CN102565015A - Method for quickly and quantitatively determining residual sulfonylurea weedicide in water sample - Google Patents
Method for quickly and quantitatively determining residual sulfonylurea weedicide in water sample Download PDFInfo
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- CN102565015A CN102565015A CN2011104395088A CN201110439508A CN102565015A CN 102565015 A CN102565015 A CN 102565015A CN 2011104395088 A CN2011104395088 A CN 2011104395088A CN 201110439508 A CN201110439508 A CN 201110439508A CN 102565015 A CN102565015 A CN 102565015A
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Abstract
The invention discloses a method for quickly and quantitatively determining residual sulfonylurea weedicide in a water sample. The method comprises the following steps: taking the water sample containing the residual sulfonylurea weedicide; adding 0.1mol/L aqueous solution of SDS (Sodium-Dodecyl Sulphate); adjusting the pH value to be 7-12; filling with distilled water to reach the volume and enabling the final concentration of the SDS to be 2.0-2.5*10<-3>mol/L and obtaining a sample solution to be determined; carrying out ultraviolet radiation on the sample solution to be determined at 25DEG C for 120-150s; then determining a fluorescent signal strength value of the sample solution to be determined by using a fluorescence spectroscopy; and quantitatively determining respectively residual amounts of sulfometuron methyl, rimsulfuron and chlorsulfuron in the sulfonylurea weedicide of the sample to be determined according to a linear standard curve. The method disclosed by the invention is short in detection time and high in sensitivity and can be used for batch detection; and the sensitivity of the method is higher than a detection limit of a high performance liquid chromatography ultraviolet detector in different mediums.
Description
(1) technical field
The present invention relates to the method for the residual quantitative determination of sulfonylurea herbicide in a kind of water sample, particularly the grand mensuration of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur.
(2) background technology
Along with the liberation of agrotechnical modernization and yield-power, chemical herbicide has become the main means of control farmland weed harm.Since the eighties in last century, E.I.Du Pont Company released first ultra high efficiency sulfonylurea herbicide (green sulphur is grand); Sulfonylurea herbicide has become the important herbicide of world today's farmland weed control; Also be widely used in China, use tribenuron-methyl+metsulfuron-methyl mixture controlling weeds as 31% rice field is arranged at jiangsu wuxi.This type herbicide consumption is low especially, and the amount of application of per hectare only needs 2～75g active component; And selectivity is strong, and very big to the sensitivity differences of Different Crop, its minimal residue can produce poisoning to late stubble sensitive crop.The residual life of swelling in soil like green sulphur, is longer, has jeopardized non-target plant, and stubble is that the wheatland of corn, soybean, cotton is disabled behind China dry farming area.In wheat rice continuous cropping district, because of the poisoning to paddy rice also can take place in improper use, nineteen ninety-five Shenyang the major accident of the grand hazard rice of green sulphur once took place, cause 533.4hm
2The rice field is injured, wherein 267hm
2Total crop failure
[6]Hebei province in 1992 uses the wheatland behind the metsulfuron-methyl, causes the large tracts of land poisoning for back stubble corn]; 1994 in Jiangsu Province the rape field use ethametsulfuron, make the poisoning of back stubble paddy rice occurrence of large-area.In China the report of many sulfonylurea herbicides to late stubble sensitive crop generation poisoning incident arranged, similar report is abroad also arranged.Given this, MRL standard (MRLs) has been formulated to herbicide residue in the farm imports in succession in developed country or areas such as the U.S., European Union, Japan.U.S.'s regulation, from February, 2007, residual the limiting the quantity of of the sulfonylurea herbicide in the rice product is 0.05mg/kg.The MRL of the flupyrsulfuron-methyl-sodium of the positive list regulation broccoli of Japan, flazasulfuron, azimsulfuron, bensulfuron-methyl is 0.02mg/kg.Foramsulfuron and flazasulfuron are 0.01mg/kg in European Union's regulation lichee.Therefore, it is significant to the residual poisoning of control sulfonylurea herbicide to inquire into the residual analysis determining method of sulfonylurea herbicide.
