CN100456023C - Method for rapid detecting sodium sulfoxylate formaldehyde in foodstuff - Google Patents

Method for rapid detecting sodium sulfoxylate formaldehyde in foodstuff Download PDF

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Publication number
CN100456023C
CN100456023C CNB2005100572622A CN200510057262A CN100456023C CN 100456023 C CN100456023 C CN 100456023C CN B2005100572622 A CNB2005100572622 A CN B2005100572622A CN 200510057262 A CN200510057262 A CN 200510057262A CN 100456023 C CN100456023 C CN 100456023C
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formaldehyde
sample
sodium
solution
foodstuff
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CN1737544A (en
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张晓凤
徐铭熙
柳亚珍
付钰洁
鲁秀敏
项锦欣
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Chongqing Institute of Technology
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Chongqing Institute of Technology
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Abstract

The present invention relates to a method for rapidly detecting sodium sulfoxylate formaldehyde in foodstuff, which comprises steps: preparing a sample, detecting formaldehyde and detecting sodium bisulfite, wherein in the step of preparing the sample, the sample foodstuff to be detected is fetched, mashed, dipped and filtered, and the volume of the sample foodstuff to be detected is fixed for later use. In the step of detecting the formaldehyde, the formaldehyde and the sodium sulfite react and generate OH-, thyme phenolphthalein as an indicator qualitatively is used for judging the existence of the formaldehyde through a color developing method according to the chemical characteristics and the electrochemical characteristics of reaction products, and the content of the formaldehyde is semi-quantitatively analyzed through a galvanic potential method. In the step of detecting the sodium bisulfite, starch is used as the indicator, NaHSO3 and I2 take place redox reaction and generate Na2, SO4 and I-, solution changes from blue state to colorless state, and the state whether NaHSO3 exists in the sample is qualitatively judged. The method for rapidly detecting sodium sulfoxylate formaldehyde in foodstuff has the advantages of novelty, high sensitivity, good selectivity, low cost, no pollution, and simple, convenient and rapid detection method.

