CN103091436B - Detection method of various pesticides in fertilizer - Google Patents
Detection method of various pesticides in fertilizer Download PDFInfo
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- CN103091436B CN103091436B CN201210429732.3A CN201210429732A CN103091436B CN 103091436 B CN103091436 B CN 103091436B CN 201210429732 A CN201210429732 A CN 201210429732A CN 103091436 B CN103091436 B CN 103091436B
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Abstract
The invention provides a detection method of various pesticides in a fertilizer. The detection method comprises the following steps of: 1) dissolving a fertilizer sample, filtering and obtaining filtrate; 2) detecting the filtrate by using a liquid chromatography-tandem mass spectrometry method; and 3) detecting contents of the pesticides in the fertilizer sample by using an external standard method. The method disclosed by the invention can perform qualitative and quantitative determination on the various pesticides in the fertilizer simultaneously, including determination of plant growth regulators and insecticides to provide effective control and detection means for the environmental protection and food safety. According to the invention, the instrument detection limits of diethyl aminoethyl hexanoate, betaine, chlormequat, avermectin and forchlorfenuron all can reach 0.01mg/L, the detection limits of 4-sodium nitrophenolate and 5-nitroguaiacol sodium salt can reach 0.01mg/L, and the detection limit of sodium naphthalene acetate can reach 0.025mg/L, and the detection limits of 2-sodium nitrophenolate and gibberellic acid can reach 0.1mg/L. The method disclosed by the invention is low in detection limit and accurate in results, can detect a variety of pesticides once, and fast and high-efficient.
Description
Technical field
The invention belongs to the field of testing by means of the physicochemical property of material, be specially a kind of method that agricultural chemicals in fertilizer is detected.
Background technology
Agricultural chemicals refers in agricultural for medicaments such as anti-cure the disease worm and coordinate plant growth, weedings.Plant growth regulator, is a class agricultural chemicals of growing for coordinate plant growth, comprises artificial synthetic compound and the natural phytohormone extracting from biology.In agricultural production, use, can effectively regulate the growing process of crop, reach stable yields volume increase, improve quality, strengthen the objects such as crop anti-adversity.Pesticide is mainly used in preventing and treating the medicine of agricultural pests and urban health insect, and at twentieth century, along with developing rapidly of agricultural, pesticide makes farm output rise higher.But nearly all pesticide all can seriously change the ecosystem, most of harmful, other meeting is concentrated in food chain.Conventional plant growth regulator and pesticide comprise: compound sodium nitrophenolate (Sodium Nitrophenolate), mainly contain 3 compositions, and comprising: 1,2-p-nitrophenol sodium, molecular formula: C
6h
4nO
3na, molecular weight: 161.09; 2,4-p-nitrophenol sodium, molecular formula: C
6h
4nO
3na, molecular weight: 161.09; 3,5-nitroguaiacol sodium salt, molecular formula: C
7h
6nO
4na, molecular weight: 191.12, be broad spectrum type plant growth regulator, can accelerate vine growth and development, short root strong sprout, flower and fruit protecting, raising output, strengthen anti-adversity ability etc., both can be used alone, again can with the composite use such as fertilizer, agricultural chemicals, feed.Diethyl aminoethyl hexanoate (DA-6, Diethyl aminoethyl hexanoate), molecular formula: C
12h
25nO
2; Molecular weight: 215.33, a small amount of DA-6 can make yield of beans increase by 60%, and the industrial crops such as beet volume increase 50%, DA-6 not only, at Promoting plant growth fundamentally, also can obviously increase fruit nature fragrance and color and luster, strengthens plant stress-resistance ability.Nafusaku (Sodium α-naphthyl acetate), molecular formula: C
12h
9o
2na, auxins plant modifying agent, obviously promote root system tip growth, induced flowering, prevent fruit drop, form seedless fruit, promote the effects such as precocity, volume increase.Gibberellin (Gibberellic acid), molecular formula: C
19h
22o
6; Molecular weight: 346.37, improve Zante currant output, break potato dormancy, meet overcast and rainy low temperature and ear when slow when late rice, process with gibberellin and can promote to ear, or in breeding of hybrid rice, regulate the florescence so that Parent flower synchronization etc.Betaine (Betaine), molecular formula C
14h
9c
l2; Molecular weight 354.49, for cotton, wheat, paddy rice, corn, tomato, fruit tree and various root crop, resistant to lodging, promote plant growth, can increase production 10%～30%, also can make potato tubers increase.Avermectin (Avermectin), molecular formula: C
48h
72o
14(B1a); Molecular weight: 873.09, mite class and insect are had to stomach toxicity and action of contace poison, be mainly used in crops, poultry, domestic animal endoparasite and ectoparasite and insect, worm as red in parasitism, Diptera, coleoptera, Lepidoptera and pest mite etc.CPPU (Forchlorfenuro), molecular formula: C
12h
10clN
3o; Molecular weight: 247.68, can be used for watermelon, grape, Kiwi berry, show and promote stem, leaf, root, fruit growth, promotion result, increase the output of the fruits and vegetables such as tomato, eggplant, apple.