Yet because the sulfonylurea herbicide consumption is low, the low and this low-residual concentration of its corresponding residual concentration characteristic just causes certain difficulty for the assay determination of this compounds in soil, water body, the crop.Therefore, the research of searching sulfonyl urea compound high-sensitivity detecting method has become one of focus of Related Research Domain.And the detection method of present existing sulfonyl urea compound, either time-consuming, or process is complicated, or rely on expensive instrument etc., and make it be difficult for popularizing, therefore be badly in need of seeking the detection method of easy relatively and rapid sensitive.
At present, measure residual mainly contain high performance liquid chromatography (HPLC), vapor-phase chromatography (GC), capillary electrophoresis, chromaticness couplet spectrometry (LC/MS), ELISA and the bioassay method of sulfonylurea herbicide in water and soil.
HPLC, GC method can detect the sample of 0.2 μ g/L, but light requirement is led detecting device, is difficult for penetration and promotion.The solsonylurea compounds thermally labile can not be with the direct assay determination of GC, must be with measuring behind the diazomethane derivatization.Recently, it is residual that usefulness LC/MS method such as Marck can detect 4 kinds of sulfonylurea herbicides of 6 μ g/kg in soil.But methods such as HPLC, GC, LC/MS all have tangible deficiency, promptly chromatographic column are had relatively high expectations, and single sample is measured consuming time longer.
Capillary electrophoresis is to adopt the liquid phase separation mensuration sulfonylurea herbicide of highfield residual; Detection method is UV, visible light, electrochemical process etc., can detect 0.5～1.0 μ g/kg, but because it adopts the electric field separates mode; Requiring detection material is ionic state or strong polarity; Can only detect the compound of ad hoc structure or the product behind the derivatization, single sample is consuming time also longer simultaneously, has limited the universality of its detection.
ELISA is to adopt chemiluminescence immunoassay method mensuration sulfonylurea herbicide residual, and detectability can reach 0.1～0.3 μ g/L, but the ELISA selectivity is strong, can only detect the compound of ad hoc structure, and the preparation of antibody is quite difficult.
Bioassay method is that effect is more direct with the sensitive plant plant of giving instruction, and it comprises earth culture biologicall test, water planting biologicall test, soil extract biologicall test and cellular incubation biologicall test.But earth culture biologicall test, soil extract biologicall test reflection is available state sulfonylurea herbicide in the soil, rather than total residual, and the cycle is longer.
Photochemistry XRF (PCF) is a kind of analytical approach that grows up the fifties in last century; Thereby be based on material absorbing ultraviolet-visible radiation generation photochemical reaction cause that the structure of material or character change; Such as form fluorescent emission functional group, take place fluorescence enhancing or quencher and fluorescent material excite and (or) emission wavelength phenomenon such as be moved; The fluoroscopic examination character of material is changed; Improve the sensitivity of fluorescence analysis and optionally a kind of method whereby, and advantage such as that XRF has is highly sensitive, the range of linearity is wide.PCF is a novel XRF of making derivative reagent with photon, has been widely used in the analysis of vitamin, agricultural chemicals, medicine and other fields at present.Guo Xiangqun etc. once reported the photochemistry fluorescence method of simultaneous determination vitamin B1, B6, and the method range of linearity is wide, and effect is better, and the detection limit of vitamin B1 and B6 is respectively 0.60 and 1.0 μ g/L.Wen Yuyun etc. have realized the residual highly sensitive detection of pyrethrin pesticide in the tealeaves with the PCF technology, have set up easy, reliable, sensitive pyrethrin pesticide method for detecting residue.Under the test condition of the best, the detection limit of five kinds of chrysanthemum ester classes can reach 12 μ g/kg].
etc. then studied under the room temperature solvent to the influence of the photochemistry fluorescence behavior of sulfamethazine; Detection limit is different with solvent variation, but is μ g/L level.PCF method detection speed is fast in addition, and usefulness PCF technology such as Sergei have at room temperature accurately detected 7 kinds of chlorophenoxy acid herbicides that are widely used in the 15min.Can find out that PCF is a kind of quick and sensitive detection method, in organic micro quantitative determination analysis, wide prospect is arranged.
