CN103698327A - Method and kit for quickly detecting dithiocarbamic acid esters pesticide residues - Google Patents
Method and kit for quickly detecting dithiocarbamic acid esters pesticide residues Download PDFInfo
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- CN103698327A CN103698327A CN201310750334.6A CN201310750334A CN103698327A CN 103698327 A CN103698327 A CN 103698327A CN 201310750334 A CN201310750334 A CN 201310750334A CN 103698327 A CN103698327 A CN 103698327A
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Abstract
The invention belongs to the field of detection of agricultural and sideline products or food, relates to detection of pesticide residues and in particular relates to a method and a kit for quickly detecting dithiocarbamic acid esters pesticide residues. More particularly, a method for detecting a dithiocarbamic acid esters compound in a sample comprises the following steps: (1) generating reaction to produce carbon disulfide; (2) measuring the concentration or the concentration range of the produced carbon disulfide, wherein preferably, the step (1) also comprises a step of extracting or separating the produced carbon disulfide. The method and the kit which are disclosed by the invention have the outstanding advantages of quickness in detection, simplicity in operation, low cost, on-site operation and the like.
Description
Technical field
The invention belongs to agricultural byproducts or food inspection field, relate to the detection of residues of pesticides, particularly, relate to the agriculture of a kind of Fast Measurement dithiocarbamate residual method and kit.
Background technology
Dithiocarbamate (Dithiocarbamates, referred to as DTCs) be the general name of a class organosulfur pesticide, be divided into the U.S. class of good fortune and Dai Sen class, to apply in the world a series bactericidal agent very widely, can be used for preventing and treating more than 70 400 multiple pathogens of planting crop, is class organic compounds that also use in a large number the earliest in history.Because this series bactericidal agent cost is low, purposes is wide, to people and animals' low toxicity, be still widely used in so far in the crops such as control fruit tree, vegetables by Phycomycetes and the caused downy mildew of Fungi Imperfecti, pinta, head blight etc.
DTCs is a kind of compound that disulfide group replaces that contains, and the structure according to compound, mainly comprises: dimethyldithiocarbamate (DMDCs), as Sodium Dimethyldithiocarbamate, fervam, ziram, thiram etc.; Ethylene dithiocarbamate (EBDCs), as Dithane A40, maneb, zineb, Mancozeb etc.; With trimethylene dithiocarbamate (PBDCs), as the third gloomy sodium, Propineb etc.
But, widespread use along with dithiocarbamate, it is found that in the metabolic process in using its food and in animal and plant body and can produce a kind of metabolite that is hexamethylene thiocarbamide (ETU), and ETU has carcinogenicity, teratogenesis and mutagenicity, and the thyroid function of energy the Long-term Effect, by U.S. state OSHA (the Occupational Health and Safety Administration) (OSrtA), as carcinogenic substance, enrolled book.In addition, dithiocarbamate has moderate to stimulate to mammal skin and respiratory apparatus, show as itch, the symptom such as sore-throat, tracheae inflammation.
To the security of dithiocarbamate, give very large concern both at home and abroad, repeatedly it has been evaluated especially, and proposed the suggestion and measure strengthen management.The high residue amount in each agricultural products limits to dithiocarbamate agricultural chemicals for many countries and international organization, as European Union stipulates its maximum residue limit(MRL) in beans, be 1mg/kg (in carbon disulphide), in mango maximum residue limit(MRL) be 2mg/kg (in carbon disulphide).The agricultural product such as the edible fungi of China's export are repeatedly return because dithiocarbamate pesticide residue exceeds standard.Therefore, reinforcement is very necessary to the detection of dithiocarbamate residual quantity in agricultural product.
The method that has in the world at present multiple analysis dithiocarbamate pesticide residue, comprises spectrophotometric method, vapor-phase chromatography and liquid phase chromatography etc.Spectrophotometric method needs special instrument, and measurement operation complex steps, and influence factor is many, and the degree of accuracy of method and repeatability are poor.Vapor-phase chromatography and liquid phase chromatography have been simplified operation, and precision and the accuracy of analysis are also improved.But said method ubiquity needs the processing of expensive instrument, sample and detection time is long, the problems such as flux of impact analysis.