As a rule, according to using dosage, the time and technique indicated on agriculture chemical registration approval label, use plant growth regulator or pesticide can not produce harm to health.If but use upper appearance lack of standardization, and may make crop excessively rapid growth, quality of agricultural product and mouthfeel are produced to certain influence; The more important thing is, produce for agricultural product, the abuse of plant growth regulator, can final harm food security.In general, in fertilizer, not allow to add pesticide, germifuge and plant growth regulator, but will produce and add according to normality condition.For example, made laws sternly to hit and in fertilizer, illegally added behaviors such as using agricultural chemicals (comprising growth regulator) and strengthen the monitoring to materials such as agricultural chemicals, detection and selective examination work in Beijing.
Vegetables and fruits, can be through interval after a while from using correctives to sell to listing, and it is residual does not measure substantially, but fertilizer is directly detected, and result can be accurately a lot.
Summary of the invention
For the problem of prior art existence, the object of the invention is to propose the detection method of Multiple Pesticides in a kind of fertilizer.
The concrete technical scheme that realizes the object of the invention is:
A detection method for Multiple Pesticides in fertilizer, comprises step:
1) fertilizer sample is dissolved, filter and get filtrate;
2) detect filtrate with Liquid Chromatography-Tandem Mass Spectrometry;
3) use typical curve external standard method to detect the content of fertilizer sample Pesticides.
Wherein, described Multiple Pesticides is one or more in compound sodium nitrophenolate, diethyl aminoethyl hexanoate, Nafusaku, gibberellin, betaine, cycocel, Avermectin and CPPU.
Wherein, described dissolving is to dissolve with acetonitrile solution.Described filtration is to use 0.2-0.4 μ m membrane filtration.
Wherein, described step 2) in the mobile phase of liquid chromatography be A: containing the aqueous solution of mass ratio 0.1-0.2% formic acid and 4-6mmol/L ammonium acetate, B: acetonitrile, column equilibration time 4-6min, flow velocity 0.2-0.4mL/min, sample size 8-12 μ L.
Wherein, described step 2) in liquid chromatography use the method for gradient elution, the program of gradient elution is:
Preferably, the program of described gradient elution is:
The % of A and B is volume ratio.
Wherein, described step 2) in Mass Spectrometer Method use electrospray ionization mass spectrum to detect, electron spray voltage be-4000 to-5000V and+5000 to+5500V.
Wherein, electron spray voltage be+5000 to the agricultural chemicals of Mass Spectrometer Method under+5500V condition be one or more (the positive ion scannings) in diethyl aminoethyl hexanoate, betaine, cycocel, Avermectin and CPPU; Electron spray voltage be-4000 to the agricultural chemicals of Mass Spectrometer Method under-4500V condition be one or more (the negative ion scannings) in compound sodium nitrophenolate, Nafusaku, gibberellin.Wherein, compound sodium nitrophenolate mainly contains 3 compositions, comprising: 1,2-p-nitrophenol sodium, 2,4-p-nitrophenol sodium, 3,5-nitroguaiacol sodium salt.