There are some researches show, chlorine sulphur is grand, chlorimuronethyl, metsulfuron-methyl and sulfometuronmethyl behind ultraviolet lighting, its fluorescence intensity is undressed 3.7～48.3 times apparently higher than undressed compound.This shows that sulfonyl urea compound ultraviolet light chemistry reaction product has fluorescent characteristic, utilizes this characteristic, can set up the residual new method of a kind of fast detecting sulfonylurea herbicide.But use report that photochemistry fluorescence method method (PCF) carries out the sulfonyl urea compound retention analysis at present seldom.
(3) summary of the invention
The object of the invention provide a kind of fast, sensitivity higher detection trace sulfonylurea herbicide sulfometuronmethyl, rimsulfuron 25 or the grand residual photochemistry fluorescence analysis method of chlorine sulphur.
The technical scheme that the present invention adopts is:
The residual method of sulfonylurea herbicide in a kind of quantitative determination water sample; Said method is: get and contain the residual water sample of sulfonylurea herbicide; Add the 0.1mol/L SDS WS, regulating the pH value is 7～12, and using the distilled water constant volume to make the SDS final concentration is 2.0～2.5 * 10
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the grand standard items of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur respectively; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur carina property typical curve respectively, quantitatively predict in the testing sample grand separately residual of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur in the sulfonylurea herbicide according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
Standard items concentration is consistent with the concentration range of corresponding residuals in the testing sample in the standard items methanol solution of said variable concentrations.
Said typical curve is drawn as follows: respectively the grand standard items of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur are used dissolve with methanol, be mixed with 1 * 10 respectively
-3Mol/L sulfometuronmethyl methanol solution, 1 * 10
-3Mol/L rimsulfuron 25 methanol solution and 1 * 10
-3Mol/L chlorine sulphur swells methanol solution, adds the 0.1mol/L SDS WS more successively, is adjusted to pH 9 with corresponding pH damping fluid respectively again, and pH 7 and pH12 make the SDS final concentration be 2.0～2.5 * 10 with the distilled water constant volume
-3Mol/L obtains concentration successively and is respectively 0,2.0 * 10
-6, 4.0 * 10
-6, 6.0 * 10
-6, 8.0 * 10
-6, 1.0 * 10
-5The sulfometuronmethyl standard solution of mol/L, Sulfometuron Methyl standard solution and chlorine sulphur swell standard solution; And under the ultraviolet condition, shining 120～150s under 25 ℃; Measure fluorescence signal intensity value separately with XRF then, draw sulfometuronmethyl linear standard curve, Sulfometuron Methyl linear standard curve and chlorine sulphur carina property typical curve respectively.
The method of sulfometuronmethyl is in the said quantitative measurement water sample: get and contain the residual water sample of sulfonylurea herbicide, add the 0.1mol/L SDS WS, regulating pH value is 9, and it is 2.0～2.5 * 10 that use distilled water constant volume makes the SDS final concentration
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the sulfometuronmethyl standard items; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw the sulfometuronmethyl linear standard curve, quantitatively predict in the testing sample residual quantity of sulfometuronmethyl in the sulfonylurea herbicide according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
The method of rimsulfuron 25 is in the said quantitative measurement water sample: get and contain the residual water sample of sulfonylurea herbicide, add the 0.1mol/L SDS WS, regulating pH value is 7, and it is 2.0～2.5 * 10 that use distilled water constant volume makes the SDS final concentration
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the rimsulfuron 25 standard items; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw the rimsulfuron 25 linear standard curve, quantitatively predict in the testing sample rimsulfuron 25 residual quantity in the sulfonylurea herbicide according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
The grand method of chlorine sulphur is in the said quantitative measurement water sample: get and contain the residual water sample of sulfonylurea herbicide, add the 0.1mol/L SDS WS, regulating pH value is 12, and it is 2.0～2.5 * 10 that use distilled water constant volume makes the SDS final concentration
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the grand standard items of chlorine sulphur; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw chlorine sulphur carina property typical curve, quantitatively predict the residual quantity that chlorine sulphur swells in the sulfonylurea herbicide in the testing sample according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
Said adjusting pH value is 7～12nd, in order effectively to measure the herbicide of simultaneous multiple sulfonylureas in the WS, makes different sulfonylureas obtain the optimal light chemical reaction condition.As contain simultaneously in the water sample that sulfometuronmethyl is residual, Sulfometuron Methyl is residual and chlorine sulphur grand when residual; Sulfometuronmethyl is residual, Sulfometuron Methyl is residual and chlorine sulphur is grand residual in order effectively to measure; Needing to use three duplicate samples and regulate pH respectively is 9,7 and 12; After the photochemical reaction, can distinguish that effective mensuration sulfometuronmethyl is residual, rimsulfuron 25 is residual and chlorine sulphur grand residual.