Description

Contain the sodium formaldehyde sulfoxylate method in the fast detecting food
Affiliated field
The present invention relates to whether contain in the fast detecting food method of sodium formaldehyde sulfoxylate, and can be qualitative and sxemiquantitative fast detecting food in contain the method for sodium formaldehyde sulfoxylate, belong to the food hygiene detection technical field.
Background technology
The chemical name of " sodium formaldehyde sulfoxylate " is rongalite (Sodium formaldehydesulfoxylate), and molecular formula is NaHSO 2CH 2O2H 2O, the bulk that is white in color or crystallinity powdery, water-soluble, comparatively stable during normal temperature; The reductibility that it is strong makes it have discoloration; Meet acid and promptly decompose, aqueous solution is decomposed just beginning more than 60 ℃, and higher temperature is decomposed into toxic gases such as formaldehyde, sulphuric dioxide and sulfuretted hydrogen, can make the people have a headache, weak, appetite is poor, when serious even can cause nasopharyngeal carcinoma etc.International cancer research organization points out, the chance of contact formaldehyde for a long time person's nasal cavity or pharynx nasalis generation tumour, canceration obviously increases.Human body takes in sulphuric dioxide for a long time or sulphite can destroy Cobastab 1, influence is grown, and easily suffers from polyneuritis, symptoms such as marrow atrophy occur, thereby produces chronic toxicity.
Under the ordering about of pecuniary benefit, some illegal manufacturers are added in the food as whitening agent with sodium formaldehyde sulfoxylate, utilize it to decompose " formaldehyde " the increase food elasticity and " sulphurous acid " that produce and have the function that brightens, color and lusters such as some food such as ground rice, flour, bean vermicelli, white fungus, pastries and bean product are bleached, what have can also strengthen toughness, is difficult for rotting.Although sodium formaldehyde sulfoxylate has whitening effect, owing to it is detrimental to health, so China forbids adding sodium formaldehyde sulfoxylate in food.
But, the present national standard method that does not detect sodium formaldehyde sulfoxylate in the food.Existing most employing phenylhydrazine hydrochloride method, acetylacetone method or AHMT method etc., and all be the content that utilizes content of formaldehyde indirect calculation sodium formaldehyde sulfoxylate, but to only with formaldehyde treated or the sample of formaldehyde background is arranged, easily produce erroneous judgement, and these methods all need to absorb detection again through distillation, complicated operating process, loaded down with trivial details, consuming time, and need support equipment.Therefore, whether there is sodium formaldehyde sulfoxylate in the judgement sample, not only to also to could judge according to formaldehyde according to sulphuric dioxide, only having detected the formaldehyde existence may be to have added due to the formaldehyde and antiseptic in the sample, only detected sulphuric dioxide exist may be add in the sample sodium sulphite (or sodium pyrosulfite) bleach anticorrosion due to, so must detect judgement respectively.2004 12 volumes of China's " oil and foodstuffs science and technology ", the 5th interim " the new assay method of sodium formaldehyde sulfoxylate in the food " utilizes ultraviolet spectrophotometry to measure formaldehyde and sodium bisulfite in the food respectively, judge that whether " sodium formaldehyde sulfoxylate " exists, consider the background values of negative sample, the judgement that makes " sodium formaldehyde sulfoxylate " content more accurately and reliably.But this detection method sample also needs to absorb detection again through distillation, and operating process is loaded down with trivial details, is difficult to realize the field quick detection of sodium formaldehyde sulfoxylate in the food.
To sum up, the subject matter that prior art exists is: when (1) was used for food " sodium formaldehyde sulfoxylate " detection, because the existence of background values easily produces erroneous judgement, accuracy was not high; (2) correctly do not recognize the residual except formaldehyde and sodium bisulfite of " sodium formaldehyde sulfoxylate " in the food, also have the existence of some low price sulphides, cause a lot " sodium formaldehyde sulfoxylate " testing results inaccurate; (3) owing to food component and form more complicated, obviously there is limitation in tradition " sodium formaldehyde sulfoxylate " detection method; (4) be difficult to realize the field quick detection of " sodium formaldehyde sulfoxylate " in the food.
Summary of the invention
At the prior art above shortcomings, the object of the invention provide a kind of accurately, contain the method for sodium formaldehyde sulfoxylate in directly perceived, the fast detecting food.
The object of the present invention is achieved like this: contain the sodium formaldehyde sulfoxylate method in the fast detecting food, comprising:
1) is equipped with sample: get that sample to be tested food is mashed, soaked, filtration, constant volume be standby;
2) detection of formaldehyde: utilizing the reaction of formaldehyde and sodium sulphite to generate OH-, according to chemical characteristic, the electrochemical properties of reaction product, is that indicator exists by development process qualitative judgement formaldehyde with the thymolphthalein, by the content of potential method semi-quantitative analysis formaldehyde;
3) detection of sodium bisulfite: with starch indicator, NaHSO 3With I 2Redox reaction takes place generate Na 2SO 4And I -, solution is become colorless by blueness, qualitatively judges in the sample to have or not NaHSO 3Exist.
The detection method of formaldehyde comprises the steps: filtrate pH value is adjusted to 7.0, respectively drips 1 sodium sulphite, thymolphthalein and sample test solution then in color comparison tube successively, is blank contrast experiment simultaneously; Observe two color comparison tubes behind 5s, filtrate is blue person's proof and contains concentration of formaldehyde greater than 5ppm; Otherwise concentration of formaldehyde is less than 5ppm.
The method of qualitative detection sodium bisulfite comprises the steps: the method for fading--in two color comparison tubes, adds 10 1% iodine-starch solution respectively, adds 2~10 samples to be tested in a color comparison tube therein, add equal-volume distilled water in another color comparison tube for blank; Observing test tube Smalt then takes off explanation and has sodium bisulfite to exist; Otherwise, do not have sodium bisulfite to exist.
The method of detection by quantitative sodium bisulfite is: nephelometry--in sample, add certain amount of H 2O 2And BaCl 2, the solution becomes muddiness is according to NaHSO in the turbidity gradient semi-quantitative analysis sample of solution 3Accurately pipette earlier 0.5mL hydrogen peroxide and 2mL barium chloride in the color comparison tube of 10mL, shake up, add 5mL again and contain SO 4 2-Amount is that a series of sodium bisulfates of 10~200 μ g form the turbidity gradients, during sample detection operation identical, observe the turbidity of solution, and contrast with the turbidity gradient, do blank test simultaneously, can determine low price sulphide content range 300~400ppm.