Therefore, need badly a kind of simple to operate, expense is cheap, detection is quick, the residual method of dithiocarbamate agriculture that can execute-in-place.
Summary of the invention
The inventor is through deep research and performing creative labour, the agriculture of a kind of fast detecting dithiocarbamate residual method and kit have been obtained, the inventor is surprised to find, and it is residual that described method or kit can be measured dithiocarbamate agriculture fast, effectively, easily.Following invention is provided thus:
An invention of the present invention relates to the method for dithio amino formate compounds in a kind of working sample, comprises the steps:
(1) reaction generates carbon disulphide;
(2) measure concentration or the concentration range of the carbon disulphide generating;
Alternatively, the step that also comprises extraction or the separated carbon disulphide generating in step (1).
Described content or the content range that obtains dithio amino formate compounds in sample that be determined as.Described sample is agricultural byproducts or food, such as tobacco, vegetables, fruit etc.
Method according to the present invention described in any one, wherein, in described step (1), adds the material reacting with dithio amino formate compounds to generate carbon disulphide; Preferably, this material is the sub-tin of acid chlorization; Preferably, acid requirement is for using hydrochloric acid, pH be 0.8-1.5 rub/liter.
Method according to the present invention described in any one, wherein, described reaction is carried out under Ultrasonic Heating condition; Particularly, ultrasonic time is 10-20min, and ultrasonic power is 300-750W, and heating-up temperature is 50-80 ℃.
Method according to the present invention described in any one, wherein, described step (1) is carried out in closed container.
Method according to the present invention described in any one, wherein, in described step (1), the reagent of extraction or separated carbon disulphide adds with the material that described reacting with dithio amino formate compounds generates carbon disulphide simultaneously.
Method according to the present invention described in any one, wherein, the reagent of described extraction or separated carbon disulphide is isooctane.
Method according to the present invention described in any one, wherein, described step (2) comprises measures carbon disulphide as the step of the substance that show color of reactant generation.
Method according to the present invention described in any one, wherein, described substance that show color is Diethylamina Dithiomothyle acid copper; Preferably, described Diethylamina Dithiomothyle acid copper is that carbon disulphide reacts generation with diethylamine under mantoquita exists; Preferably, described mantoquita is copper acetate; Preferably, described diethylamine and copper acetate (can be made into chromophoric solution) are excessive.
Method according to the present invention described in any one, wherein, by colorimetric card, measure concentration or the concentration range of substance that show color, calculate concentration or the concentration range of carbon disulphide, then calculate concentration or the concentration range of dithio amino formate compounds in sample.
Method according to the present invention described in any one, it meets following 1)-7) in any one or multinomial:
1) described sample is got 1-10g;
2) described closed container is the 100-250mL conical flask of band plug;
3) consumption of described isooctane is 25-50mL;
4) addition of the sub-tin of described acid chlorization is 25-50mL;
5) described heating-up temperature is 50-80 ℃;
6) described ultrasonic time is 10-20min, and ultrasonic power is 300-750W.
7) chromophoric solution is by 0.01-0.05g copper acetate, and the dissolving of 2-5mL diethylamine constant volume are formulated in ethanol (95% ethanol 50mL), and addition is 1-3mL.
Those skilled in the art can, according to the cumulative volume of isooctane and example weight, calculate the residual content of dithiocarbamate agriculture.
In one embodiment of the invention, described method as shown in Figure 1.
In one embodiment of the invention, taking a certain amount of testing sample is contained in closed container, add successively the sub-solution of tin of a certain amount of isooctane and acid chlorization, Ultrasonic Heating a period of time, after stratification, taking out a certain amount of upper strata drop enters to fill in the color comparison tube of copper acetate-diethylamine-ethanol chromophoric solution, after jolting colour developing, with colorimetric card colorimetric.
Be not limited to theoretical restriction, isooctane is the CS that reaction is generated
2from water back extraction out, thereby separated with the offal in water, to get rid of its interference to chromogenic reaction.Although CS
2be dissolved in some organic solvents, such as ethanol, ether etc., still, the inventor, by deep researching and analysing, finds only have isooctane to dissolve carbon disulphide and do not allow other impurity and and aqueous phase separation.