Said sulfometuronmethyl is residual, rimsulfuron 25 is residual and the grand residual LDL of chlorine sulphur is respectively 3 μ g/L, 0.4 μ g/L and 0.5 μ g/L.
The grand content of sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur calculates as follows according to formula (1) in the testing sample according to the invention:
In the formula (1): sulfometuronmethyl, rimsulfuron 25 or the grand volumetric molar concentration (mol/L) of chlorine sulphur in the testing sample that ρ-calculating obtains according to typical curve;
V
1---draw the volume (mL) of testing sample;
V
2---the liquor capacity (mL) of volumetric flask;
The molal weight (g) that m---sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur are grand;
Compared with prior art; Beneficial effect of the present invention is mainly reflected in: the present invention is according to the advantage of PCF rapid sensitive; And sulfonyl urea compound ultraviolet light chemistry reaction product has fluorescent characteristic, set up the PCF rapid analysis of the grand minimal residue of sulfonylurea herbicide sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur, and has been applied to the express-analysis of natural water sample; Detection time is short; Highly sensitive, but batch detection is highly sensitive in the detection limit value of high performance liquid chromatography UV-detector in different medium.
(4) description of drawings
Fig. 1 sulfometuronmethyl content and I
FThe linear standard curve of value
Fig. 2 rimsulfuron 25 content and I
FThe linear standard curve of value
Grand content of Fig. 3 chlorine sulphur and I
FThe linear standard curve of value
(5) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
(1) medicament and reagent
Sulfometuronmethyl (sulfometuron-methyl), rimsulfuron 25 (rimsulfuron) and chlorine sulphur swell (chlorsulfuron) standard items, and producer is a du pont company.
Neopelex (SDS), methyl alcohol are that analysis is pure.
Volume fraction is 20% series standard pH value damping fluid, and producer is a German Merck company.
(2) key instrument
XRF (Tianjin, island RF5301-PC); (the lamp group has 12, illumination 2.924mW/cm to contain the photochemical reaction device of uviol lamp group
2, Zhejiang University's environment and resource institute self-control experimental facilities, patent No. ZL200820120401); Quartz cuvette (1cm * 1cm * 5cm), pH meter.
(3) solution preparation
The preparation of the grand standard solution of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur: the grand standard items of a certain amount of sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur are used dissolve with methanol respectively, be mixed with 1 * 10
-3The standard solution of mol/L, 4 ℃ keep in Dark Place in refrigerator.
The SDS WS is mixed with the SDS WS of 0.1mol/L with distilled water.
(4) testing conditions
At final concentration is 2.0～2.5 * 10
-3Mol/L, certain potential of hydrogen (sulfometuronmethyl pH 9; Rimsulfuron 25 pH 7 and chlorine sulphur swell pH 12) the SDS WS in; Contain the grand sample of sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur respectively through ultraviolet ray irradiation 120～150s, measure its fluorescence signal intensity (I with XRF then
F) value, calculate the quantitative concentrations that obtains sulfonylurea herbicide through typical curve.
