The method of nitrate salt and nitrite in the detection sauerkraut
Technical field
The present invention relates to a kind of method of detection.
Background technology
Sauerkraut is raw material as the common salted vegetables in a kind of north with Chinese cabbage, adopts the method storage of pickling, with this shortage of replenishing winter vegetable.In curing process, ferment by natural certain micro-organisms attached to vegetable surface, under the effect of reduction bacterium, the nitrate salt in the vegetables can be reduced into nitrite.There are some researches show
[1], vegetables are in the process of pickling, and the content of its nitrite presents the back downward trend that rises earlier.The sauerkraut that exceeds standard when the edible nitrite content of people, nitrite poisoning together, the lighter's giddy, palpitaition, vomiting, cyanotic lips, are twitched, are short of breath at weight person obnubilation, but the untimely threat to life of rescue.In addition, nitrite forms nitrosamines with the effect of secondary amine class inside and outside human body
[2], it is carcinogenic, teratogenesis, mutagenic material when in human body, reaching doses, but the serious harm HUMAN HEALTH.
About nitrate salt, the extraction of nitrite, traditional extraction process has solvent-extraction process
[3], hot water extraction method, vibration extraction method
[4]Deng, but they have the some shortcomings part in leaching process, for example, extraction time long (15~20min), extraction yield low (75%~85%), complicated operation etc.
At present, the method for directly measuring nitrate salt is less, mainly is it to be reduced into nitrite measure.Reduction nitrate salt majority is to adopt the cadmium post to reduce, though this method reduction efficiency height, system cadmium grain, the dress post, reduction, washing, mensuration and activation step are loaded down with trivial details, length consuming time.
Have a variety ofly about the nitrite detection method, the method that detects nitrite at present mainly contains the griess reagent colourimetry, the catalysis light-intensity method, and oscilloscopic polarography etc., these method sensitivity are low, and interference is many, is subject to shortcomings such as reagent color influence.The method for quick of nitrite such as test kit, rapid detection appearance, shortcoming such as it is narrow to have linearity range again, and detection limit is low.
Summary of the invention
The objective of the invention is in order to solve existing nitrate salt, the efficient low complicated operation problem long in the sauerkraut of extracting, reach detection method and have shortcomings such as complex process, length consuming time, linearity range be narrow with nitrite method lifetime.
The method of nitrate salt and nitrite of extracting among the present invention in the sauerkraut is undertaken by following step: sauerkraut is rubbed, get 1g then and join 2.5mL borax saturated solution and stir adding 10mL zero(ppm) water through rubbing sauerkraut after handling; Then at extracting through microwave heating 5min; The temperature of microwave heating is 80 ℃, and adding potassium ferrocyanide solution and the 1mL concentration that 1mL concentration is 0.25mol/L again is the acetic acid zinc solution of 1mol/L, constant volume; Static filtration is collected filtrating and is obtained extracting solution; Promptly accomplish nitrate salt and nitrite extraction in the sauerkraut.
The said extracted method is under the microwave field effect; Separated from matrix or system with nitrite by nitrate salt through the difference that absorbs the microwave ability is feasible; Enter into that specific inductivity is less, the borax saturated solution of microwave absorption capacity relative mistake; Thereby accomplished the extraction of nitrate salt and nitrite, it has, and simple, the consuming time weak point of technology, extraction yield are high, equipment is simple, applied widely, favorable reproducibility, save time, save reagent, pollute characteristics such as little.The extraction time of the inventive method is 5min, and nitrate salt and nitrite extraction yield are all more than 90%.