Wherein, step 2) middle parent ion and the daughter ion pair that detects each agricultural chemicals in described filtrate, if its chromatography of ions peak retention time is consistent with standard operation solution; And the relative abundance of two daughter ions and the relative abundance of the suitable standard solution of concentration of target compound is consistent in deviation is no more than 30% scope in filtrate (sample), judges and in this sample, have this kind of agricultural chemicals; If above-mentioned two conditions meet when different, judgement is not containing this kind of agricultural chemicals.
Wherein, described step 3) Plays curve is to be formulated as respectively standard solution with the described agricultural chemicals of variable concentrations, with Liquid Chromatography-Tandem Mass Spectrometry detect its chromatographic peak area and typical curve.Taking concentration as horizontal ordinate, the right chromatographic peak area of quota ion is the typical curve that ordinate is drawn respectively each agricultural chemicals, adopts this curve to calculate respectively the content of 10 kinds of agricultural chemicals in fertilizer sample to be measured with external standard method.
Beneficial effect of the present invention is:
Method of the present invention can be carried out to the Multiple Pesticides existing in fertilizer the mensuration of quantitative and qualitative analysis simultaneously, comprises the mensuration to plant growth regulator and pesticide, for environmental protection and food security provide effective control detection means.This method can reach 0.01mg/L to the instrument detection limit of 4-p-nitrophenol sodium and 5-nitroguaiacol sodium salt, and Nafusaku can reach 0.025mg/L, and 2-p-nitrophenol sodium and gibberellin can reach 0.1mg/L.This method detection limit is low, and result is accurate, can one-time detection Multiple Pesticides, and quickness and high efficiency.
Brief description of the drawings
Fig. 1 is 5 kinds of agricultural chemicals: the positive ion scanning total ions chromatogram of diethyl aminoethyl hexanoate, betaine, cycocel, Avermectin and CPPU.
Fig. 2-6 are respectively the ion pair extraction chromatography figure of diethyl aminoethyl hexanoate, betaine, cycocel, Avermectin, CPPU.
Fig. 7 is 5 kinds of agricultural chemicals Nafusakus, gibberellin, 1,2-p-nitrophenol sodium, 2,4-p-nitrophenol sodium, 3, the negative ion scanning total ions chromatogram of 5-nitroguaiacol sodium salt.
Fig. 8-11 are respectively the chromatography of ions figure of 4-p-nitrophenol sodium, 2-p-nitrophenol sodium, 5-nitroguaiacol sodium salt, Nafusaku, gibberellin.
Embodiment
Now with following most preferred embodiment, the present invention is described, but is not used for limiting the scope of the invention.
The ultrasonic treatment facility using in embodiment is Kunshan KQ-200KDE type ultrasonoscope;
Solid phase extraction column is purchased from Féraud door company of the U.S.;
0.22 μ m filter membrane is purchased from Tianjin Jin Teng experimental facilities company limited.
Embodiment 1: the detection of water soluble fertilizer sample Pesticides
1. sample pretreatment
The vibration of water soluble fertilizer sample is mixed, take about 0.5g sample in 100mL volumetric flask, with acetonitrile/water (50/50, v/v) vibration dissolving, constant volume, mix rear mistake 0.22 μ m filter membrane in sample introduction bottle, upper LC-MS/MS measures.The sample that exceedes the range of linearity for content further dilutes constant volume solution, so that its content goes up that LC-MS/MS measures after in the instrument range of linearity again and quantitatively.
2.LC-MS/MS measures
Tri-grades of quadrupole rod tandem mass spectrum combined instruments of instrument: Agilent 1200 high performance liquid chromatography (U.S., Agilent)-API2000 (U.S., AB SCIEX), are equipped with electron spray (ESI) ion gun;
Chromatographic column: Agilent XDB C18,4.6 × 150mm, particle diameter 5 μ m;
Mobile phase: (A) water (containing the ammonium acetate of 0.1% formic acid and 5mmol/L); (B) acetonitrile;
Flow velocity: 0.3mL/min;
Sample size: 10 μ L;
Column temperature: room temperature (approximately 26 DEG C);
The column equilibration time (before next sample feeding): 5min(positive ion scanning) and the scanning of 4min(negative ion);
Gradient elution program is as table 1 and table 2.