Embodiment 1 typical curve is drawn
(1) sulfometuronmethyl linear standard curve
Get 1 * 10 of above-mentioned preparation respectively
-3Mol/L sulfometuronmethyl standard solution 0,10,20,30,40,50 μ L are in the volumetric flask of 6 5mL; Add the 0.1mol/L SDS WS of the above-mentioned preparation of 125 μ L, add 1mL standard pH damping fluid again, transfer to best pH 9; Be settled to 5mL with distilled water, make the SDS final concentration be 2.5 * 10
-3Mol/L obtains concentration and is respectively 0,2.0 * 10
-6, 4.0 * 10
-6, 6.0 * 10
-6, 8.0 * 10
-6, 1.0 * 10
-5Mol/L sulfometuronmethyl standard model; The standard model of above-mentioned sulfometuronmethyl is respectively got 3mL place quartz cuvette; Under 25 ℃, Continuous irradiation 120s in photochemical reaction device is put into postradiation standard model and measures its fluorescence signal intensity (I in the XRF
F) value, draw sulfometuronmethyl content and I
FThe linear standard curve of value, the result sees Fig. 1.
(2) rimsulfuron 25 linear standard curve
The same step of measuring method (1), rimsulfuron 25 pH regulator to 7, shown in Figure 2.
(3) chlorine sulphur carina property typical curve
The same step of measuring method (1), chlorine sulphur are swelled pH regulator to 12, and be shown in Figure 3.
The mensuration of embodiment 2 natural water samples
What the glass fiber filter of learning from else's experience respectively removed by filter suspension contains 3 parts of the residual natural water-likes of sulfonylurea herbicide (through the known sulfometuronmethyl of high-performance liquid chromatogram determination; The grand concentration of rimsulfuron 25 and chlorine sulphur be respectively 1.1,1.3 and 1.4mg/L), in the volumetric flask of 5mL; The 0.1mol/L SDS WS 125 μ L that add above-mentioned preparation respectively; Add 1mL standard pH damping fluid, transfer to best pH (sulfometuronmethyl pH 9, rimsulfuron 25 pH 7 and chlorine sulphur swell pH 12) respectively; Use the distilled water constant volume, making the SDS final concentration is 2.5 * 10
-3Mol/L obtains 3 parts of testing samples, and above-mentioned 3 parts of testing samples are respectively got 3mL place quartz cuvette, under 25 ℃, Continuous irradiation 120s in photochemical reaction device, the fluorescence signal intensity (I of the postradiation testing sample of mensuration in XRF
F) value, according to above-mentioned typical curve, calculating the grand content of sulfometuronmethyl in the water sample, rimsulfuron 25 or chlorine sulphur according to formula (1), the result is respectively 1.09,1.31 and 1.39mg/L, the result compares favorable reproducibility with high-performance liquid chromatogram determination.
The grand content of sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur calculates as follows according to formula (1) in the testing sample:
In the formula (1): sulfometuronmethyl, rimsulfuron 25 or the grand volumetric molar concentration (mol/L) of chlorine sulphur in the testing sample that ρ-calculating obtains according to typical curve;
V
1---draw the volume (mL) of testing sample;
V
2---the liquor capacity (mL) of volumetric flask;
The molal weight (g) that m---sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur are grand;
Confirming of embodiment 3 detectabilities
With 1 * 10 of above-mentioned preparation
-3Mol/L sulfometuronmethyl standard solution, 1 * 10
-3Mol/L rimsulfuron 25 standard solution and 1 * 10
-3The grand standard solution of mol/L chlorine sulphur is divided into 3 groups; Get 0.2,0.5,1.0,2.0,4.0,8.0,16.0,24.0,36.0 μ L respectively in the volumetric flask that places 5mL respectively for every group; Adopt above-mentioned typical curve same procedure to measure the grand concentration of sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur; Adopt least square method that data are carried out regretional analysis, confirm the detectability of this method.Result such as table 1; Can know that by table 1 the grand typical curve correlation coefficient r of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur is respectively 0.9998,0.9997 and 0.9998; Photochemistry fluorescence method method detection sulfometuronmethyl, rimsulfuron 25 and the grand LDL (LOD) of chlorine sulphur reach 3 μ g/L, 0.4 μ g/L and 0.5 μ g/L respectively simultaneously; MRL standard (0.01～0.05mg/L) less than sulfonylurea herbicide; And be lower than the detection limit value (10～20 μ g/L) of high performance liquid chromatography UV-detector in different medium, show that the photochemistry fluorescence analysis method is the effective ways of the grand minimal residue of micro-sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur in a kind of quantitative determination water sample.
