duration W0 to the first weighing interval duration W01 by using a first interval duration adjustment coefficient W1, set w01=w0+w1, and the second weighing interval adjustment manner is to increase the weighing interval duration W0 to the second weighing interval duration W02 by using a second interval duration adjustment coefficient W2, set w02=w0+w2, set that the first interval duration adjustment coefficient is smaller than the second interval duration adjustment coefficient, and set that W1 < W2 < 12h.
Specifically, in the step S2, the surface area of the freeze-dried sample is compared with a preset standard parameter Δva1 of the difference of the surface area of the first freeze-dried sample and a preset standard parameter Δva2 of the difference of the surface area of the second freeze-dried sample, and grinding precision is determined according to the comparison result,
setting the polishing accuracy to J1 if Δva < Δva1;
setting the grinding precision to J2 if DeltaVa1 is less than or equal to DeltaVa < DeltaVa2;
setting the grinding precision to J3 if DeltaVa2 is less than or equal to DeltaVa;
wherein J1 is less than J2 and less than J3.
Specifically, in step S3, the BPA isotope is 13 C 12 A BPA isotope;
in step S8, in the step S8, the liquid chromatography measurement method is ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for detecting the concentration of each novel bisphenol compound in the agricultural product sample, and controlling the working parameters of the ultra-high performance liquid chromatography includes:
Liquid chromatography parameters, adopting an ACQUITYUPLCBEHShieldRP18 chromatographic column with a length of 150mm, an inner diameter of 2.1mm, a particle diameter of 1.7 μm, a sample injection amount of 5 μl, and a chromatographic column temperature of 55deg.C;
the mobile phase parameters, the inorganic phase A of the mobile phase is an aqueous solution containing 0.1% ammonia water, the organic phase B is chromatographic grade pure methanol, and the ultrasonic treatment is carried out for 20 minutes before the mobile phase is put on the machine, so that the gas interference in the solution is removed, the influence on the detection of an instrument is reduced or avoided, and the flow rate of the mobile phase is set to be 0.3mL/min;
the gradient of the mobile phase was such that the initial phase was 70% a and 30% b, the organic phase was raised to 80% b for 1.5min, held for 1.5min, then raised to 950% b, held for 0.5min, lowered to 30% b at 3.5min, and returned to the initial mobile phase state;
mass spectrum parameters, adopting an ESI source negative ion mode, wherein the gas curtain gas is 30.0Psi, the ion source temperature is 500 ℃, the spray gas is 50Psi, the auxiliary heating gas is 50Psi, the ionization voltage is-4500 v, and the collision gas Medium is sprayed;
the novel bisphenol compounds comprise BPA, BPC, BPF, BPS, BPAF, BPAP 13 C 12 -BPA。
Specifically, in the embodiment of the invention, the step S3 is executed, the input amount of the sieved sample added into the centrifuge tube is 0.5g, and the sample is added into 13 C 12 The initial addition of BPA isotope was 5ng and the duration of the vortex was 5min.
Specifically, in the embodiment of the invention, step S4 is executed, and the adding amount of the chromatographic pure methanol extraction solvent is 2.5mL, the swirling time is 5min, and the initial time of the microwave extraction is 20min.
Specifically, in the embodiment of the invention, step S4 is executed, if the centrifuge tube of the sample after microwave extraction is placed in a constant temperature oscillating box to oscillate for 30min at the speed of 250r/min, the centrifuge tube is placed in a low temperature high speed centrifuge to centrifuge for 10min at the speed of 8000r/min, and the supernatant is transferred to a 50mL clean pp centrifuge tube.
Specifically, in the embodiment of the present invention, step S6 is performed, and a preferable scheme is to dilute the mixed clear solution with pure water, dilute the mixed clear solution with Milli-Q water to 500mL, and then implement the operation of re-collecting the mixed clear solution.
Specifically, in the embodiment of the invention, when step S6 and step S8 are executed, before solid phase extraction is carried out on the diluted mixed clear liquid, the HC-C18 solid phase extraction column is sequentially activated by 10mL of methanol (chromatographic purity) and 10mL of lmili-Q water, solid phase extraction purification and target enrichment are carried out on the diluted mixed clear liquid at a flow rate of 1-2 drops per second, after the whole mixed clear liquid passes through the column, the solid phase extraction column is leached by 10mL of aqueous solution containing 5% of methanol to remove impurity interference in a sample, then moisture remained in the solid phase extraction column is vacuumized to ensure that no moisture is contained when the organic solvent elutes the sample, the time is 5min, then 10mL of chromatographic grade methanol is used for eluting target compounds on the solid phase extraction column, the eluent is slowly dried by high-purity nitrogen at 40 ℃, finally, the volume of methanol/water (volume ratio is 1:1) is fixed to 500 mu L, and the solid phase extraction column is transferred to a 2mL sample feeding bottle after the solid phase extraction column passes through a 0.22 mu m membrane, so as to obtain filtrate.