The gradient elution program that table 1: embodiment 1 positive ion detects
| Sequence number | Time (min) | A（%） | B（%） |
| 1 | 0 | 70 | 30 |
| 2 | 3.0 | 10 | 90 |
| 3 | 13.0 | 10 | 90 |
| 4 | 13.1 | 70 | 30 |
| 5 | 18.0 | 70 | 30 |
The gradient elution program that table 2: embodiment 1 negative ion detects
| Sequence number | Time (min) | A（%） | B（%） |
| 1 | 0 | 70 | 30 |
| 2 | 3.0 | 10 | 90 |
| 3 | 10.0 | 10 | 90 |
| 4 | 10.1 | 70 | 30 |
| 5 | 16.0 | 70 | 30 |
3. mass spectrum parameter
Scan mode: many reactive ion monitorings (MRM) scanning;
Ion source temperature TEM:450.00 DEG C;
Electron spray voltage IS:+5500V;-4500V;
Gas curtain gas CUR:25.00;
Atomization gas GS1:45.00;
Dry gas GS2:65.00;
Collision gas CAD:4.00;
The ion pair parameter of the target agricultural chemicals that MRM detects is in table 3 and table 4.Wherein Q1 is three grades of quadrupole rod first order, and Q3 is three grades of quadrupole rod third level, detects respectively parent ion and the daughter ion of target agricultural chemicals.Time, DP, CE represent ion residence time (ms), separate bunch voltage (V) and impact energy (V).
Table 3MRM positive ion detects ion pair parameter
Table 4MRM negative ion detects ion pair parameter
* be quota ion pair.
4, Qualitative Identification
For parent ion and the daughter ion pair of each agricultural chemicals, under identical condition, if the chromatography of ions peak retention time consistent with standard operation solution (variation range is within ± 2.5%) in sample; In sample, the relative abundance of two of target compound daughter ions is consistent with the relative abundance of the suitable standard solution of concentration, and relative abundance deviation is no more than 30%, can in judgement sample, have this kind of agricultural chemicals.The ion current chromatogram of the agricultural chemicals of standard is shown in Fig. 1-11, and the ordinate of each figure is intensity (Intensity, cps).
In the present embodiment, in the sample detecting, scan by positive ion the existence that detects diethyl aminoethyl hexanoate, betaine, cycocel, scan the existence that has detected 2-p-nitrophenol sodium, 4-p-nitrophenol sodium, 5-nitroguaiacol sodium salt, Nafusaku by negative ion.
5, quantitatively calculate
Prepare with acetonitrile/water (50/50, v/v) solution that concentration is 0.05,0.1,0.2,0.5,1.0, each agricultural chemicals mixed standard solution of 5.0mg/L.
Measure by above-mentioned ion scan method sample introduction, taking concentration as horizontal ordinate, the chromatographic peak area of quota ion is the typical curve equation that ordinate draws respectively each agricultural chemicals: diethyl aminoethyl hexanoate y=1310x+3840, betaine y=2950x+42700, cycocel y=25900x+29600, Avermectin y=71.5x+470, CPPU y=3550x-11400,1,2-p-nitrophenol sodium y=7.11x-566,2,4-p-nitrophenol sodium y=1710x+38800,3,5-nitroguaiacol sodium salt y=334x-12800, Nafusaku y=80x+2990, gibberellin y=1.63x+32.3.Adopt above-mentioned typical curve to calculate respectively the content of various agricultural chemicals in water soluble fertilizer sample to be measured with external standard method.2 Duplicate Samples of sample preparation of the water soluble fertilizer of surveying, upper machine represents the content of this sample Pesticides with mean value after measuring, the deviation of measured value is all less than 5%.Detecting sample, there is chromatographic peak at 8.47min, 4.10min, the 4.26min of the scanning of retention time positive ion at 9.73min, 10.84min, 9.77min, the 10.42min of negative ion scanning in it.By the chromatographic peak area obtaining, according to the linear standard curve equation of each agricultural chemicals, try to achieve the content of each agricultural chemicals in machine solution, be scaled the content of various medicines in water soluble fertilizer sample with extension rate in sample preparation process and sampling amount, be respectively diethyl aminoethyl hexanoate 21.54mg/kg, betaine 109.4mg/kg, cycocel 5.51mg/kg, 2-p-nitrophenol sodium 476.49mg/kg, 4-p-nitrophenol sodium 28.13mg/kg, 5-nitroguaiacol sodium salt 41.49mg/kg, Nafusaku 106.48mg/kg, Avermectin, CPPU and gibberellin do not detect.