Be not limited to theoretical restriction, the effect of the sub-tin of acid chlorization is and disulfide group generation reduction reaction that the disulfide group that dithiocarbamate agriculture is residual is converted into CS
2, acidity is the needs of Reduction with Stannous Chloride disulfide group.
Acid requirement is for being used hydrochloric acid; PH be 0.8-1.5 rub/liter; Be preferably 0.8-1.2 to rub/liter, for example 0.8,0.9,1.0,1.1 or 1.2 rub/liter; More preferably 1 rubs/liter.
It is 37% hydrochloric acid that the sub-solution of tin of described acid chlorization can be dissolved in 250-500mL volumetric concentration with 10-25g stannous chloride, and is that 1L is formulated with distilled water constant volume.
The sub-tin of acid chlorization and isooctane preferably add simultaneously, and the inventor finds by research, the CS that can make like this reaction generate
2fully by isooctane, adsorbed.
Be not limited to theoretical restriction, Ultrasonic Heating is in order to promote reduction reaction, do not adopt or adopt separately ultrasonic or heating also can, but reaction time that need be longer.Under Ultrasonic Heating condition of the present invention, reaction carries out more fully, rapid.
Be not limited to theoretical restriction, mechanism of the present invention is: the dithiocarbamate agricultural chemicals in sample is total to after heat in tin chloride solution, and the generation carbon disulfide gas that is decomposed, is adsorbed by isooctane.Under mantoquita (copper acetate) exists, carbon disulphide and diethylamine effect, the Diethylamina Dithiomothyle acid copper of generation yellowish-brown, estimates its content range with colorimetric card colorimetric.
Dithio amino formate compounds (agriculture is residual)+SnCl
2+ HCl → SnCl
4+ CS
2
CS
2+2NH(C
2H
5)
2→(C
2H
5)
2N-CS
2H·NH(C
2H
5)
2
2(C
2H
5)
2N-CS
2H.NH(C
2H
5)
2+Cu(CH
3COO)
2→[(C
2H
5)
2N·CS+S]2Cu+2CH
3COOH+2NH(C
2H
5)
2。
Another aspect of the present invention relates to the kit of dithio amino formate compounds in a kind of working sample, comprising: isooctane 25-50mL, the sub-solution of tin 25-50mL of acid chlorization, 0.01-0.05g copper acetate, dissolve with 2-5mL diethylamine; Preferably, also comprise colorimetric card, and described colorimetric card is with reference to CS
2the color range of gradient standard solution gained after chromogenic reaction occurring generate Diethylamina Dithiomothyle acid copper is made.
In one embodiment of the invention, CS
2gradient standard solution is respectively 0,5,10,20,50,100,200,500 μ g/mL(with CS
2meter).
In one embodiment of the invention, the copper acetate of use and diethylamine are excessive.
In one embodiment of the invention, colour developing card can reference example 1 be prepared, and can carry out qualitative, semiquantitative visual colorimetric determination.
In one embodiment of the invention, the effective range that can measure agricultural chemicals can be 1-500 μ g/g or 1-1000 μ g/g or larger scope (in carbon disulphide).
The beneficial effect of the invention
Adopt isooctane by the CS producing
2extract, separated with solid, convenient further mensuration.The present invention is without expensive instrument, and sense cycle shortens greatly.The present invention have detect quick, simple to operate, expense is cheap, can execute-in-place etc. outstanding advantages.
Accompanying drawing explanation
Fig. 1: accompanying drawing is operating process schematic diagram of the present invention.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example is only for the present invention is described, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person in embodiment, carries out according to the condition of normal condition or manufacturer's suggestion.The unreceipted person of production firm of agents useful for same or instrument, being can be by the conventional products of commercial acquisition.
embodiment 1: the preparation and application of colorimetric card
Under copper acetate exists, carbon disulphide and diethylamine effect, can generate the Diethylamina Dithiomothyle acid copper of yellowish-brown.The Diethylamina Dithiomothyle acid copper and the CS that generate
2concentration linear, so the shade of the color of Diethylamina Dithiomothyle acid copper can characterize CS
2concentration.
Colorimetric card is with reference to CS
2the color range of gradient standard solution gained after there is chromogenic reaction is made, and colour atla is posted in art post paperboard, and corresponding concentration is that 0,5,10,20,50,100,200,500 μ g/mL(are with CS successively
2meter).The copper acetate and the diethylamine that use are excessive.