Specifically, in the step S8, the following is acquired 13 C 12 -BPA isotope recovery, calculated as 13 C 12 -BPA isotope recovery and presetting 13 C 12 -difference in recovery Δp of standard recovery of BPA isotopes, and comparing said difference in recovery ΔpComparing the obtained product with a first BPA isotope recovery rate difference standard parameter delta P1 and a second BPA isotope recovery rate difference standard parameter delta P2, judging whether the adding amount of the BPA isotope is required to be optimized, whether the adding amount of the chromatographic pure methanol extraction solvent is required to be optimized and whether the extraction duration of the microwave extraction is required to be optimized according to comparison results,
if the delta P is less than the delta P1, judging that the extraction duration of the microwave extraction needs to be optimized;
if delta P1 is less than or equal to delta P < deltaP 2, judging that the adding amount of the chromatographic pure methanol extraction solvent needs to be optimized;
if delta P2 is less than or equal to delta P, judging that the adding amount of the BPA isotope needs to be optimized.
Specifically, in the step S8, if it is determined that the extraction duration of the microwave extraction needs to be optimized, the method is performed according to the following steps 13 C 12 Recovery of BPA isotope 13 C 12 Determining a mode of optimizing the extraction duration of the microwave extraction by comparing the percentage ΔPa of the standard recovery rate of the BPA isotope with a first extraction duration adjustment percentage standard parameter ΔPa1 and a second extraction duration adjustment percentage standard parameter ΔPa2, wherein ΔPa2 > - ΔPa1,
If delta Pa < [ delta ] Pa1, determining to adjust the extraction time length by adopting a first extraction time length adjustment mode;
if delta Pa1 is less than or equal to delta Pa2 and less than or equal to delta Pa2, determining to adjust the extraction time by adopting a second extraction time adjustment mode;
if delta Pa2 is less than or equal to delta Pa, determining to adjust the extraction time by adopting a third extraction time adjustment mode;
in this embodiment, the first extraction duration adjustment manner is to increase the extraction duration A0 to a first extraction duration adjustment value a01 by using a first extraction duration adjustment coefficient a1, a01=a0× (1+a1) is set, the second extraction duration adjustment manner is to increase the extraction duration A0 to a second extraction duration adjustment value a02 by using a second extraction duration adjustment coefficient a2, a02=a0× (1+a2) is set, the third extraction duration adjustment manner is to increase the extraction duration A0 to a third extraction duration adjustment value a03 by using a third extraction duration adjustment coefficient a3, a03=a0× (1+a3) is set, and the first extraction duration adjustment coefficient is smaller than the second extraction duration adjustment coefficient and is smaller than the third extraction duration adjustment coefficient, and both belong to the interval [5%,15% ].
Specifically, in the step S8, if it is determined that the addition amount of the chromatographic pure methanol extraction solvent needs to be optimized, the method is performed according to the following steps 13 C 12 Determining a mode when optimizing the addition of the chromatographic pure methanol extraction solvent by comparing the percentage DeltaPb of the BPA isotope recovery accounting for the standard parameter DeltaP 1 of the difference value of the first BPA isotope recovery with the standard percentage DeltaPb 1 of the adjustment of the addition of the first chromatographic pure methanol extraction solvent and the standard percentage DeltaPb 2 of the addition of the second chromatographic pure methanol extraction solvent, wherein DeltaPb 2 > DeltaPb1,
if DeltaPb < DeltaPb1, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a first chromatographic pure methanol extraction solvent adding amount adjusting mode;
if delta Pb1 is less than or equal to delta Pb2, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a second chromatographic pure methanol extraction solvent adding amount adjusting mode;
if delta Pb2 is less than or equal to delta Pb, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a third chromatographic pure methanol extraction solvent adding amount adjusting mode;
in this embodiment, the first pure methanol extraction solvent addition amount adjustment mode is to increase the addition amount B0 of the pure methanol extraction solvent to a first addition amount adjustment value B01 with a first pure methanol extraction solvent addition amount adjustment coefficient B1, b01=b0× (1+b1) is set, the second pure methanol extraction solvent addition amount adjustment mode is to increase the addition amount B0 of the pure methanol extraction solvent to a second addition amount adjustment value B02 with a second pure methanol extraction solvent addition amount adjustment coefficient B2, b02=b0× (1+b2) is set, the third pure methanol extraction solvent addition amount adjustment mode is to increase the pure methanol extraction solvent addition amount A0 to a third addition amount adjustment value B03 with a third pure methanol extraction solvent addition amount adjustment coefficient a3, b03=b0× (1+b3) is set, the first pure methanol extraction solvent addition amount adjustment coefficient is smaller than the second pure methanol extraction solvent addition amount adjustment coefficient is smaller than the third pure methanol extraction solvent addition amount adjustment coefficient, and all belong to 15% ] to the third pure phase section.