Photochemistry fluorescence spectrometry sulfometuronmethyl, rimsulfuron 25 and the grand result of chlorine sulphur in the table 1SDS colloidal dispersion system
The mensuration of embodiment 4 natural water sample recovery rates
(1) sulfometuronmethyl typical curve
To take from Hua Jiachi in the Zhejiang University and remove by filter the natural water samples 100mL of suspension through glass fiber filter; Add 0.0035g sulfometuronmethyl standard items; Sonic oscillation 15min, obtaining the sulfometuronmethyl mass concentration is the natural water body standard reserving solution of 35.0mg/L, keeps in Dark Place.Get 0,5,10,15,20,25,30 μ L storing solutions respectively in the volumetric flask of 7 5mL, add the 0.1mol/LSDS WS 125 μ L respectively, add 1mL standard pH damping fluid more respectively and transfer pH to 9; Be settled to 5mL with distilled water, obtain the standard solution of sulfometuronmethyl series concentration, get 3mL respectively and place serial quartz cuvette; Under 25 ℃; Continuous irradiation 120s in photochemical reaction device measures its fluorescence signal intensity (IF) value, draws the sulfometuronmethyl typical curve.
(2) rimsulfuron 25 typical curve
The same step of method for drafting (1), obtaining the rimsulfuron 25 mass concentration is 25.0mg/L natural water body standard reserving solution, transfers pH to 7, other operate same step (1), draw the rimsulfuron 25 typical curve.
(3) the grand typical curve of chlorine sulphur
The same step of method for drafting (1), obtaining the grand mass concentration of chlorine sulphur is 25.0mg/L natural water body standard reserving solution, transfers pH to 12, other operate same step (1), draw the grand typical curve of chlorine sulphur.
(4) water sample test
Water sample to be measured the same (taking from Hua Jiachi in the Zhejiang University); That is: gathered and remove by filter in the suspension natural water body through glass fiber filter; Add the sulfometuronmethyl (1.75,4.24,31.87,58.74,151.62,234.50 μ L) of 35.0mg/L, the rimsulfuron 25 (0.84,2.08,6.02,16.16,45.54,62.82 μ L) of 25.0mg/L or grand (0.64,2.28,8.08,18.52,49.72,100.02 μ L) standard natural water body standard reserving solution of chlorine sulphur of 25.0mg/L respectively, addition is seen table 1.Adopt embodiment 2 same procedure to measure replication 3 times, calculate recovery rate.The result sees table 2.Can know by table 2; Sulfometuronmethyl, rimsulfuron 25 and the grand average recovery rate of chlorine sulphur are respectively 97.0% ± 2.3%, 98.9% ± 3.7% and 98.7% ± 4.3% under 6 interpolation levels; Show that the SDS colloidal dispersion system PCF analytical approach of being set up is more satisfactory to the grand detection effect of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur in the natural water samples, can be used for the grand residual mensuration of sulfometuronmethyl in the natural water samples, rimsulfuron 25 and chlorine sulphur.
Table 2 SDS colloidal dispersion system photochemistry fluorescence method is measured the result to having added the grand natural water samples of sulfometuronmethyl, rimsulfuron 25 or chlorine sulphur
Claims (8)
1. the residual method of sulfonylurea herbicide in the quantitative determination water sample; It is characterized in that said method is: get and contain the residual water sample of sulfonylurea herbicide; Add the 0.1mol/L SDS WS, regulating the pH value is 7～12, and using the distilled water constant volume to make the SDS final concentration is 2.0～2.5 * 10
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the grand standard items of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur respectively; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur carina property typical curve respectively, quantitatively predict in the testing sample the grand residual quantity separately of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur in the sulfonylurea herbicide according to typical curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
2. the residual method of sulfonylurea herbicide in the quantitative determination water sample according to claim 1; It is characterized in that said linear standard curve draws as follows: respectively the grand standard items of sulfometuronmethyl, rimsulfuron 25 and chlorine sulphur are used dissolve with methanol, be mixed with 1 * 10 respectively
-3Mol/L sulfometuronmethyl methanol solution, 1 * 10
-3Mol/L rimsulfuron 25 methanol solution and 1 * 10
-3Mol/L chlorine sulphur swells methanol solution, adds the 0.1mol/L SDS WS more successively, regulates pH 9 respectively, and pH 7 and pH 12 make the SDS final concentration be 2.0～2.5 * 10 with the distilled water constant volume respectively
-3Mol/L obtains concentration successively and is respectively 0,2.0 * 10
-6, 4.0 * 10
-6, 6.0 * 10
-6, 8.0 * 10
-6, 1.0 * 10
-5The sulfometuronmethyl standard solution of mol/L, Sulfometuron Methyl standard solution and chlorine sulphur swell standard solution; And under the ultraviolet condition, shining 120～150s under 25 ℃; Measure fluorescence signal intensity value separately with XRF then, draw sulfometuronmethyl linear standard curve, rimsulfuron 25 linear standard curve and chlorine sulphur carina property typical curve respectively.