Detecting in the sauerkraut nitrate salt among the present invention accomplishes by following step with nitrite: one, the preparation of o-aminophthalylhydrazide analytic liquid: absorption 7.5mL concentration is 1 * 10
-3The mol/L luminol solution uses concentration to obtain the o-aminophthalylhydrazide analytic liquid as the NaOH solution constant volume of 0.25mol/L; Two, the mensuration of nitrite: get the extracting solution that 5.00mL extracts from sauerkraut as stated above, the potassium bromate solution, the 3.00mL concentration that add 10.00mL concentration then and be 0.06mol/L are 5 * 10
-3The YD 30 of mol/L (EDTA) solution and 2.50mL concentration are the H of 0.5mol/L
2SO
4Solution; Constant volume; Obtain treating the test sample solution A, the o-aminophthalylhydrazide analytic liquid and the 2.00mL of 2.00mL step 1 preparation treated that the test sample solution A joins in the wink maidenliness attitude Chemiluminescence Apparatus successively measure the glow peak signal that record reacts; Read peak area Y, bring peak area Y into concentration X that regression equation promptly obtains nitrite then
1Three, the mensuration of nitrate salt: get the extracting solution that the 20mL aforesaid method extracts from sauerkraut; Add 5mL ammonia property buffered soln, 0.2g zinc powder and 0.4mL cadmium chloride solution; Zinc powder and Cadmium chloride fine powder mass ratio are 1: 2, the 40min that under oscillation frequency 180 commentaries on classics/min, 50 ℃ of water bath with thermostatic control conditions, vibrates then, filter, behind the constant volume solution B; Get the 10.00mL solution B then, the potassium bromate solution, the 3.00mL concentration that add 10.00mL concentration again and be 0.06mol/L are 5 * 10
-3The EDTA solution of mol/L and 2.50mL concentration are the H of 0.5mol/L
2SO
4Solution, constant volume obtains treating the test sample solution C; The o-aminophthalylhydrazide analytic liquid of 2.00mL step 1 preparation and 2.00mL are treated that the test sample solution C joins in the wink maidenliness attitude Chemiluminescence Apparatus successively to be measured; The glow peak signal of record reaction reads peak area Y, brings peak area Y into regression equation calculation then and goes out X
2, with (X
2-X
1The concentration that promptly obtains nitrate salt is calculated in) * 1.232; Nitrate salt and nitrite detection in the sauerkraut have promptly been accomplished; Wherein step 2 and three described regression equations: when instrument parameter is chosen as negative high voltage is 325V and 5.74 * 10
7≤Y≤1.13 * 10
9The time bring Y into Y=4.66 * 10
6+ 1.08 * 10
9X, r=0.9947 is 300V and 2.11 * 10 when instrument parameter is chosen as negative high voltage
8≤Y≤1.14 * 10
9The time bring Y into Y=2.02 * 10
7+ 9.38 * 10
6X, r=0.9930.
Above-mentioned detection method is utilized zinc-cadmium water-bath vibration reduction nitrate salt, and the nitrate reduction rate reaches 92.65%, detection method have simple, the consuming time weak point of technology (40min), highly sensitive, linearity range is wide, the simple advantage of plant and instrument.
Embodiment
Embodiment one: the method for nitrate salt and nitrite of extracting in this embodiment in the sauerkraut is undertaken by following step: sauerkraut is rubbed; Getting the sauerkraut of 1g after rub handling then joins 2.5mL borax saturated solution and stirs; Add 10mL zero(ppm) water, then at extracting through microwave heating 5min, the temperature of microwave heating is 80 ℃; Adding potassium ferrocyanide solution and the 1mL concentration that 1mL concentration is 0.25mol/L again is the acetic acid zinc solution of 1mol/L; Constant volume, static filtration is collected filtrating and is obtained extracting solution; Promptly accomplish nitrate salt and nitrite extraction in the sauerkraut.
Nitrate and nitrite recovery rate are all more than 90% in the present embodiment.Recording the content that extracts nitrite in the sauerkraut is 3.95mg/kg, and (2.79mg/kg) compares with National Standard Method, improved 41.6%.
Embodiment two: what this embodiment and embodiment one were different is: the time of said rubbing sauerkraut is 2min, and used rotating speed is 1400r/min.