Specifically, in the step S8, if it is determined that the amount of the BPA isotope to be added needs to be optimized, the method is performed based on the following conditions 13 C 12 -comparing the percentage ΔPc of the recovery of the BPA isotope to the standard parameter ΔP2 of the difference in recovery of the second BPA isotope with the standard parameter ΔP1 of the adjustment of the initial addition amount of the first BPA isotope and the standard parameter ΔPc2 of the adjustment of the initial addition amount of the second BPA isotope to determine the manner in which the addition amount of the BPA isotope is optimized, wherein ΔPc1 < ΔPc2 < ΔPc1 < ΔPc2)
If ΔPc < ΔP1, then the first is determined to be employed 13 C 12 -means for adjusting the amount of added BPA isotope;
if ΔPc1 is less than or equal to ΔPc2, then determining to use a second 13 C 12 -means for adjusting the amount of added BPA isotope;
if ΔPc2 is less than or equal to ΔPc, then determining to use a third 13 C 12 -means for adjusting the amount of added BPA isotope;
in this embodiment, the first 13 C 12 The mode of adding the BPA isotope is that a first mode is adopted 3 C 12 -increasing the BPA isotope addition quantity adjustment coefficient c1 by 3 C 12 -adding amount C0 of BPA isotope to first isotope adding amount adjustment value C01, c01=c0× (1+c1), said second 13 C 12 The mode of adding the BPA isotope is to adopt a second mode 3 C 12 -increasing the BPA isotope addition quantity adjustment coefficient c2 3 C 12 -adding amount C0 of BPA isotope to second isotope adding amount adjustment value C02, c02=c0× (1+c2), the third 13 C 12 The mode of adjusting the adding amount of the BPA isotope adopts a third mode 3 C 12 -BPA isotope additionThe quantity adjustment coefficient c3 increases the 3 C 12 -adding amount of BPA isotope to a third isotope addition amount adjustment value C03, c03=c0× (1+c3), the first isotope addition amount being set to 3 C 12 -BPA isotope addition level adjustment coefficient is less than said second 3 C 12 -BPA isotope addition level adjustment coefficient is less than said third 3 C 12 BPA isotope addition amount adjustment coefficient, and all belong to the interval [5%,15%]。
Specifically, the sample recovery rate and the detection limit and the quantification limit of the detection method in the embodiment of the invention are as follows: the recovery rate of the method is calculated by taking corn kernels as a matrix, adding low, medium and high concentration standard samples, wherein the concentrations are respectively 2ng/g, 20ng/g and 200ng/g, the actual content of bisphenol compound standard samples in the samples is respectively measured, and 6 standard samples are parallel to each other. Recovery of 7 BPs is shown in table 1.
Table 1, 7 recovery rate of BPs
Specifically, the optimization in step S8 is performed, and the final determination is made 13 C 12 The addition amount of the BPA isotope is 20ng, the addition amount of the chromatographic pure methanol extraction solvent is 10mL, the ultrasonic time is 20min, and the extraction time is 30min.
Thus far, the technical solution of the present invention has been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of protection of the present invention is not limited to these specific embodiments. Equivalent modifications and substitutions for related technical features may be made by those skilled in the art without departing from the principles of the present invention, and such modifications and substitutions will be within the scope of the present invention.