3. the residual method of sulfonylurea herbicide in the quantitative determination water sample according to claim 1; The method that it is characterized in that sulfometuronmethyl in the said quantitative measurement water sample is: get and contain the residual water sample of sulfonylurea herbicide; Add the 0.1mol/L SDS WS; Regulating the pH value is 9, and using the distilled water constant volume to make the SDS final concentration is 2.0～2.5 * 10
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the sulfometuronmethyl standard items; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw the sulfometuronmethyl linear standard curve, quantitatively predict in the testing sample residual quantity of sulfometuronmethyl in the sulfonylurea herbicide according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
4. the residual method of sulfonylurea herbicide in the quantitative determination water sample according to claim 1; The method that it is characterized in that rimsulfuron 25 in the said quantitative measurement water sample is: get and contain the residual water sample of sulfonylurea herbicide; Add the 0.1mol/L SDS WS; Regulating the pH value is 7, and using the distilled water constant volume to make the SDS final concentration is 2.0～2.5 * 10
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the rimsulfuron 25 standard items; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw the rimsulfuron 25 linear standard curve, quantitatively predict in the testing sample rimsulfuron 25 residual quantity in the sulfonylurea herbicide according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
5. the residual method of sulfonylurea herbicide in the quantitative determination water sample according to claim 1; It is characterized in that the grand method of chlorine sulphur in the said quantitative measurement water sample is: get and contain the residual water sample of sulfonylurea herbicide; Add the 0.1mol/L SDS WS; Regulating the pH value is 12, and using the distilled water constant volume to make the SDS final concentration is 2.0～2.5 * 10
-3Mol/L obtains analyte sample fluid, and under 25 ℃, ultraviolet irradiation 120～150s measures the fluorescence signal intensity value of testing sample then with XRF with analyte sample fluid; Become the standard items methanol solution of variable concentrations to replace water sample with dissolve with methanol the grand standard items of chlorine sulphur; Prepare standard model liquid down with preparation analyte sample fluid the same terms; And use the fluorescence signal intensity value of XRF testing standard sample under the same conditions; Draw chlorine sulphur carina property typical curve, quantitatively predict the residual quantity that chlorine sulphur swells in the sulfonylurea herbicide in the testing sample according to linear standard curve; Said water sample removes by filter suspension through glass fiber filter, and residual sulfometuronmethyl, rimsulfuron 25 and the chlorine sulphur of comprising of said sulfonylurea herbicide is grand.
6. like the residual method of sulfonylurea herbicide in claim 1 or the 3 said quantitative determination water samples, it is characterized in that the residual lowest detection of said sulfometuronmethyl is limited to 3 μ g/L.
7. like the residual method of sulfonylurea herbicide in claim 1 or the 4 said quantitative determination water samples, it is characterized in that the residual lowest detection of said rimsulfuron 25 is limited to 0.4 μ g/L.
8. like the residual method of sulfonylurea herbicide in claim 1 or the 5 said quantitative determination water samples, it is characterized in that the grand residual lowest detection of said chlorine sulphur is limited to 0.5 μ g/L.
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Application publication date: 20120711 |