CN103411953B - A kind of method of farm chemical emulsion preparation being carried out to field quick detection - Google Patents
A kind of method of farm chemical emulsion preparation being carried out to field quick detection Download PDFInfo
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Abstract
The present invention relates to Pesticides Testing technical field, particularly relate to a kind of method of farm chemical emulsion preparation being carried out to field quick detection, the present invention is based on Raman spectrum principle, the effective constituent of Site Detection farm chemical emulsion preparation, whether containing forbidden amphetamine and constituent concentration, distinguishable composition comprises more than 30 kind of common pesticides and more than 10 and plants forbidding or limit the use of agricultural chemicals, and monocyte sample test can complete in 30 minutes.Verify through contrasting with the objective results of the testing result comprising Pesticides Testing authoritative institution, qualitative recall rate of the present invention reaches 76.7%, total rate of accuracy reached 73.3%, the rate of accuracy reached 59.3% of quantitative measurment error within 30%, the rate of accuracy reached 48.1% of quantitative measurment error within 20%.The chromatogram in contrast test laboratory, mass spectrometry method, have simple to operate, can on-the-spot test, the advantages such as the test duration is short.
Description
Technical field
The present invention relates to Pesticides Testing technical field, particularly relate to a kind of method of farm chemical emulsion preparation being carried out to field quick detection.
Background technology
On-the-spot Fast Detection Technique is not still can be used at present in field of pesticide detection, on market, the monitoring of agricultural chemicals generally adopts sampling to deliver to the method for the test experience Spot detection of agricultural sector, main detection means is chromatograph, chromaticness interlock instrument, because checkout equipment is expensive, detection technique is complicated, the check point possessing qualification is little, many places only have prefecture-level city even provincial organization just can detect, cause that censorship cost is high, problem that feedback time is long, have a strong impact on basic unit's monitoring, law enforcement agency hit work efficiency that is violated, the agricultural chemicals that exceeds standard.
Raman spectroscopy is nearly technology grown up for 10 years, there is the advantages such as quick, easy, harmless and direct-detection sample, be well suited for as field quick detection means, but current all Raman spectrometers are only equipped with pure material spectrum data storehouse, the function of Object Classification is still confined to the category of pure material identification, can not be directly used in the detection detecting this potpourri of agricultural chemicals.Scientific research institution and universities and colleges are used for the research of Pesticides Testing for Raman spectrum, major part is still confined to the preliminary feasibility study few kind, known composition agricultural chemicals being done to qualitative and quantitative analysis, and whether to multiple types, composition the unknown, complicated agricultural chemicals, there is detection and resolving ability for Raman spectroscopy, there is not yet systematic study report.
Therefore, need the defect for prior art badly, provide a kind of and carry out that multiple types, composition are unknown based on Raman spectroscopy, complicated agricultural chemicals carries out the method that detects.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, and provide a kind of based on Raman spectrum principle, can on-the-spot method of farm chemical emulsion preparation being carried out to detect fast.
The present invention is realized by following technology the present invention.
Farm chemical emulsion preparation is carried out to a method for field quick detection, it comprises the following steps:
A. prepare: collect the raman signatures of several farm chemical emulsion preparation at solution system, differentiate feature for several farm chemical emulsion preparation distributes, by these features stored in database, call when carrying out composition identification for data processing software;
B. prepare Fluorescence Quenching Agent, measure the density of farm chemical emulsion preparation;
C. first round test: get farm chemical emulsion preparation to sample bottle, add Fluorescence Quenching Agent by multiple, then start the test procedure of Raman spectrometer, test farm chemical emulsion preparation; When observe signal base line be on close level 30000 time, start the first round test, follow-on test three times also records extension rate, store data;
D. second take turns test: after the first round tested, then add Fluorescence Quenching Agent by multiple and farm chemical emulsion preparation is surveyed in examination, when observe signal base line be on close level 20000 time, follow-on test three times also records extension rate, stores data;
E. Data Management Analysis: by data processing software process data, obtain each qualitative test result, taking turns test if a certain to have twice or more result display containing certain composition, then judge that farm chemical emulsion preparation contains this composition.
Wherein, in described step b, preparation Fluorescence Quenching Agent is specially: 50mg fluorescence is eliminated former medicament and dissolves in 1ml water, injects 9ml pure acetone, fully mix, be mixed with Fluorescence Quenching Agent after dissolving completely.Fluorescence eliminates the product being numbered YZ-903 that former medicament provides for Shanghai Shen Zhi Chemical Industry Science Co., Ltd, it is macromolecule sulphur silicon compound, be the Fluorescence Quenching Agent of the more widely used a kind of fluorescer of a kind of textile industry, it can produce with fluorescence functional group reacts and is translated into non-fluorescence group; It is white granular, slightly penetrating odor, and water solubility can reach 20%, and 1% pH value of water solution is 6-7.When sour environment (pH is 4) and higher water temperature (60 DEG C), effect is better.
Wherein, in described step b, the density measuring farm chemical emulsion preparation is specially: sample bottle is placed on electronic balance, and clear 0, get 1ml farm chemical emulsion preparation, inject sample bottle completely, record now quality; Then clear 0, repeat above step twice, finally ask the mean value of three inferior qualities to draw the density of farm chemical emulsion preparation.
Wherein, in described step c, the test procedure starting Raman spectrometer is specially setting: start Raman spectrometer, open testing software interface, setting laser light intensity is 100%, and integral time is 2 × 35000 milliseconds.
Further, after described step e, also comprise step f converted score value: the peak intensity provided according to density and the data processing of extension rate, farm chemical emulsion preparation, and peak intensity and concentration relationship formula, converse the concentration value of farm chemical emulsion preparation.
