CN102455293A - Method for determining trace lead in textile products - Google Patents
Method for determining trace lead in textile products Download PDFInfo
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- CN102455293A CN102455293A CN2011103764210A CN201110376421A CN102455293A CN 102455293 A CN102455293 A CN 102455293A CN 2011103764210 A CN2011103764210 A CN 2011103764210A CN 201110376421 A CN201110376421 A CN 201110376421A CN 102455293 A CN102455293 A CN 102455293A
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Abstract
The invention discloses a method for determining trace lead in textile products, which comprises the following steps of: after a heavy metal Pb in a textile product is extracted by using acidic perspiration, gathering a trace heavy metal Pb in an extracting solution by using nano TiO2; and then, carrying out determination by using an ICP-OES (inductively coupled plasma optical emission spectroscopy) method. Because the content of the heavy metal Pb in the solution subjected to gathering is high, the determination sensitivity is improved, and a determination operation can be performed by using an ICP (inductively coupled plasma) emission spectrum; and in the process of gathering, the salt content in a textile-product extracting solution is reduced, thereby reducing the matrix interference in the process of spectrum determination.
Description
Technical field
The invention belongs to inspection and quarantine field, be specifically related to a kind of method of measuring trace lead in the textile.
Background technology
China is maximum in the world fabric clothing producing country, exported country and country of consumption, and textile industry is China's foreign exchange earning mainstay industry.Show that according to Chinese customs statistics during the 1-11 month in 2007, China's textile kimonos takes on 1606.51 hundred million dollars of mouthful total values, accounts for 60.28% of national favourable trade balance total value.At present; The part country of the U.S., Japan, Hong Kong and European Union is the main exporting country of China's textile product; And these countries and regions usually the safety of textile, sanitary index as one of major criterion of weighing its inherent quality; Through promulgate a decree, form such as compulsory standard, textile has been formulated multiple Environmental security project demand, have only the product that satisfies its requirement just to be allowed to get into its market.For this reason; Strengthen and accelerate the detection method of poisonous and harmful substance (like heavy metal) in the textile and, help improving the detection technique level of China, to ensureing human health and protection environment in existence form (valence state, form) research; Improve China's textile ecological criteria level rapidly; Break the foreign technology barrier, the development that promotes the ecological textile of China will play a significant role, and has crucial meaning.
Textile is snugness of fit and the colour fastness that improves textile in printing and dyeing and back arrangement process, and textile often will use various chemical assistants in process, makes residual poisonous and harmful substance in the textile, and one of them is exactly a poisonous and harmful heavy metallic.These heavy metals have serious cumulative toxicity to human body.In recent years, formulated ecological textile relevant laws and regulations and standard both at home and abroad, the content of heavy metals such as the Pb in the strict restriction textile, Hg, As, Ni, Cu, Co, Cd, Cr, Cr (VI), Sb is prohibited the substandard product immigration.Content to the harmful heavy metal that can extract in the textile in China's standard GB/T 18885-2002 " ecological textile technical requirement " also has clear and definite qualification.
In the world Determination of Heavy Metal in the textile is mainly contained: 1). colorimetric analysis 2). atomic absorption spectrophotometry 3). atomic fluorescence spectrum.4). inductively coupled plasma emission spectrography (ICP-OES method).5). inductively coupled plasma mass spectrometry (ICP-MS method).But colorimetric method for determining sexavalent chrome serious interference, sensitivity is not high; Atomic absorption spectrophotometry can not be carried out multielement simultaneous determination, and detection speed is slow; Matrix effect is serious, needs to use matrix modifier, comparatively trouble; And some element determination sensitivity is not high; It is limited that atomic fluorescence spectrum can be surveyed element, can not measure multielement simultaneously; The ICP-MS method is owing to cost an arm and a leg, and maintenance cost is high, present less employing.Now, because the ICP-OES method can carry out multielement simultaneous determination, and measure when being widely used in the textile various heavy element.But because it belongs to the instrument of microanalysis, for trace analysis, sensitivity does not reach requirement, for example, when the Pb ion concentration is lower than 10ng/mL, accurately measures and has difficulties insufficient sensitivity.This instrument is for the higher sample of salt (containing a large amount of salinities in the acidic sweat) simultaneously, and matrix effect is serious.