The present invention is based on sodium formaldehyde sulfoxylate and resolves into formaldehyde and sodium bisulfite under acid condition, by the content of sodium formaldehyde sulfoxylate in the accurate judgement food of detecting respectively of formaldehyde and sodium bisulfite.
The inventive method is compared with existing sodium formaldehyde sulfoxylate detection technique and is had the following advantages:
(1) method novelty, detection method has novelty, has overcome the loaded down with trivial details characteristics such as time-consuming of operated in accordance with conventional methods; Can realize the detection of formaldehyde and sodium bisulfite by development process, the method for fading or nephelometry;
(2) highly sensitive, can realize the qualitative and semi-quantitative analysis of formaldehyde and sodium bisulfite.According to the blue depth degree of color comparison tube, can whether there be formaldehyde in the qualitative analysis sample, the quilitative method concentration limit is 5ppm, detects to be limited to 0.25 μ g.Change according to solution potential, but utilize miniature pH meter semi-quantitative analysis content of formaldehyde, concentration limit is 20ppm, detects to be limited to 10 μ g.But according to sodium bisulfite in the blue qualitative analysis sample that whether disappears of color comparison tube, the quilitative method concentration limit is 10ppm, detects to be limited to 10 μ g.But utilize turbidity gradient semi-quantitative analysis bisulfite sodium content, concentration limit is 50ppm, detects and is limited to 10 μ g.
(3) selectivity is good, mutual interference mutually when adopting the method for fading or nephelometry to avoid formaldehyde to detect with sodium bisulfite, and the detection respectively of two components makes " sodium formaldehyde sulfoxylate " testing result more reliable.
(4) testing result is accurate, utilizes nephelometry, can record the total amount that adds sodium formaldehyde sulfoxylate in the food, rather than residual volume, and this method is not subjected to the interference of other component, therefore the more real sodium formaldehyde sulfoxylate content that reacted.
(5) the detection method cost is low, pollution-free, only need cheap when potential method detects and acidometer that widely use, chemical method can carry out in the 1.0mL centrifuge tube when detecting, agents useful for same is few, the expense of finishing one-time detection work is below 1.0 yuan, and the detection method non-environmental-pollution does not influence operator's health.
(6) easy quicklook, detection method is easy, quick, and testing is generally finished in 1-2min; No matter it is be that the outward appearance phenomenon that instrument is indicated or chemical reaction presented is all fairly obvious in the detection, directly perceived.
Embodiment
Embodiment 1
Buy bean curd in the market of farm produce, adopt the technology of the present invention--" method of fading " field quick detection sodium formaldehyde sulfoxylate, each entrained reagent is preprepared, only need bean curd is mashed, filtered, in two color comparison tubes, add 10 iodine-starch solution respectively, wherein a color comparison tube adds sample to be tested (about 2~10), adds equal-volume distilled water in another color comparison tube for blank, and coupon Smalt is taken off explanation has sodium bisulfite to exist;
Simultaneously, adopt the formaldehyde field fast detection method, filtrate pH value is adjusted to 7.0, in color comparison tube, respectively drip 1 sodium sulphite, thymolphthalein and sample test solution then successively, color comparison tube is blue behind the 5s, do blank assay and draw that concentration of formaldehyde should be greater than 5ppm in the filtrate, two kinds of method qualitative detection results conform to, and show in this bean curd to be added with sodium formaldehyde sulfoxylate.
Embodiment 2
Buy steamed bun in the market of farm produce, adopt the technology of the present invention--" nephelometry " field quick detection sodium formaldehyde sulfoxylate, each entrained reagent is preprepared, take by weighing and mash steamed bun, soak, filter, constant volume accurately pipettes adding 0.5mL hydrogen peroxide and 2mL barium chloride in the color comparison tube of 10mL, shakes up, add the 5mL sample to be tested again, observe the turbidity of solution, contrast, do blank test simultaneously with the turbidity gradient, the steamed bun sample is sulfide content scope 200-300ppm at a middle or low price, shows in this steamed bun to be added with sodium formaldehyde sulfoxylate.
Embodiment 3
Buy certain bean vermicelli from the supermarket, adopt the technology of the present invention--" method of fading " field quick detection sodium formaldehyde sulfoxylate, each entrained reagent is preprepared, gets the chopping bean vermicelli, soaks, filter, add 10 iodine-starch solution in two color comparison tubes respectively, wherein a color comparison tube adds sample to be tested (about 2~10), adds equal-volume distilled water in another color comparison tube for blank, coupon Smalt is not taken off, and illustrates not to be added with sodium formaldehyde sulfoxylate in the bean vermicelli.
Embodiment 4
Buy certain white sugar in the market of farm produce, adopt the technology of the present invention--" nephelometry " field quick detection formaldehyde, each entrained reagent is preprepared, takes by weighing quantitative white sugar, the dissolving constant volume, accurately pipette adding 0.5mL hydrogen peroxide and 2mL barium chloride in the color comparison tube of 10mL, shake up, add the 5mL sample to be tested again, observe the turbidity of solution, contrast with the turbidity gradient, do blank test simultaneously, the white sugar product are sulfide content scope 300-400ppm at a middle or low price; Simultaneously, adopt formaldehyde field quick detection technology, measure with potential method that content of formaldehyde is 350-380ppm in the liquid to be measured, two kinds of method half-quantitative detection results conform to, and show that this white sugar handled with sodium formaldehyde sulfoxylate.
The present invention is highly sensitive, and the sensitivity of development process can reach 5ppm in color comparison tube, and the sensitivity of current potential detection method can reach 20ppm, and nephelometry sensitivity can reach 50ppm.
Realize the qualitative and semi-quantitative analysis of sodium formaldehyde sulfoxylate, when detecting formaldehyde and sodium bisulfite respectively, the quilitative method concentration limit is 10ppm, detects to be limited to 10 μ g, and the quantivative approach concentration limit is 50ppm, detects to be limited to 10 μ g.