Wherein, in described step f converted score value, the assay method of peak intensity and concentration relationship is specially: Fluorescence Quenching Agent is dissolved in the agent of pesticide original medicine sterling, be made into five groups of solution that concentration is respectively 0.5%, 1%, 2%, 5%, 10% respectively, testing often organizing solution, in triplicate, then processing often organizing data, obtain the peak value at the ionization meter peak often organizing solution, get the average peak that three mean value draws the ionization meter peak often organizing solution; Obtain the interior mark peak-to-peak signal 1706cm often organizing solution equally
-1peak value, get three mean values, averaging of income peak value obtains the acetone 1706cm of 100% concentration divided by 9/10
-1average peak; The average peak at the ionization meter peak often organized and the acetone 1706cm of 100% concentration
-1the ratio of average peak is the relative intensity of this group solution, and the concentration of the relative intensity and this group of getting five groups of solution carries out linear regression analysis, obtains the linear relationship of peak intensity and concentration relationship.
Wherein, in described step f, the assay method of peak intensity and concentration relationship is specially: Fluorescence Quenching Agent is dissolved in the agent of pesticide original medicine sterling, be made into six groups of solution that concentration is respectively 0.5%, 1%, 2%, 5%, 10%, 25% respectively, testing often organizing solution, in triplicate, then processing often organizing data, obtain the peak value at the ionization meter peak often organizing solution, get the average peak that three mean value draws the ionization meter peak often organizing solution; Obtain the interior mark peak-to-peak signal 1706cm often organizing solution equally
-1peak value, get three mean values, averaging of income peak value obtains the acetone 1706cm of 100% concentration divided by 9/10
-1average peak; The 1706cm of the average peak at the ionization meter peak often organized and the acetone of 100% concentration
-1the ratio of average peak is the relative intensity of this group solution, and the concentration of the relative intensity and this group of getting six groups of solution carries out linear regression analysis, obtains the linear relationship of peak intensity and concentration relationship.
Wherein, in described step f, the concentration value conversing farm chemical emulsion preparation is specially: according to the intensity level at echo signal peak, the concentration value after going out to dilute by peaks relative intensities and concentration relationship formula scales, and the concentration value after dilution is multiplied by quality extension rate and obtains the concentration value before diluting.
Wherein, described peaks relative intensities equals the intensity level at echo signal peak and the acetone 1706cm of 100% concentration
-1the ratio of signal; The acetone volume accounting in solution is extrapolated, the acetone 1706cm of actual measurement according to extension rate
-1signal intensity just converses the acetone 1706cm of 100% concentration divided by acetone volume accounting
-1the intensity of interior mark signal; Wherein, acetone volume accounting and extension rate close and are
quality extension rate and extension rate close and are
Wherein, in described step a, farm chemical emulsion preparation comprises following 49 kinds: D.D.T. (dichloro-diphenyl-trichloroethane) T, dicofol, γ-benzene hexachloride, D.D.T. (dichloro-diphenyl-trichloroethane) D, Aldicarb, carbofuran, terbufos, acephatemet, isocarbophos, Isofenphos methyl, α-benzene hexachloride, parathion-methyl, parathion, D.D.T. (dichloro-diphenyl-trichloroethane) E, fenvalerate, Azodrin, phosphamidon, ethiprole, phonetic mould amine, orthene, methidathion, malathion, fenifrothion, decis, cypermethrin, DDVP, Rogor, Fenpropathrin, chlopyrifos, diazinon, Profenofos, Difenoconazole, Methomyl, carbaryl, Hostathion, Imidacloprid, pyridaben, triazolone, Biphenthrin, diflubenzuron, phoxim, Phosalone, gamma cyhalothrin, Avermectin, procymidone, iprodione, vinclozolin, determine worm amidine, Bravo.
Compared with prior art, the present invention has the following advantages:
Method of farm chemical emulsion preparation being carried out to field quick detection of the present invention, based on Raman spectrum principle, scene is detected fast to farm chemical emulsion preparation, the effective constituent of Site Detection farm chemical emulsion preparation, whether containing forbidden amphetamine and constituent concentration, distinguishable composition comprises more than 30 kind of common pesticides and more than 10 and plants forbidding or limit the use of agricultural chemicals (covering scope easily extensible), and monocyte sample test can complete in 30 minutes.Verify through contrasting with the objective results of the testing result comprising Pesticides Testing authoritative institution, qualitative recall rate of the present invention reaches 76.7%, total rate of accuracy reached 73.3%, the rate of accuracy reached 59.3% of quantitative measurment error in 30%, quantitative measurment error is rate of accuracy reached 48.1% within 20%.The chromatogram in contrast test laboratory, mass spectrometry method, have simple to operate, can on-the-spot test, the advantages such as the test duration is short; Contrast traditional Raman spectroscopy, the present invention is extended to potpourri category its Object Classification function by pure material, is the huge progress to Raman spectroscopy application.
Accompanying drawing explanation
Fig. 1 is that the Raman shift values of the Raman spectrum of chlopyrifos solution of 10% and the Raman spectrum of the chlopyrifos of sterling contrasts and illustrates.
Fig. 2 3% determines worm amidine solution Raman signal graph under different diluting condition and shows.
Fig. 3 is the dark signal diagram that Raman spectrometer obtains.
Fig. 4 is the original signal diagram that Raman spectrometer obtains.
Fig. 5 is the signal diagram after reducing dark signal.
Fig. 6 is the signal diagram before and after round and smooth process.
Fig. 7 is the tendency polarity diagram of the spectral line of Raman spectrum.
Fig. 8 is that Rogor sterling dissolves in the 658cm determining worm amidine solution and acetone
-1the relation of signal intensity and concentration illustrates.
Fig. 9 is the acetone volume accounting that obtains of acetone diluted dimethylbenzene and 1706cm
-1the relation diagram of signal intensity.
Figure 10 is the acetone volume accounting that obtains of acetone diluted efficient cyhalothrin emulsifiable concentrate (GLFQ) and 1706cm
-1the relation diagram of signal intensity.