In general; Because it is very low to the heavy metal limit in the textile in the world; Bring very big difficulty to testing; Present method equipment purchasing total expenses, safeguard that total expenses and personnel's total expenses are all very expensive, be difficult to realize that highly sensitive, low-cost, multielement detects simultaneously, press for and set up the mensuration new method highly sensitive, that detection speed is fast, cost is low.Also do not see relevant nano-TiO at present
2Be used for textile enriched with trace heavy metal Pb, then the bibliographical information measured of using plasma emission spectrometry.
Summary of the invention
Technical matters to be solved by this invention provides a kind of method of measuring trace lead in the textile.This method is after the heavy metal lead in the textile is extracted with acidic sweat, to adopt nano titanium oxide (TiO
2) trace heavy metal plumbous (Pb) in the extracting and enriching liquid, the Pb in the extract is concentrated, make its concentration can reach the sensitivity of inductive coupling plasma emission spectrograph.Solved when the Pb ion concentration is lower than 10ng/mL, also can adopt inductively coupled plasma emission spectrography (ICP-OES) to measure the problem of the trace Pb in the textile, this method can accurately be measured in the extract Pb concentration below 5ng/mL.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is:
A kind of method of measuring trace lead in the textile, this method may further comprise the steps:
(1) with the acidic sweat is extract, soaks textile;
(2) lead in the employing nano titanium oxide extracting and enriching liquid;
(3) adopt inductively coupled plasma emission spectrography to measure plumbous content.
Further, in the step (2), adopt the concrete steps of lead in the nano titanium oxide extracting and enriching liquid to be:
A. get the extract 30ml ~ 70mL that obtains in the step (1), regulate pH4 ~ 7, add at least 0.03 g nano titanium oxide, shake 5min at least, static then 30min, centrifugal, remove supernatant, obtain the nano titanium oxide sediment; Be preferably: add 0.03 g ~ 0.07g nano titanium oxide, concussion 5min ~ 15min;
B. add in said nano titanium oxide sediment at least that the concentration of 3ml is 0.5 ~ 2mol/L hydrochloric acid, shake 5min at least, static then 30min, centrifugal, obtain supernatant, to be determined.Be preferably: the concentration that adds 3ml ~ 6ml is 0.5 ~ 2mol/L hydrochloric acid, concussion 5min ~ 15min;
Further, the prescription of said acidic sweat is: contain L-histidine 0.5 g in every 1L water, sodium chloride 5 g, two hypophosphite monohydrate sodium dihydrogens, 2.2 g.
Further, in the step (1), be extract with the acidic sweat, the condition of soaking textile is: 37 ℃ are soaked 60min, take out textile, and extract is cooled to room temperature, filter for use.
Beneficial effect of the present invention:
(1) after the present invention extracts the heavy metal lead in the textile with acidic sweat, adopts nano-TiO
2Trace heavy metal Pb in the extracting and enriching liquid measures with the ICP-OES method then.Because content of beary metal height in the solution has improved mensuration sensitivity after the enrichment, can adopt the ICP emission spectrum to measure.
(2) use the instrument of microanalysis just can accomplish trace analysis, practiced thrift funds.
(3) in the enrichment process, salinity reduces in the textile extract, and the matrix when therefore having reduced spectroscopic assay disturbs.
Below in conjunction with Figure of description and embodiment the present invention is described further, does not limit the present invention in any way.Every any this area of carrying out according to the disclosure of invention is equal to replacement, all belongs to protection scope of the present invention.
Description of drawings
Fig. 1 adsorption rate and nanometer Ti O
2The graph of a relation of consumption;
The graph of a relation of Fig. 2 adsorption rate and adsorbing medium acidity;
Fig. 3 measured value and parsing time relation figure;
The graph of a relation of Fig. 4 measured value and concentration of hydrochloric acid.