The foregoing description is only of the preferred embodiments of the invention and is not intended to limit the invention; various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for detecting trace bisphenol compounds in agricultural products, comprising the steps of:
step S1, freeze-drying a sample to obtain a sample weight R1, and determining a weighing interval duration according to the sample weight R1 and a freeze-drying temperature C1 of a freeze-drying device so as to determine whether the sample is freeze-dried according to the result of each weighing of the sample;
Step S2, grinding the freeze-dried sample to obtain the surface area of the freeze-dried sample, determining grinding precision based on the surface area of the freeze-dried sample, obtaining a ground sample after finishing grinding the sample, and sieving the ground sample to obtain a sieved sample;
s3, placing the sieved sample into a centrifuge tube, adding an initial adding amount of BPA isotope into the centrifuge tube to obtain a quality control sample, and carrying out vortex mixing and standing on the sample added with the BPA isotope to obtain a standing sample;
s4, adding an initial addition amount of chromatographic pure methanol extraction solvent into the sample after standing, carrying out vortex mixing, then carrying out microwave extraction to obtain an extracted solution, carrying out vibration and centrifugal treatment on the extracted solution, and extracting supernatant;
step S5, repeating the step S4, and mixing the supernatant extracted by the centrifugal treatment twice to obtain a mixed supernatant;
s6, diluting the mixed clear liquid with pure water to obtain diluted mixed clear liquid, and extracting and eluting the diluted mixed clear liquid through a solid phase extraction column to obtain eluent;
s7, drying the eluent by a nitrogen blower, re-dissolving the eluent by using a mixed solution of methanol and water to obtain a re-solution, and filtering the re-solution by using a 0.22 mu m microporous filter membrane to obtain a filtrate;
Step S8, carrying out liquid chromatography measurement on the filtrate by adopting a liquid chromatography measurement method, and judging whether the adding amount of the BPA isotope is required to be optimized, whether the adding amount of the chromatographic pure methanol extraction solvent is required to be optimized and whether the extraction duration of the microwave extraction is required to be optimized under a first preset condition;
and determining the content of bisphenol compounds in the sample under a second preset condition;
the sample is maize or wheat in a mature period, the first preset condition is that the recovery rate of the BPA isotope belongs to a first recovery rate interval, the second preset condition is that the recovery rate of the BPA isotope is in a second recovery rate interval, the upper limit of the first recovery rate interval is set to be smaller than the lower limit of the second recovery rate interval, and the second recovery rate interval belongs to a standard recovery rate range;
in the step S3, the BPA isotope is 13 C 12 A BPA isotope;
in the step S8, the method comprises the steps of 13 C 12 -BPA isotope recovery, calculated as 13 C 12 -BPA isotope recovery and presetting 13 C 12 A recovery difference DeltaP of standard recovery of BPA isotopes, and comparing the recovery difference DeltaP with a first BPA isotope recovery difference standard parameter DeltaP 1 and a second BPA isotope recovery difference standard parameter DeltaP 2, and judging whether the adding amount of the BPA isotopes needs to be optimized, whether the adding amount of the chromatographic pure methanol extraction solvent needs to be optimized and whether the extraction duration of the microwave extraction needs to be optimized according to comparison results, wherein,
If the delta P is less than the delta P1, judging that the extraction duration of the microwave extraction needs to be optimized;
if delta P1 is less than or equal to delta P < deltaP 2, judging that the adding amount of the chromatographic pure methanol extraction solvent needs to be optimized;
if delta P2 is less than or equal to delta P, judging that the adding amount of the BPA isotope needs to be optimized.
2. The method for detecting trace bisphenol compounds in agricultural products according to claim 1, wherein in said step S1, a weighing interval parameter M is calculated according to formula (1),
in the formula (1), R10 represents the weight of a preset standard sample, and C10 represents the preset standard freeze-drying temperature;
and comparing the weighing interval parameter M with a preset first weighing interval parameter standard M1 and a second weighing interval parameter standard M2, and determining the weighing interval duration according to the comparison result, wherein M1 is smaller than M2,
if M is less than M1, setting the weighing interval duration to be T1;
if M1 is less than or equal to M2, setting the weighing interval duration to be T2;
if M2 is less than or equal to M, setting the weighing interval duration to be T3;
wherein T1 is less than T2 and less than T3.