Figure 11 is the acetone volume accounting that obtains of acetone diluted toluene and 1706cm
-1the relation diagram of signal intensity.
Figure 12 is that the relation that Rogor sterling dissolves in 658/1706 relative intensity and concentration of determining worm amidine solution and acetone illustrates.
Figure 13 is the concentration curve diagram of determining worm amidine.
Figure 14 is the concentration curve diagram of chlopyrifos.
Embodiment
Below in conjunction with the drawings and the specific embodiments, the present invention is described in detail.
Invention comprises hardware unit and software systems, and hardware comprises as lower part:
One, Portable Raman spectrometer 1
Parameter: excitation wavelength: 785nm ± 1nm, spectral range: 175cm
-1-3150cm
-1, spectral resolution 10cm
-1912nm, detecting device: TE refrigeration ccd array, pixel 2048 × 1 pixel14 μm × 200 μm each pixels, laser output power >300mW, integral time 5 Hao Miao – 2 minutes.
Two, diameter 22mm sample bottle, solvent bottle are some; 5ml pipettor 1, is equipped with transfer pipet some; Portable electronic balance 1; The former medicament of Fluorescence Quenching Agent (solid, the product being numbered YZ-903 provided by Shanghai Shen Zhi Chemical Industry Science Co., Ltd), analysis pure acetone, distilled water are some.
Three, test fixture.
A kind of concrete grammar step of farm chemical emulsion preparation being carried out to the method for field quick detection of the present invention is as follows:
A. prepare:
Collect the raman signatures of 49 kinds of farm chemical emulsion preparations at solution system, be that 49 kinds of farm chemical emulsion preparations distribute resolution feature, by these features stored in database, call when carrying out composition identification for data processing software.
49 kinds of farm chemical emulsion preparations are: D.D.T. (dichloro-diphenyl-trichloroethane) T, dicofol, γ-benzene hexachloride, D.D.T. (dichloro-diphenyl-trichloroethane) D, Aldicarb, carbofuran, terbufos, acephatemet, isocarbophos, Isofenphos methyl, α-benzene hexachloride, parathion-methyl, parathion, D.D.T. (dichloro-diphenyl-trichloroethane) E, fenvalerate, Azodrin, phosphamidon, ethiprole, phonetic mould amine, orthene, methidathion, malathion, fenifrothion, decis, cypermethrin, DDVP, Rogor, Fenpropathrin, chlopyrifos, diazinon, Profenofos, Difenoconazole, Methomyl, carbaryl, Hostathion, Imidacloprid, pyridaben, triazolone, Biphenthrin, diflubenzuron, phoxim, Phosalone, gamma cyhalothrin, Avermectin, procymidone, iprodione, vinclozolin, determine worm amidine, Bravo.
B. prepare Fluorescence Quenching Agent, measure the density of farm chemical emulsion preparation:
B1. prepare Fluorescence Quenching Agent: 50mg fluorescence is eliminated former medicament and dissolves in 1ml water, inject 9ml pure acetone after dissolving completely, fully mix, the Fluorescence Quenching Agent (hereinafter referred to as " 0.6% Fluorescence Quenching Agent ") of obtained mass percent about 0.6%;
B2. the density of farm chemical emulsion preparation is measured: the sample bottle of load sample is placed on electronic balance, clear 0,1ml sample is got with pipettor, inject sample bottle completely, record now quality, then clear 0, repeat above step twice, finally ask three inferior quality mean values to be exactly the density of farm chemical emulsion preparation.
C. first round test:
C1. get farm chemical emulsion preparation to sample bottle, add Fluorescence Quenching Agent by multiple;
Be in particular: pipette 0.5ml farm chemical emulsion preparation to sample bottle with pipettor, (amount of the Fluorescence Quenching Agent at every turn added is the multiple of farm chemical emulsion preparation to add Fluorescence Quenching Agent by multiple, as 0.5ml, 1ml, 1.5ml, 2ml etc.), sample bottle is placed into test point, sample bottle center line is aimed at order probe laser window center, window distance sample bottle surface 2 ~ 3mm, window height center should higher than sample pellet layer surface at least 1mm; 1 minute should be left standstill to the front sample of test after adding Fluorescence Quenching Agent at every turn;
C2. start the test procedure of Raman spectrometer, open Raman spectrometer, open testing software interface, setting laser light intensity is 100%, and integral time is 2 × 35000 milliseconds;
C3. farm chemical emulsion preparation is tested; When observe signal base line be on close level 30000 time, start the first round test, follow-on test three times also records extension rate, store data; The complete rear rotation sample bottle of each survey is about an angle of 90 degrees, then measures next time.
D. second take turns test: after the first round tested, then add Fluorescence Quenching Agent by multiple and farm chemical emulsion preparation is surveyed in examination, when observe signal base line be on close level 20000 time, follow-on test three times also records extension rate, stores data; The complete rear rotation sample bottle of each survey is about an angle of 90 degrees, then measures next time.
E. Data Management Analysis: by data processing software process data, obtain each qualitative test result, taking turns test if a certain to have twice or more result display containing certain composition, then judge that farm chemical emulsion preparation contains this composition.
F converted score value: the peak intensity provided according to density and the data processing of extension rate, farm chemical emulsion preparation, and peak intensity and concentration relationship formula, converse the concentration value of farm chemical emulsion preparation.
The assay method of peak intensity and concentration relationship is specially: Fluorescence Quenching Agent is dissolved in the agent of pesticide original medicine sterling, is made into five groups of solution that concentration is respectively 0.5%, 1%, 2%, 5%, 10% respectively; If the concentration of farm chemical emulsion preparation is higher, then increase the solution that concentration is respectively 25%.Testing often organizing solution, in triplicate, then processing often organizing data, obtaining the peak value at the ionization meter peak often organizing solution, get the average peak that three mean value draws the ionization meter peak often organizing solution; Obtain the interior mark peak-to-peak signal 1706cm often organizing solution equally
-1peak value, get three mean values, averaging of income peak value obtains the acetone 1706cm of 100% concentration divided by 9/10
-1average peak; The average peak at the ionization meter peak often organized and the acetone 1706cm of 100% concentration
-1the ratio of average peak is the relative intensity of this group solution, and the concentration of the relative intensity and this group of getting five groups of (six groups) solution carries out linear regression analysis, obtains the linear relationship of peak intensity and concentration relationship.