The specific embodiment mode
1 instrument and reagent
Prodigy XP inductively coupled plasma atomic emission spectrometer (Leeman company), its condition of work: power is 1.2 KW, atomization gas pressure 28 psi, secondary air amount 0.1 LPM, cooling gas flow: 20 LPM; Pump speed: 1.5 mL/min, Pb detects wavelength 220.353 nm.
The Pb standard solution is provided by national standard material center.
It is pure or analyze pure that the various conventional reagent of experiment usefulness is top grade.
Experimental water is 18.2 M Ω cm ultrapure waters.
Nanometer Ti O
2(mean grain size≤25 nm) is available from Hangzhou ten thousand scape new material company limiteds.
The preparation of acidic sweat: take by weighing L-histidine 0.5g, sodium chloride 5g, two hypophosphite monohydrate sodium dihydrogens, 2.2 g dissolve in beaker, are transferred in the 1L volumetric flask.
2 experimental techniques
2.1 nano-TiO
2Handle
With nano-TiO
2Be put in the beaker, the nitric acid dousing 30min with 5mol/L is washed till neutrality with ultrapure water, after the oven dry, keeps in Dark Place.
2.2 sample pre-treatments
Cloth specimen is shredded to 5mm ⅹ 5mm, and mixing takes by weighing the 4.00g sample, places tool plug Erlenmeyer flask.Add the 80mL acidic sweat, fiber is fully soaked, put into 37 ℃ of water bath with thermostatic control oscillators 60min that vibrates, after the taking-up, leave standstill and be cooled to room temperature, filter, filtrating (extract) is used for the concentration and separation experiment.
2.3 experimental technique
In 50mL tool plug centrifuge tube, add the extract in the 30mL step 2.2, add certain amount of nano TiO again
2, mechanical oscillation leaves standstill 30min, and the centrifugal 15min of 5300r/min removes supernatant liquor.
Nano-TiO after centrifuging
2Accurately add a certain amount of certain density HCl in the sediment, mechanical oscillation leaves standstill 30min once more, and the centrifugal 15min of 5300r/min gets supernatant and measures wherein plumbous content with ICP-OES.
3. the selection of condition
3.1 adsorption conditions
3.1.1 nano-TiO
2Consumption
Respectively at add 0.01,0.02,0.03,0.04,0.05 in six centrifuge tubes, the nano titanium oxide of 0.07g, operate by 2.3 experimental technique, the result sees Fig. 1.The consumption that shows nano material titania gets final product more than 0.03g, but considers experimental cost, too much add nano titanium oxide and have no meaning, so the consumption of nano titanium oxide is preferably 0.03g ~ 0.07g.
3.1.2 adsorption time:
Operate according to 2.3 experimental techniques, vibrate 5,10,15,20,25 respectively, leave standstill 30min behind the 30min, can obtain better absorption more than showing vibration 5min, but consider control, be preferably concussion 5-30min whole experimental period.
3.1.3 absorption acidity
Add a certain amount of acidic sweat in 6 centrifuge tubes respectively, regulate the pH value and be respectively 1,2,3,4,5.5,7, operate according to 2.3 experimental techniques then, the result sees Fig. 2.Show that the pH scope is 4～7, absorption better.
3.2 desorption condition
3.2.1 desorption time
With the nano-TiO after the centrifuging
2Sediment adds a certain amount of 0.5mol/mL HCl, vibrates 5,10,15,25 respectively, and 30 min operate according to 2.3 experimental techniques then, and the result sees Fig. 3.Can obtain better desorption effect more than showing vibration 5min, but consider control, be preferably concussion 5-30min whole experimental period.
3.2.2 desorb acidity
The centrifugal sediment that obtains is added 6 mL0.05 respectively, 0.1,0.5,1,1.5,2mol/mL HCl operates by 2.3 experimental techniques, and Pb content in the supernatant is measured in centrifugal back, and the result sees Fig. 4.Show that concentration of hydrochloric acid is better in 0.5 ~ 2mol/L desorb.