What colorimetric card represented is the color of Diethylamina Dithiomothyle acid copper, and what it directly reacted is the color of the Diethylamina Dithiomothyle acid copper of generation, corresponding to the concentration of Diethylamina Dithiomothyle acid copper.
In addition, copper acetate intrinsic colour is more shallow, is the Essential colour of colorimetric card.
During use, if relatively after actual sample reaction the color of gained in the centre of any two colour atlas, just can infer between the concentration that its concentration range characterizes at these two colour atlas.Also can make according to actual conditions the colour atla of variable concentrations scope in actual use.
It is the concentration range of carbon disulphide in extract that colorimetric card records, and according to after the cumulative volume of the isooctane using and samples weighing, can calculate the content range of sample Pesticides.
The colorimetric card using in the following examples 2-4 is the colorimetric card that embodiment 1 makes.
embodiment 2: the residual detection of DTCs agriculture of Tea Samples
The Tea Samples that takes 2g is contained in the 100mL conical flask of band plug, adding successively 25mL isooctane and being dissolved in 250mL volumetric concentration with 10g stannous chloride is 37% hydrochloric acid, and be the sub-solution of tin 25mL of the formulated acid chlorization of 1L with distilled water constant volume, Ultrasonic Heating 20min under temperature 50 C power 300W condition, after stratification, taking out 1mL isooctane splashes into and fills 1mL by 0.01g copper acetate, the dissolving of 2mL diethylamine constant volume are in the color comparison tube of the formulated chromophoric solution of ethanol, after jolting colour developing, with colorimetric card colorimetric.
After jolting, be light yellowish brown, with corresponding colorimetric card colorimetric, infer that in this Tea Samples, the residual content of dithiocarbamate agriculture is 100 μ g/mL-200 μ g/mL (in carbon disulphide).Can calculate thus, in this sample, DTCs content is about 125-250 μ g/g.
embodiment 3: the residual detection of DTCs agriculture of tobacco sample
The offal sample that takes 5g is contained in the 250mL conical flask of band plug, adding successively 30mL isooctane and being dissolved in 250mL volumetric concentration with 20g stannous chloride is 37% hydrochloric acid, and be the sub-solution of tin 30mL of the formulated acid chlorization of 1L with distilled water constant volume, Ultrasonic Heating 10min under 80 ℃ of power 750W conditions of temperature, after stratification, taking out 2mL isooctane splashes into and fills 2mL by 0.05g copper acetate, the dissolving of 5mL diethylamine constant volume are in the color comparison tube of the formulated chromophoric solution of ethanol, after jolting colour developing, with colorimetric card colorimetric.
After jolting, be yellowish-brown, with corresponding colorimetric card colorimetric, infer that in this tobacco sample, the residual content of dithiocarbamate agriculture is 200 μ g/mL-500 μ g/mL (in carbon disulphide).Can calculate thus, in this sample, DTCs content is about 1200-3000 μ g/g.
embodiment 4: the residual detection of DTCs agriculture of fruit (apple) sample
The apple sample that takes 10g is contained in the 250mL conical flask of band plug, adding successively 50mL isooctane and being dissolved in 500mL volumetric concentration with 25g stannous chloride is 37% hydrochloric acid, and be the sub-solution of tin 50mL of the formulated acid chlorization of 1L with distilled water constant volume, Ultrasonic Heating 15min under temperature 60 C power 500W condition, after stratification, taking out 3mL isooctane splashes into and fills 3mL by 0.03g copper acetate, the dissolving of 3mL diethylamine constant volume are in the color comparison tube of the formulated chromophoric solution of ethanol, after jolting colour developing, with colorimetric card colorimetric.
After jolting, be faint yellow, with corresponding colorimetric card colorimetric, infer that in this apple sample, the residual content of dithiocarbamate agriculture is 20 μ g/mL-50 μ g/mL (in carbon disulphide).Can calculate thus, in this sample, DTCs content is about 100-250 μ g/g.