The concentration value conversing farm chemical emulsion preparation is specially: according to the intensity level at echo signal peak, the concentration value after going out to dilute by peaks relative intensities and concentration relationship formula scales, and the concentration value after dilution is multiplied by quality extension rate and obtains the concentration value before diluting.
Wherein, described peaks relative intensities equals the intensity level at echo signal peak and the acetone 1706cm of 100% concentration
-1the ratio of signal; The acetone volume accounting in solution is extrapolated, the acetone 1706cm of actual measurement according to extension rate
-1signal intensity just converses the acetone 1706cm of 100% concentration divided by acetone volume accounting
-1the intensity of interior mark signal; Wherein, acetone volume accounting and extension rate close and are
quality extension rate and extension rate close and are
A kind of principle of work of farm chemical emulsion preparation being carried out to the method for field quick detection of the present invention is as follows:
To detect from farm chemical emulsion preparation and whether contain a certain composition, just need to know this composition raman signatures in solution system.The raman signatures of the farm chemical emulsion preparation of sterling can partly be covered in solution system, but its main feature still can manifest, and Raman shift values is substantially constant, contrasted from the Raman spectrum of chlopyrifos solution of 10% of Fig. 1 and the Raman shift values of the Raman spectrum of the chlopyrifos of sterling and illustrate, upper figure in Fig. 1 is the Raman spectrum of the chlopyrifos solution of 10%, and figure below is the Raman spectrum of the chlopyrifos of sterling.
The farm chemical ingredients recognition methods that the present invention adopts, be different from the full spectrum discrimination method of traditional Raman spectroscopy for pure material completely, carry out based on the several resolution features extracted by its solution system raman signatures to the identification of a certain composition, this method has higher reliability in limited detection material category, and sensing range is identified with the resolution feature of more material and easily extensible.
The present invention have collected 18 kinds of forbiddings altogether, limit the use of agricultural chemicals and 31 kinds of common pesticides in the raman signatures of solution system is assigned with resolution feature for all agricultural chemicals, and these features are stored into database confession data processing software and call and carry out composition identification.
18 kinds of forbiddings, limit the use of agricultural chemicals and comprise: D.D.T. (dichloro-diphenyl-trichloroethane) T, dicofol, γ-benzene hexachloride, D.D.T. (dichloro-diphenyl-trichloroethane) D, Aldicarb, carbofuran, terbufos, acephatemet, isocarbophos, Isofenphos methyl, α-benzene hexachloride, parathion-methyl, parathion, D.D.T. (dichloro-diphenyl-trichloroethane) E, fenvalerate, Azodrin, phosphamidon, ethiprole.
31 kinds of common pesticides comprise: phonetic mould amine, orthene, methidathion, malathion, fenifrothion, decis, cypermethrin, DDVP, Rogor, Fenpropathrin, chlopyrifos, diazinon, Profenofos, Difenoconazole, Methomyl, carbaryl, Hostathion, Imidacloprid, pyridaben, triazolone, Biphenthrin, diflubenzuron, phoxim, Phosalone, gamma cyhalothrin, Avermectin, procymidone, iprodione, vinclozolin, determine worm amidine, Bravo.
As a kind of field fast detection method, what the present invention was equipped with is Portable Raman spectrometer, in general the use test condition of Portable Raman spectrometer is very wide, but owing to needing higher signal to noise ratio (S/N ratio) to the constituent analysis of farm chemical emulsion preparation, the present invention still carries out necessary optimization to test condition and determines, comprise light intensity, integral time, sample container, probe and sample distance, fixture for testing etc., all subsidiary condition all meet execute-in-place requirement.
Test condition after optimization be 100% light intensity, 2 × 35 second integral time, by the sample bottle load sample of diameter 22mm and probe distance sample bottle 2 ~ 3mm.
Most farm chemical emulsion preparation contains a large amount of fluorescent materials, can be produced strong fluorescence during test by the laser irradiation of Raman spectrometer, and interference even covers Raman signal.The present invention adopts interpolation Fluorescence Quenching Agent weaken the method that missible oil dilutes or eliminate fluorescence, relative to polarization modulation method, shift frequency excitation method, HF modulation method, gate method etc. conventional in Raman spectrum test, have simple, effective, do not need reforming equipment and low cost and other advantages.Fluorescence Quenching Agent formula of the present invention, is optimized for varying environment temperature effect, stable in properties and do not impact test result, disturb.Fig. 2 be 3% determine worm amidine solution under different diluting condition Raman signal diagram, be followed successively by 3% from top to bottom and determine worm amidine stoste (curve with ◇ mark in figure), 3% determines worm amidine under acetone 24 times of diluting conditions, 3% determine worm amidine under Fluorescence Quenching Agent 10 times of diluting conditions (in figure be with+mark curve), 3% determine worm amidine under Fluorescence Quenching Agent 20 times of diluting conditions (in figure with ■ mark curve) Raman signal, test condition is 100% light intensity, 2 × 35 second integral time, and display Fluorescence Quenching Agent is to the eliminating effect of fluorescence.
Consider the factors such as the difficulty of enforcement, cost, the present invention adopts that the simple algorithm processing signals of independent development is round and smooth, peak identification, baseline value calculates, peak intensity calculates and qualitatively judges, the quantitative task such as calculating, the method is short for operation time, be easy to realize automatic process, and provide cosmic rays vestiges and eliminate this unique function, there is larger help to minimizing erroneous judgement.