3. The method for detecting trace bisphenol compounds in agricultural products according to claim 2, wherein in said step S1, weights of two adjacent weighings are determined to calculate a weight difference Δw, and the weight difference Δw is compared with a preset first weight difference standard parameter Δw1 and a second weight difference standard parameter Δw2, and whether the sample is freeze-dried is determined based on the comparison result,
If DeltaW < DeltaW1, determining that freeze drying of the sample is complete;
if DeltaW 1 is less than or equal to DeltaW < DeltaW2, determining to adjust the weighing interval time by adopting a first weighing interval adjustment mode;
if delta W2 is less than or equal to delta W1, determining to adjust the weighing interval time length by adopting a second weighing interval adjustment mode;
the first weighing interval adjustment mode is to increase the weighing interval time by adopting a first interval time adjustment coefficient, the second weighing interval adjustment mode is to increase the weighing interval time by adopting a second interval time adjustment coefficient, and the first interval time adjustment coefficient is set to be smaller than the second interval time adjustment coefficient.
4. The method for detecting trace bisphenol compounds in agricultural products according to claim 3, wherein in the step S2, the surface area of the freeze-dried sample is compared with a predetermined standard parameter DeltaVa 1 for the difference of the surface area of the first freeze-dried sample and a predetermined standard parameter DeltaVa 2 for the difference of the surface area of the second freeze-dried sample, and the grinding accuracy is determined based on the comparison result,
setting the polishing accuracy to J1 if Δva < Δva1;
setting the grinding precision to J2 if DeltaVa1 is less than or equal to DeltaVa < DeltaVa2;
Setting the grinding precision to J3 if DeltaVa2 is less than or equal to DeltaVa;
wherein J1 is less than J2 and less than J3.
5. The method for detecting trace amounts of bisphenol compounds in agricultural products according to claim 1, wherein in the step S8, the liquid chromatography measuring method is ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for detecting the concentration of each bisphenol compound in agricultural product samples, and controlling the operating parameters of the ultra-high performance liquid chromatography comprises:
liquid chromatography parameters, adopting an ACQUITYUPLCBEHShieldRP18 chromatographic column with a length of 150mm, an inner diameter of 2.1mm, a particle diameter of 1.7 μm, a sample injection amount of 5 μl, and a chromatographic column temperature of 55deg.C;
mobile phase parameters, wherein an inorganic phase A of the mobile phase is an aqueous solution containing 0.1% ammonia water, an organic phase B is chromatographic grade pure methanol, the mobile phase is subjected to ultrasonic treatment for 20min before being put on a machine so as to remove gas interference in the solution, and the flow rate of the mobile phase is set to be 0.3mL/min;
the gradient of the mobile phase was such that the initial phase was 70% a and 30% b, the organic phase was raised to 80% b for 1.5min, held for 1.5min, then raised to 950% b, held for 0.5min, lowered to 30% b at 3.5min, and returned to the initial mobile phase state;
mass spectrum parameters, adopting an ESI source negative ion mode, wherein the gas curtain gas is 30.0Psi, the ion source temperature is 500 ℃, the spray gas is 50Psi, the auxiliary heating gas is 50Psi, the ionization voltage is-4500 v, and the collision gas Medium is sprayed.
6. The method for detecting trace bisphenol compounds in agricultural products according to claim 5, wherein in said step S8, if it is determined that the extraction duration of said microwave extraction is to be optimized, it is determined that the method is based on said steps of 13 C 12 Recovery of BPA isotope 13 C 12 Determining a mode of optimizing the extraction duration of the microwave extraction by comparing the percentage ΔPa of the standard recovery rate of the BPA isotope with a first extraction duration adjustment percentage standard parameter ΔPa1 and a second extraction duration adjustment percentage standard parameter ΔPa2, wherein ΔPa2 > - ΔPa1,
if delta Pa < [ delta ] Pa1, determining to adjust the extraction time length by adopting a first extraction time length adjustment mode;
if delta Pa1 is less than or equal to delta Pa2 and less than or equal to delta Pa2, determining to adjust the extraction time by adopting a second extraction time adjustment mode;
if delta Pa2 is less than or equal to delta Pa, determining to adjust the extraction time by adopting a third extraction time adjustment mode;
the first extraction time length adjusting mode is to increase the extraction time length by adopting a first extraction time length adjusting coefficient, the second extraction time length adjusting mode is to increase the extraction time length by adopting a second extraction time length adjusting coefficient, the third extraction time length adjusting mode is to increase the extraction time length by adopting a third extraction time length adjusting coefficient, and the first extraction time length adjusting coefficient is smaller than the second extraction time length adjusting coefficient and is smaller than the third extraction time length adjusting coefficient, and the first extraction time length adjusting coefficient and the second extraction time length adjusting coefficient are all in a range of [5%,15% ].