Embodiment three: detect in the sauerkraut nitrate salt in this embodiment and accomplish by following step with nitrite: one, the preparation of o-aminophthalylhydrazide analytic liquid: absorption 7.5mL concentration is 1 * 10
-3The mol/L luminol solution uses concentration to obtain the o-aminophthalylhydrazide analytic liquid as the NaOH solution constant volume 50mL of 0.25mol/L; Two, the mensuration of nitrite: get the extracting solution that 5.00mL extracts from sauerkraut by embodiment one said method, the potassium bromate solution, the 3.00mL concentration that add 10.00mL concentration then and be 0.06mol/L are 5 * 10
-3The YD 30 of mol/L (EDTA) solution and 2.50mL concentration are the H of 0.5mol/L
2SO
4Solution; Constant volume 50mL; Obtain treating the test sample solution A, the o-aminophthalylhydrazide analytic liquid and the 2.00mL of 2.00mL step 1 preparation treated that the test sample solution A joins in the wink maidenliness attitude Chemiluminescence Apparatus successively measure the glow peak signal that record reacts; Read peak area Y, bring peak area Y into concentration X that regression equation promptly obtains nitrite then
1Three, the mensuration of nitrate salt: get the extracting solution that 20mL embodiment one said method is extracted from sauerkraut; Add 5mL ammonia property buffered soln, 0.2g zinc powder and 0.4mL cadmium chloride solution; Zinc powder and Cadmium chloride fine powder mass ratio are 1: 2, the 40min that under oscillation frequency 180 commentaries on classics/min, 50 ℃ of water bath with thermostatic control conditions, vibrates then, filter, behind the constant volume 50mL solution B; Get the 10.00mL solution B then, the potassium bromate solution, the 3.00mL concentration that add 10.00mL concentration again and be 0.06mol/L are 5 * 10
-3The EDTA solution of mol/L and 2.50mL concentration are the H of 0.5mol/L
2SO
4Solution, constant volume 50mL treats the test sample solution C; The o-aminophthalylhydrazide analytic liquid of 2.00mL step 1 preparation and 2.00mL are treated that the test sample solution A joins in the wink maidenliness attitude Chemiluminescence Apparatus successively to be measured; The glow peak signal of record reaction reads peak area Y, brings peak area Y into regression equation calculation then and goes out X
2, with (X
2-X
1The concentration that promptly obtains nitrate salt is calculated in) * 1.232; Nitrate salt and nitrite detection in the sauerkraut have promptly been accomplished; Wherein step 2 and three described regression equations: when instrument parameter is chosen as negative high voltage is 325V and 5.74 * 10
7≤Y≤1.13 * 10
9The time bring Y into Y=4.66 * 10
6+ 1.08 * 10
9X, r=0.9947 is 300V and 2.11 * 10 when instrument parameter is chosen as negative high voltage
8≤Y≤1.14 * 10
9The time bring Y into Y=2.02 * 10
7+ 9.38 * 10
6X, r=0.9930.
The content that this method detects nitrite in the sauerkraut is 2.84mg/kg,, 11 replicate(determination) results' RSD is 2.90%, and recovery of standard addition is 101.00%, and nitrate content is 7.32mg/kg.
Change into the effect of nitrite through following this embodiment of verification experimental verification nitrate salt: get 20mL nitrate salt standardized solution (solution is equivalent to 5 μ g Sodium Nitrites for every milliliter) in Erlenmeyer flask; Adding 5mL ammonia property buffered soln (pH=9.6~9.7) and solid-to-liquid ratio are 1: 2 zinc powder and (1.5%) cadmium chloride solution; 50 ℃ of temperature; Under the condition of oscillation frequency 180 commentaries on classics/min, vibration 40min.Calculating the nitrate reduction rate is 92.65%, and meeting the nitrate reduction rate should be greater than 90% requirement.
Regression equation can obtain as follows in this embodiment: sulfuric acid concentration is 0.05mol/L, and potassium bromate concentration is 0.06mol/L, and o-aminophthalylhydrazide concentration is 1.50 * 10
-4Mol/L, NaOH concentration are under the 0.25mol/L condition, and the relative luminous intensity of this system is maximum.NO
2 -Concentration is in 0.001~0.1mg/L scope, and obtaining corresponding nitrite typical curve is Y=4.66 * 10
6+ 1.08 * 10
9X (r=0.9947), NO
2 -Concentration is in 0.1~10mg/L scope, and obtaining corresponding nitrite typical curve is Y=2.02 * 10
7+ 9.38 * 10
6X (r=0.9930).Nitrite is good linear relationship with luminous intensity (area) in 0.001~10mg/L scope.
Embodiment four: what this embodiment and embodiment three were different is: pH value=9.6~9.7 of the described ammonia property buffered soln of step 3.Other step is identical with embodiment three with parameter.