Quantitative measurment of the present invention is by substance for calculation characteristic peak intensity and converts according to this material peak intensity and concentration relationship and realize, find in research that different solution systems has a significant impact peak intensity and concentration relationship, use internal standard method can more effectively lower this impact.The internal standard method that the present invention uses with general adopt in system, add fixing internal standard compound different, it directly adopts the acetone 1706cm of Fluorescence Quenching Agent
-1characteristic signal, does not need to add internal standard compound in addition, enormously simplify operation.But this characteristic signal intensity changes because of extension rate, dynamic, the present invention then according to this characteristic signal intensity and the volume accounting of acetone in solution system proportional, converse the signal intensity of corresponding acetone 100% concentration as interior mark signal intensity, thus address this problem.
Raman spectrometer is not opened at laser also can receive some signals to during sample irradiation, and main source is the high energy spectral line comprising cosmic rays, is called " dark signal ", and Fig. 3 is the dark signal diagram that Raman spectrometer obtains.When Raman spectrometer is tested, first carry out dark signal scanning when laser shutdown and tracer signal, and then open laser and carry out signal scanning, the original signal of acquisition is reduced as final test signal after dark signal, and Fig. 4 is the original signal diagram that Raman spectrometer obtains.As shown in Figure 3, Fig. 3 is the dark signal diagram that Raman spectrometer obtains, and can see in dark signal and have the king-sized spectral line of some intensity to be exactly cosmic rays, and its feature is intensity and instability, even cuts in and out.The integral time adopted due to the present invention is larger, interval between dark signal scanning and signal scanning is larger, each spectral line of dark signal of twice sweep will be caused, especially cosmic ray intensity value is unequal, cause and to stay after reducing or the signal " vestiges " of negative or positive, affect the judgement of signal, will manage to eliminate for this reason.When cosmic rays occurs, long (Raman shift) intensity of single step increases suddenly, then suddenly declines at next step again.Therefore can arrange " dark signal intensity slope (DarkR) " of a sign dark signal change rate of strength, its numerical value is this step dark signal intensity and the ratio of previous step intensity difference with two step spacing, then one threshold values r is set, when when this step DarkR is greater than r, next step DarkR is less than-r, namely judge originally to walk out of existing cosmic rays.For the beans-and bullets shooter occurring cosmic rays, no matter its final signal intensity how, all rigid mean value being set to back and next step intensity, so just can effective erasure signal " vestiges ".Fig. 5 is the signal diagram after reducing dark signal, and Fig. 6 is the signal diagram after round and smooth process, can be seen, by 1513cm by Fig. 6
-1" vestiges " that the cosmic rays that place occurs causes " have been erased " through above method process.
For " final signal " of other beans-and bullets shooter that spectrometer provides, littlely to beat for eliminating some, the present invention adopts following methods to do further round and smooth process, if In, In-1, In+1 is respectively this step, previous step, next step " final signal " intensity, then this step signal intensity Ins after round and smooth is: Ins=0.15 × (In-1)+0.7 × In+0.15 × (In+1).
The identification at peak is mainly through judging whether the pattern formed by the spectral line tendency polarity in a segment limit meets the threshold requirements of specifying and come.First (intensity added value is divided by two step spacing to calculate this intensity added value (SLP) walking relative previous step and intensity increment rate, SLPR), positive and negative again according to SLPR, judge the tendency polarity of this step, SLPR is timing, be designated as P, be designated as N time negative, Fig. 7 is the tendency polarity diagram of the spectral line of Raman spectrum.When processing practical problems, can find to there are some beans-and bullets shooters, its SLPR, very close to 0, greatly between-20 to 20, is difficult to judge that it belongs to rising or downward trend.Such point, if there is in summit position, often destroys the complete procedure that a peak is formed, affects peak identification, and in fact such point just causes due to signal random fluctuation.Therefore the present invention specifies a threshold values p, and when SLPR is between-p to p, the tendency polarity of this step follows previous step, and serious offense p is P, and little mistake-p is N, to avoid this impact.
After determining the tendency polarity of each step, after investigating a bit of spectral line, a series of polar mode will be produced, as PPNN represents that continuous two steps that rise connect two steps that decline again, set the threshold values of corresponding SLP or SLPR again for each pattern, just can judge whether peak occurs.The peak condition for identification of current use is as shown in table 1.
Table 1
| Polar mode | Peak Conditions |
| PNP | The SLPR value that the SLPR value of N is less than-150, the second P is greater than 75 |
| NPN | The SLPR value of P is greater than 150, and the SLPR value of second N is less than-75 |
| PPNN | The SLP value summation of two P is greater than 300, and the SLP value summation of two N is less than-300 |
| PPPNN | The SLP value summation of three P is greater than 225, and the SLP value summation of two N is less than-225 |
| PPPPNN | The SLP value summation of four P is greater than 150, and the SLP value summation of two N is less than-150 |
| PPPPNNN | The SLP value summation of four P is greater than 150, and the SLP value summation of three N is less than-150 |
| PPNNN | The SLP value summation of two P is greater than 225, and the SLP value summation of three N is less than-255 |
| PPNNNN | The SLP value summation of two P is greater than 150, and the SLP value summation of four N is less than-150 |
| PPPNNNN | The SLP value summation of three P is greater than 150, and the SLP value summation of four N is less than-150 |
Iting is noted that the threshold values set in the algorithm, is the empirical value repeatedly contrasting with actual conditions according to result of calculation and draw, is not unalterable, should make adjustment according to the change of the factor such as equipment state, Spectral Characteristic.If equipment is after Long-Time Service, laser power declines, and signal weakens, and now can consider that the testing result of according to standard sample suitably reduces threshold values.The and for example Spectral Characteristic of current system, 1750cm
-1baseline afterwards comparatively before simple, smooth, material property peak rises and falls also comparatively mild, therefore can consider 1750cm
-1peak identification afterwards adopts lower threshold values.In a word, the agriculture products of threshold values ensures that result of calculation is as far as possible close to actual conditions exactly, is adjustable, but must ensure simultaneously the standard checked be stablize constant, reliable.Should consider that when algorithm for design software threshold values is existed in the citable database that can conveniently revise.