Above embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various modification and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (3)
1. a detection method for Multiple Pesticides in fertilizer, comprises step:
1) fertilizer sample is dissolved, filter and get filtrate, described dissolving is to dissolve with acetonitrile solution;
2) detect filtrate with Liquid Chromatography-Tandem Mass Spectrometry;
In described liquid chromatography, its mobile phase is A: containing the aqueous solution of mass ratio 0.1-0.2% formic acid and 4-6mmol/L ammonium acetate, B: acetonitrile, column equilibration time 4-6min;
Described liquid chromatography is used the method for gradient elution, and the program of gradient elution is:
Detect parent ion and the daughter ion pair of each agricultural chemicals in described filtrate, if its chromatography of ions peak retention time is consistent with standard operation solution; And the relative abundance of two daughter ions of target compound is consistent in deviation is no more than 30% scope with the relative abundance of the suitable standard solution of concentration, wherein there is this plant growth regulators in judgement; If above-mentioned two conditions meet when different, judgement is not containing this kind of agricultural chemicals;
Described Mass Spectrometer Method is used electrospray ionization mass spectrum to detect, and electron spray voltage be-4000 to-5000V and+5000 to+5500V;
Wherein, electron spray voltage be+5000 to the agricultural chemicals of Mass Spectrometer Method under+5500V condition be one or more in diethyl aminoethyl hexanoate, betaine, cycocel, Avermectin and CPPU; Electron spray voltage be-4000 to the agricultural chemicals of Mass Spectrometer Method under-4500V condition be one or more in compound sodium nitrophenolate, Nafusaku, gibberellin;
3) use typical curve external standard method to detect the content of Multiple Pesticides in fertilizer sample
Wherein, described Multiple Pesticides is one or more in compound sodium nitrophenolate, diethyl aminoethyl hexanoate, Nafusaku, gibberellin, betaine, cycocel, Avermectin and CPPU.
2. detection method as claimed in claim 1, is characterized in that, the program of described gradient elution is:
3. detection method as claimed in claim 1 or 2, it is characterized in that, described step 3) Plays curve is to be formulated as respectively standard solution with the described agricultural chemicals of variable concentrations, with Liquid Chromatography-Tandem Mass Spectrometry detect its chromatographic peak area and typical curve.
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| CN103399115B (en) * | 2013-08-13 | 2015-03-04 | 河北圣雪大成制药有限责任公司 | Method for detecting content of moxidectin based on liquid chromatograph |
| CN103969363A (en) * | 2014-04-09 | 2014-08-06 | 温州市质量技术监督检测院 | Detection method for plant growth regulator residues in fruits |
| CN109613151A (en) * | 2018-11-14 | 2019-04-12 | 温州科技职业学院 | In a kind of detection solid fertilizer in the preprocess method of growth regulator and detection liquid fertilizer growth regulator preprocess method |
| CN109541114B (en) * | 2019-01-24 | 2021-01-22 | 山东省烟台市农业科学研究院 | Method for detecting residual quantity of compound sodium nitrophenolate in fruits and vegetables |
| CN110940760A (en) * | 2019-12-28 | 2020-03-31 | 上海市农业技术推广服务中心 | Method for measuring plant growth regulator in water-soluble fertilizer through UPLC-QTOF-MS |
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Inventor after: Zhao Lu Inventor after: Zhao Yongzhi Inventor after: Cheng Yanjun Inventor after: Li Changwei Inventor after: Qiu Jing Inventor after: Ha Xuejiao Inventor after: Sun Jifeng Inventor after: Jiang Zeng Inventor after: Zhang Tengfei Inventor before: Zhao Lu Inventor before: Zhao Yongzhi Inventor before: Cheng Yanjun Inventor before: Li Changwei Inventor before: Qiu Jing Inventor before: Ha Xuejiao Inventor before: Sun Jifeng Inventor before: Jiang Zeng Inventor before: Zhang Tengfei |
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