7. The method for detecting trace bisphenol compounds in agricultural products according to claim 6, wherein in step S8, if it is determined that the addition amount of the chromatographically pure methanol extraction solvent is required to be optimized, the method is based on the following steps 13 C 12 -BPA isotope recovery accounting for said first BPAThe comparison result of the percentage DeltaPb of the isotope recovery rate difference standard parameter DeltaP 1 and the first chromatographic pure methanol extraction solvent addition amount adjustment standard percentage DeltaPb 1 and the second chromatographic pure methanol extraction solvent addition amount adjustment standard percentage DeltaPb 2 determines the mode when optimizing the addition amount of the chromatographic pure methanol extraction solvent, wherein DeltaPb 2 > DeltaPb1,
if DeltaPb < DeltaPb1, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a first chromatographic pure methanol extraction solvent adding amount adjusting mode;
if delta Pb1 is less than or equal to delta Pb2, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a second chromatographic pure methanol extraction solvent adding amount adjusting mode;
if delta Pb2 is less than or equal to delta Pb, determining to adjust the adding amount of the chromatographic pure methanol extraction solvent by adopting a third chromatographic pure methanol extraction solvent adding amount adjusting mode;
The first chromatographic pure methanol extraction solvent addition amount adjustment mode is to increase the chromatographic pure methanol extraction solvent addition amount by adopting a first chromatographic pure methanol extraction solvent addition amount adjustment coefficient, the second chromatographic pure methanol extraction solvent addition amount adjustment mode is to increase the chromatographic pure methanol extraction solvent addition amount by adopting a second chromatographic pure methanol extraction solvent addition amount adjustment coefficient, the third chromatographic pure methanol extraction solvent addition amount adjustment mode is to increase the chromatographic pure methanol extraction solvent addition amount by adopting a third chromatographic pure methanol extraction solvent addition amount adjustment coefficient, and the first chromatographic pure methanol extraction solvent addition amount adjustment coefficient is smaller than the second chromatographic pure methanol extraction solvent addition amount adjustment coefficient and is smaller than the third chromatographic pure methanol extraction solvent addition amount adjustment coefficient, and all belong to the interval [5%,15% ].
8. The method for detecting trace bisphenol compounds in agricultural products according to claim 7, wherein in said step S8, if it is determined that the addition amount of said BPA isotope is to be optimized, then according to said 13 C 12 -BPA isotope recovery accounts for the second BPA isotope recovery difference criterionThe comparison result of the percentage ΔPcof the parameter ΔP2 with the initial addition amount adjustment percentage standard parameter ΔPc1 of the first BPA isotope and the initial addition amount adjustment percentage standard parameter ΔPc2 of the second BPA isotope determines the manner when optimizing the addition amount of the BPA isotopes, wherein ΔPc1 < ΔPc2 < ΔPc1 < ΔPb2)
If ΔPc < ΔP1, then the first is determined to be employed 13 C 12 -means for adjusting the amount of added BPA isotope;
if ΔPc1 is less than or equal to ΔPc2, then determining to use a second 13 C 12 -means for adjusting the amount of added BPA isotope;
if delta Pc2 is less than or equal to delta Pc, determining to adopt a third 13C12-BPA isotope addition amount adjustment mode;
the first 13C12-BPA isotope addition amount adjustment mode is to increase the addition amount of the 3C12-BPA isotope by adopting a first 3C12-BPA isotope addition amount adjustment coefficient, the second 13C12-BPA isotope addition amount adjustment mode is to increase the addition amount of the 3C12-BPA isotope by adopting a second 3C12-BPA isotope addition amount adjustment coefficient, the third 13C12-BPA isotope addition amount adjustment mode is to increase the addition amount of the 3C12-BPA isotope by adopting a third 3C12-BPA isotope addition amount adjustment coefficient, the first 3C12-BPA isotope addition amount adjustment coefficient is smaller than the second 3C12-BPA isotope addition amount adjustment coefficient is smaller than the third 3C12-BPA isotope addition amount adjustment coefficient, and the first and the second 13C12-BPA isotope addition amount adjustment coefficient and the third 3C12-BPA isotope addition amount adjustment coefficient belong to a section [5%,15% ].
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