A kind of composition, by differentiating feature by after qualitative distinguishing, obtain its concentration, namely realize quantitative measurment, just must know the peak intensity of its a certain characteristic peak, also will know the corresponding relation of peak intensity and concentration, just can converse concentration.Does is the problem that first the present invention proposes the relation which factor affects peak intensity and concentration when discussing the relation of peak intensity and concentration? according to the principle of Raman spectrum, raman scattering spectrum not only with the component of sample, also relevant with the factor such as structure, form.For the actual commercially available agricultural chemical cream preparation that will measure, even same effective constituent, other assistant agent formula also has bigger difference, therefore to whole solution system, component, structure, form have very big difference, same composition is in the background that difference is larger, and it is completely possible that its signal intensity is affected.Theoretical in order to confirm this, the present invention is dissolved in pure acetone respectively Rogor sterling and is determined in worm amidine solution, then at variable concentrations horizontal survey Rogor 658cm through fluorescence Processing for removing (with 0.6% Fluorescence Quenching Agent dilution)
-1signal intensity.Fig. 8 is that Rogor sterling dissolves in the 658cm determining worm amidine solution and acetone
-1the relation of signal intensity and concentration illustrates, and as seen from Figure 8, Rogor sterling dissolves in the 658cm determining worm amidine solution
-1relation (with the lines that ■ marks in the figure) formula of signal intensity and concentration is y=5E-06x+0.006, R
2=0.99; Rogor sterling dissolves in the 658cm of pure acetone
-1relation (lines be with in figure ▲ marked) formula of signal intensity and concentration is y=4E-06x+0.001, R
2=0.998.As shown in table 2, under different concentration levels, Rogor is at the 658cm of two kinds of solution systems
-1signal intensity has larger difference, and which demonstrating different solution systems has impact to the twocomponent signal intensity of dissolving in wherein really.
Table 2
| Concentration | Determine worm amidine 658cm -1Mean intensity | Acetone 658cm -1Mean intensity | Deviation |
| 0.2% | - | 530 | - |
| 0.5% | - | 967 | - |
| 1.0% | 1453 | 1999 | 37.6% |
| 2.0% | 2152 | 4160 | 93.3% |
| 5.0% | 9337 | 12886 | 38.0% |
| 10.0% | 19465 | 24840 | 27.6% |
For the impact caused of fluctuating because of measurement system inherence or external factor, in measuring technology, conventional internal standard method is eliminated or is offset, and its principle is, chooses internal standard compound signal intrinsic in system as with reference to signal, forms relative signal intensity with echo signal.When system factors vary, it also acts on reference signal to the impact of echo signal, therefore will be weakened on the impact of relative signal intensity.In the present invention, due to the use of Fluorescence Quenching Agent, using acetone as internal standard compound, and the 1706cm of acetone
-1signal is because of very suitable to interior mark reference signal with other known features peak-to-peak signal zero lap.
But general internal standard compound its content in system is all constant, and the concentration of acetone in system changes because required extension rate (the volume accounting of acetone in system) is different, how to obtain corresponding fixed concentration (100%) signal value by measured signal intensity?
Have studied acetone and dilute toluene, dimethylbenzene, efficient cyhalothrin emulsifiable concentrate (GLFQ) and the acetone volume accounting obtained and 1706cm respectively
-1the relation of signal intensity, Fig. 9 ~ Figure 11 is acetone 1706cm
-1intensity and volume accounting relation illustrate, from the data of Fig. 9 ~ Figure 11, for different solution, the volume accounting of acetone all with 1706cm
-1signal intensity has good linear proportional relation.Fig. 9 is the acetone volume accounting that obtains of acetone diluted dimethylbenzene and 1706cm
-1relation (lines with ■ mark in the figure) formula of signal intensity is y=37404x, R
2=0.960; Figure 10 is the acetone volume accounting that obtains of acetone diluted efficient cyhalothrin emulsifiable concentrate (GLFQ) and 1706cm
-1relation (lines be with in figure ▲ marked) formula of signal intensity is y=38773x, R
2=0.909; Figure 11 is the acetone volume accounting that obtains of acetone diluted toluene and 1706cm
-1relation (being with in figure ◆ the lines of the mark) formula of signal intensity is y=38164x, R
2=0.956.As long as therefore know the acetone volume accounting of surveyed solution, the 1706cm of 100% acetone under this condition just can be provided
-1signal value, as interior mark reference signal value.
Internal standard method is adopted to process the data of Rogor again, obtain result shown in Figure 12, Figure 12 is that the relation that Rogor sterling dissolves in 658/1706 relative intensity and concentration of determining worm amidine solution and acetone illustrates, relation (lines be with in figure ▲ marked) formula that Rogor sterling dissolves in 658/1706 relative intensity and the concentration of determining worm amidine solution is y=0.148x+0.007, R
2=0.991; Rogor sterling dissolves in 658/1706 relative intensity of pure acetone and relation (being with in figure ◆ the lines of the mark) formula of concentration is y=0.142x+0.001, R
2=0.999.From table 3, adopt internal standard method process, when concentration is higher (5%, 10%), deviation obviously reduces.