Claims (3)

1, contain the sodium formaldehyde sulfoxylate method in the fast detecting food, it is characterized in that:
1) is equipped with sample: get sample to be tested food and mash, soak, filter that also constant volume is standby;
2) pH value with spare test piece is adjusted to acidity;
3) detection of formaldehyde: utilize the reaction of formaldehyde and sodium sulphite to generate OH -, according to the chemical characteristic of reaction product, be indicator with the thymolphthalein, can qualitatively judge formaldehyde by development process and exist, by the content of potential method semi-quantitative analysis formaldehyde;
4) detection of sodium bisulfite: the method for fading---with starch is indicator, NaHSO 3With I 2Redox reaction takes place generate Na 2SO 4And I -, solution is become colorless by blueness, qualitatively judges through step 2) handle in the resulting sample and have or not NaHSO 3Exist; Nephelometry---through step 2) handle in the resulting sample and add certain amount of H 2O 2Solution and BaCl 2Solution, reaction back sample solution becomes muddy, according to NaHSO in the turbidity gradient semi-quantitative analysis sample of reaction back solution 3Content.
2, contain the sodium formaldehyde sulfoxylate method in the fast detecting food according to claim 1, it is characterized in that the detection method of described formaldehyde comprises the steps:
Will be through claim 1 step 2) the sample pH value that obtains after handling is adjusted to 7.0, and the sample solution after dropping 1 sodium sulphite, thymolphthalein and pH value is adjusted to neutrality in a color comparison tube then is blank contrast experiment in another color comparison tube; Observe two color comparison tubes behind 5s, reaction back sample solution is blue, and then proof contains concentration of formaldehyde greater than 5ppm; Otherwise concentration of formaldehyde is less than 5ppm.
3, contain the sodium formaldehyde sulfoxylate method in the fast detecting food according to claim 1, it is characterized in that described nephelometry comprises the steps:
Accurately move into 0.5mlH 2O 2Solution and 2mlBaCl 2Solution shakes up in the 10ml color comparison tube, adds 5ml again through claim 1 step 2) sample that obtains after handling, observe the turbidity of solution, contrast with the turbidity gradient, do blank test simultaneously, can determine the content range of low price sulphide.
CNB2005100572622A 2005-09-09 2005-09-09 Method for rapid detecting sodium sulfoxylate formaldehyde in foodstuff Expired - Fee Related CN100456023C (en)

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Cited By (1)

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CN102269711A (en) * 2010-06-02 2011-12-07 北京市食品安全监控中心 Method for detecting whether wheat flour contains sodium bisulfoxylate formaldehyde

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CN102128862B (en) * 2010-01-18 2014-04-23 惠碁生物科技股份有限公司 Detecting method, detecting test piece and detector for redox materials in food
CN102967660A (en) * 2012-03-15 2013-03-13 福建中烟工业有限责任公司 Method for rapid determination of sodium formaldehyde sulfoxylate in food additive
CN102841064B (en) * 2012-09-10 2014-08-13 云南东昌金属加工有限公司 Measurement method of inorganic germanium content in carboxyethylated germanium sesquioxide
CN102967598A (en) * 2012-11-02 2013-03-13 苏州金宏气体股份有限公司 Method for detecting total sulfite content in high-purity ammonia
CN103499597B (en) * 2013-10-14 2015-10-21 无锡艾科瑞思产品设计与研究有限公司 Based on the detection method of sodium formaldehyde sulfoxylate in the flour of toxic gas detection
CN105136794A (en) * 2015-08-17 2015-12-09 陈志� Method used for rapid detection of noodle acidity
CN105717112B (en) * 2016-01-28 2018-07-17 北京沃邦医药科技有限公司 A kind of detection method of sulphite limit
CN105823774B (en) * 2016-03-22 2018-12-21 河北安捷仑生物科技有限公司 Formaldehyde in food rapid detection method
CN107764819A (en) * 2016-08-18 2018-03-06 深圳市爱能森科技有限公司 The detection method of carbanion content in a kind of nitrite
CN111426662B (en) * 2020-04-10 2023-01-24 江西理工大学 Fluorescence detection method of sodium formaldehyde sulfoxylate (rongalite)
CN111521606B (en) * 2020-06-05 2023-12-22 广州海关技术中心 Rapid detection method for talcum powder in flour

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CN102269711B (en) * 2010-06-02 2014-10-15 北京市食品安全监控中心 Method for detecting whether wheat flour contains sodium bisulfoxylate formaldehyde

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