Although the specific embodiment of the present invention has obtained detailed description, it will be understood to those of skill in the art that.According to disclosed all instructions, can carry out various modifications and replacement to those details, these change all within protection scope of the present invention.Four corner of the present invention is provided by claims and any equivalent thereof.
Claims (10)
1. a method for dithio amino formate compounds in working sample, comprises the steps:
(1) reaction generates carbon disulphide;
(2) measure concentration or the concentration range of the carbon disulphide generating;
Alternatively, the step that also comprises extraction or the separated carbon disulphide generating in step (1).
2. method according to claim 1, wherein, in described step (1), adds the material reacting with dithio amino formate compounds to generate carbon disulphide; Preferably, this material is the sub-tin of acid chlorization; Preferably, acid requirement is for using hydrochloric acid, pH be 0.8-1.5 rub/liter.
3. method according to claim 2, wherein, described reaction is carried out under Ultrasonic Heating condition; Particularly, ultrasonic time is 10-20min, and ultrasonic power is 300-750W, and heating-up temperature is 50-80 ℃.
4. method according to claim 1, wherein, described step (1) is carried out in closed container.
5. method according to claim 2, wherein, in described step (1), extracts or the reagent of separated carbon disulphide adds with the described material that reacts generation carbon disulphide with dithio amino formate compounds simultaneously.
6. method according to claim 5, wherein, the reagent of described extraction or separated carbon disulphide is isooctane.
7. method according to claim 1, wherein, described step (2) comprises the step of measuring the substance that show color that carbon disulphide generates as reactant.
8. method according to claim 7, wherein, described substance that show color is Diethylamina Dithiomothyle acid copper; Preferably, described Diethylamina Dithiomothyle acid copper is that carbon disulphide reacts generation with diethylamine under mantoquita exists; Preferably, described mantoquita is copper acetate; Preferably, described diethylamine and copper acetate are excessive.
9. method according to claim 7, wherein, by colorimetric card, measure concentration or the concentration range of substance that show color, calculate concentration or the concentration range of carbon disulphide, then calculate concentration or the concentration range of dithio amino formate compounds in sample.
10. a kit for dithio amino formate compounds in working sample, comprising: isooctane 25-50mL, the sub-solution of tin 25-50mL of acid chlorization, 0.01-0.05g copper acetate, dissolve with 2-5mL diethylamine; Preferably, also comprise colorimetric card, and described colorimetric card is to make with reference to the color range of CS2 gradient standard solution gained after chromogenic reaction occurring generate Diethylamina Dithiomothyle acid copper.
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Cited By (5)
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| CN104181152A (en) * | 2014-08-06 | 2014-12-03 | 中山大学 | Device and method for online detecting residue of dithio carbamate bactericide |
| CN106124279A (en) * | 2016-09-09 | 2016-11-16 | 福建中烟工业有限责任公司 | Pre-treatment and detection method containing dithio amino formate compounds sample |
| CN108489968A (en) * | 2018-03-31 | 2018-09-04 | 中国热带农业科学院分析测试中心 | A kind of method of easy detection dithiocarbamates pesticide |
| CN111830167A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and determination of phosphine and dithiocarbamate compounds |
| CN111830165A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104181152A (en) * | 2014-08-06 | 2014-12-03 | 中山大学 | Device and method for online detecting residue of dithio carbamate bactericide |
| CN106124279A (en) * | 2016-09-09 | 2016-11-16 | 福建中烟工业有限责任公司 | Pre-treatment and detection method containing dithio amino formate compounds sample |
| CN106124279B (en) * | 2016-09-09 | 2019-08-02 | 福建中烟工业有限责任公司 | The pre-treatment of the sample containing dithio amino formate compounds and detection method |
| CN108489968A (en) * | 2018-03-31 | 2018-09-04 | 中国热带农业科学院分析测试中心 | A kind of method of easy detection dithiocarbamates pesticide |
| CN111830167A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and determination of phosphine and dithiocarbamate compounds |
| CN111830165A (en) * | 2020-07-22 | 2020-10-27 | 福建中烟工业有限责任公司 | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances |
| CN111830165B (en) * | 2020-07-22 | 2022-12-20 | 福建中烟工业有限责任公司 | Method for pretreatment and simultaneous measurement of phosphine and dithiocarbamate substances |
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Application publication date: 20140402 |