Table 3
| Concentration | Determine worm amidine 658/1706 mean intensity | Acetone 658/1706 mean intensity | Deviation |
| 0.2% | - | 1.4% | - |
| 0.5% | - | 2.6% | - |
| 1.0% | 3.8% | 5.5% | 44.9% |
| 2.0% | 5.5% | 11.4% | 107.8% |
| 5.0% | 30.9% | 34.1% | 10.4% |
| 10.0% | 61.5% | 69.0% | 12.1% |
From discussing above, for reducing background solution to the impact of peak intensity, when carrying out the mensuration of the peak intensity of each farm chemical emulsion preparation sample and concentration relationship, the solution used should as far as possible close to solution during actual measurement, 0.6% Fluorescence Quenching Agent must be used to dilute to eliminate the impact of fluorescence to farm chemical emulsion preparation due to during actual measurement, extension rate most cases is greater than more than 3 times, during actual measurement, solution is by containing relatively large Fluorescence Quenching Agent composition, and therefore selected 0.6% Fluorescence Quenching Agent of the present invention is as mensuration solution.
Raman signatures peak-to-peak signal for quantitative measurment is selected from a certain feature differentiated in feature, the principle selected is that this peak-to-peak signal must be comparatively strong and to be stablely not easily disturbed, and the peak between each composition selects there is not too much overlap, because if two compositions with overlapping ionization meter peak occur simultaneously, directly will affect measuring accuracy, certainly, such probability is not too large.
The assay method of peak intensity and concentration relationship is as follows: sterling is dissolved in 0.6% Fluorescence Quenching Agent, is first made into 0.5% strength solution and tests by optimal conditions, in triplicate, then progressively increase concentration.General point 0.5%, 1%, 2%, 5%, 10% etc. 5 groups, if the concentration of the cream preparation of this agricultural chemicals is higher, also can increase test 25% concentration group.Processing often organizing data, obtaining the peak value at ionization meter peak, get three times on average.Obtain interior mark peak-to-peak signal 1706cm equally
-1peak value, gets three times on average.Because 0.6% Fluorescence Quenching Agent water and acetone ratio are 1:9, averaging of income peak value also just will obtain the acetone 1706cm of 100% concentration divided by 9/10
-1peak value.The average peak at ionization meter peak and 1706cm
-1the ratio of average peak is exactly the relative intensity of this group, gets 5 groups of (or 6 groups) relative intensities and carries out linear regression analysis with corresponding concentration, just can obtain both linear relationships as shown in Figure 13,14.For 50 kinds of farm chemical ingredients, the overwhelming majority has good linear relationship, R
2general all more than 0.95.Draw the concentration conversion of linear relationship formula for actual measurement of each composition.
During actual measurement, as long as know the intensity level at echo signal peak, just concentration value can be gone out, in conversion process by peak strength and concentration relationship formula scales, certainly the acetone volume accounting in solution also will be extrapolated according to extension rate, then 1706cm corresponding when conversing 100% concentration
-1the intensity of interior mark signal.For the situation of use 0.6% Fluorescence Quenching Agent, acetone volume accounting and extension rate relation as follows:
The concentration value conversed through previous step is after dilution, also needs to be multiplied by the concentration value that extension rate is only stoste.In practical operation, conveniently, what adopt is by volume quantitative method, namely measure 0.6% certain Fluorescence Quenching Agent volume with pipettor to dilute, and general concentration value is measured by mass, therefore also volume dilution multiple will be converted to quality extension rate, this just needs the density knowing former farm chemical emulsion preparation and 0.6% Fluorescence Quenching Agent.The density of 0.6% Fluorescence Quenching Agent is substantially constant and known, the density of stoste farm chemical emulsion preparation then needs to measure, and method gets 1ml missible oil with pipettor, weighs its quality with portable electronic balance, average in triplicate, this method also can be implemented at the scene.
Adopt a kind of method of farm chemical emulsion preparation being carried out to field quick detection of the present invention to carry out quick detection validation to 37 kinds of pesticide samples, wherein commercially available agricultural chemical cream preparation is bought in 9 markets, makes qualitative reaction according to the test of its nominal composition.Commercially available agricultural chemical cream preparation and 13 certain agriculture inspection institute regular inspection commercially available agricultural chemical cream preparations are bought in other 8 markets, and first with the present invention's test, then hand over certain agriculture to examine qualitative and quantitative measurement of doing, qualitative determination uses chromatographic mass spectrometry interlock instrument.There are 7 to buy commercially available agricultural chemical sample in market again, mix a certain amount of variety classes banned pesticides pure sample product, test oneself and do quantitative and qualitative inspection.Result is summed up as shown in table 4.
Table 4
According to test result, can following judgement be made to the present invention and evaluate:
Of the present inventionly measure rate 76.7%(rate of failing to report: 23.3%), measuring rear accuracy rate is 95.7%(rate of false alarm: 4.3%), and qualitative total accuracy rate is 73.3%.Failing to report main cause is that the rear constituent concentration of stoste or dilution is low.
Have 3 samples to contain 3 kinds or 4 kinds of effective constituents (all containing pyridaben, ethiprole), qualitative test is except a kind of composition cannot be measured, and other is all correct, and display the present invention mixes solution to multicomponent to be had and detect resolution characteristic preferably.
For resolution feature at 1750cm
-1above composition, has stronger detectability as determined worm amidine, ethiprole, Bravo etc.As 9 qualitative detectings for ethiprole, have and fail to report (original liquid concentration is only 0.05%) for 1 time, 2 wrong reports (wherein once find the Interference Peaks 17.19 at closely ethiprole peak on chromaticness interlock instrument, ethiprole peak is 17.22), detection limit can reach stoste 3%.
7 forbidden amphetamine doped samples (are respectively in 40% this phoxim vertical and mix 26% Azodrin, 40% speed is slaughtered in methidathion and is mixed 9.7% dicofol, 5% determines to mix 8.7% γ-benzene hexachloride in worm amidine-NYJC12154, 15.5% parathion-methyl is mixed in 48% Le Siben chlopyrifos, 40% speed is slaughtered in methidathion and is mixed 21.1% Isofenphos methyl, 5% determines to mix 23.2% Aldicarb in worm amidine-NYJC12154, mix 28.4% carbofuran in 2.5% dragon letter gamma cyhalothrin) in 5 can be detected (Azodrin and Aldicarb undetected), visible the present invention has good detectability to the agricultural chemicals having forbidden amphetamine to adulterate.
Finally should be noted that; above embodiment is only for illustration of technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (6)
1. farm chemical emulsion preparation is carried out to a method for field quick detection, it is characterized in that: it comprises the following steps:
A. prepare: collect the raman signatures of several farm chemical emulsion preparation at solution system, differentiate feature for several farm chemical emulsion preparation distributes, by these features stored in database, call when carrying out composition identification for data processing software;
B. prepare Fluorescence Quenching Agent, measure the density of farm chemical emulsion preparation; Preparation Fluorescence Quenching Agent is specially: 50mg fluorescence is eliminated former medicament and dissolves in 1ml water, injects 9ml pure acetone, fully mix, be mixed with Fluorescence Quenching Agent after dissolving completely;
C. first round test: get farm chemical emulsion preparation to sample bottle, add Fluorescence Quenching Agent by multiple, then start the test procedure of Raman spectrometer, test farm chemical emulsion preparation; When observe signal base line be on close level 30000 time, start the first round test, follow-on test three times also records extension rate, store data;
D. second take turns test: after the first round tested, then add Fluorescence Quenching Agent by multiple and farm chemical emulsion preparation is surveyed in examination, when observe signal base line be on close level 20000 time, follow-on test three times also records extension rate, stores data;
E. Data Management Analysis: by data processing software process data, obtain each qualitative test result, taking turns test if a certain to have twice or more result display containing certain composition, then judge that farm chemical emulsion preparation contains this composition;
F. converted score value: according to extension rate, the peak intensity that the density of farm chemical emulsion preparation and data processing provide, and peak intensity and concentration relationship formula, converse the concentration value of farm chemical emulsion preparation, in described step f converted score value, the assay method of peak intensity and concentration relationship is specially: pesticide original medicine sterling is dissolved in Fluorescence Quenching Agent, be made into concentration respectively and be respectively 0.5%, 1%, 2%, 5%, five groups of solution of 10% or be made into concentration respectively and be respectively 0.5%, 1%, 2%, 5%, 10%, six groups of solution of 25%, test often organizing solution, in triplicate, then process often organizing data, obtain the peak value at the ionization meter peak often organizing solution, get the average peak that three mean value draws the ionization meter peak often organizing solution, obtain the interior mark peak-to-peak signal 1706cm often organizing solution equally
-1peak value, get three mean values, averaging of income peak value obtains the acetone 1706cm of 100% concentration divided by 9/10
-1average peak, the average peak at the ionization meter peak often organized and the acetone 1706cm of 100% concentration
-1the ratio of average peak is the relative intensity of this group solution, and the concentration of the relative intensity and this group of getting five groups of solution or six groups of solution carries out linear regression analysis, obtains the linear relationship of peak intensity and concentration relationship.
2. a kind of method of farm chemical emulsion preparation being carried out to field quick detection according to claim 1, it is characterized in that: in described step a, described farm chemical emulsion preparation comprises following 49 kinds: D.D.T. (dichloro-diphenyl-trichloroethane) T, dicofol, γ-benzene hexachloride, D.D.T. (dichloro-diphenyl-trichloroethane) D, Aldicarb, carbofuran, terbufos, acephatemet, isocarbophos, Isofenphos methyl, α-benzene hexachloride, parathion-methyl, parathion, D.D.T. (dichloro-diphenyl-trichloroethane) E, fenvalerate, Azodrin, phosphamidon, ethiprole, phonetic mould amine, orthene, methidathion, malathion, fenifrothion, decis, cypermethrin, DDVP, Rogor, Fenpropathrin, chlopyrifos, diazinon, Profenofos, Difenoconazole, Methomyl, carbaryl, Hostathion, Imidacloprid, pyridaben, triazolone, Biphenthrin, diflubenzuron, phoxim, Phosalone, gamma cyhalothrin, Avermectin, procymidone, iprodione, vinclozolin, determine worm amidine, Bravo.
3. a kind of method of farm chemical emulsion preparation being carried out to field quick detection according to claim 1, it is characterized in that: in described step b, the density measuring farm chemical emulsion preparation is specially: sample bottle is placed on electronic balance, clear 0, get 1ml farm chemical emulsion preparation, inject sample bottle completely, record now quality; Then clear 0, repeat above step twice, finally ask the mean value of three inferior qualities to draw the density of farm chemical emulsion preparation.
4. a kind of method of farm chemical emulsion preparation being carried out to field quick detection according to claim 1, it is characterized in that: in described step c, the test procedure starting Raman spectrometer is specially setting: start Raman spectrometer, open testing software interface, setting laser light intensity is 100%, and integral time is 2 × 35000 milliseconds.
5. a kind of method of farm chemical emulsion preparation being carried out to field quick detection according to claim 1, it is characterized in that: in described step f, the concentration value conversing farm chemical emulsion preparation is specially: according to the intensity level at echo signal peak, concentration value after going out to dilute by peaks relative intensities and concentration relationship formula scales, the concentration value after dilution is multiplied by quality extension rate and obtains the concentration value before diluting.
6. a kind of method of farm chemical emulsion preparation being carried out to field quick detection according to claim 5, is characterized in that: described peaks relative intensities equals the intensity level at echo signal peak and the acetone 1706cm of 100% concentration
-1the ratio of signal; The acetone volume accounting in solution is extrapolated, the acetone 1706cm of actual measurement according to extension rate
-1signal intensity just converses the acetone 1706cm of 100% concentration divided by acetone volume accounting
-1the intensity of interior mark signal; Wherein, acetone volume accounting and extension rate close and are
; Quality extension rate and extension rate close and are
.
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| CN104142321A (en) * | 2014-07-24 | 2014-11-12 | 江西农业大学 | Method for fast detecting surface enhancing Raman spectrums of pesticide residues in tea leaves |
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