3.3.3 hydrochloric acid consumption
To adsorb, add respectively in the centrifugal sediment that obtains the 0.5mol/mL HCl of 3,4,5,6 mL through nano material, and operate by 2.3 experimental procedures, the result sees table 1.Show that the hydrochloric acid consumption gets final product more than 3mL, but consider experimental cost, too much add hydrochloric acid and have no meaning, so concentration is that the consumption of 0.5mol/mL HCl is preferably 3 ~ 6ml.
Table 1 hydrochloric acid consumption
| 0.5N HCl consumption/mL | Addition/ug | Measured value/ug | The recovery/% |
| 3 | 0.3 | 0.2976 | 99.2 |
| 4 | 0.3 | 0.3036 | 101.2 |
| 5 | 0.3 | 0.301 | 100.3 |
| 6 | 0.3 | 0.3012 | 100.4 |
4. detection lower bound, the recovery and the precision of method
Respectively at adding nano titanium oxide in 7 centrifuge tubes, add 0.3ugPb standard solution, a certain amount of acid acidic sweat more respectively, making Pb concentration is 5ng/mL, operates by 2.3 experimental procedures, the result sees table 2.This result shows: when the concentration of Pb was low to moderate 5ng/mL, the recovery of this method was between 87% ~ 101%, and relative standard deviation is below 6%.The Pb that is low to moderate 5ng/mL can be accurately measured in explanation.
The recovery of table 2 method and precision
Obviously, the above embodiment of the present invention only be for clearly the present invention is described and is done for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (5)
1. a method of measuring trace lead in the textile is characterized in that, this method may further comprise the steps:
(1) with the acidic sweat is extract, soaks textile;
(2) lead in the employing nano titanium oxide extracting and enriching liquid;
(3) adopt inductively coupled plasma emission spectrography to measure plumbous content.
2. the method for trace lead is characterized in that in the mensuration textile according to claim 1, in the step (2), adopts the concrete steps of lead in the nano titanium oxide extracting and enriching liquid to be:
A. get the extract 30ml ~ 70mL that obtains in the step (1), regulate pH4 ~ 7, add at least 0.03 g nano titanium oxide, shake 5min at least, static then 30min, centrifugal, remove supernatant, obtain the nano titanium oxide sediment;
B. add in said nano titanium oxide sediment at least that the concentration of 3ml is 0.5 ~ 2mol/L hydrochloric acid, shake 5min at least, static then 30min, centrifugal, obtain supernatant, to be determined.
3. the method for trace lead is characterized in that in the mensuration textile according to claim 2, in the step (2), adopts the concrete steps of lead in the nano titanium oxide extracting and enriching liquid to be:
A. get the extract 30ml ~ 70mL that obtains in the step (1), regulate pH4 ~ 7, add 0.03 g ~ 0.07g nano titanium oxide, concussion 5min ~ 30min, static then 30min, centrifugal, remove supernatant, obtain the nano titanium oxide sediment;
B. the concentration that in said nano titanium oxide sediment, adds 3ml ~ 6ml is 0.5 ~ 2mol/L hydrochloric acid, concussion 5min ~ 30min, and static then 30min, centrifugal, obtain supernatant, to be determined.
4. according to the method for trace lead in claim 1, the 2 or 3 arbitrary described mensuration textiles, it is characterized in that the prescription of said acidic sweat is: contain L-histidine 0.5 g in every 1L water, sodium chloride 5 g, two hypophosphite monohydrate sodium dihydrogens, 2.2 g.
5. according to the method for trace lead in claim 1, the 2 or 3 arbitrary described mensuration textiles, it is characterized in that, in the step (1); With the acidic sweat is extract, and the condition of soaking textile is: 37 ℃ are soaked 60min, take out textile; Extract is cooled to room temperature, filters for use.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103389317A (en) * | 2013-07-28 | 2013-11-13 | 浙江出入境检验检疫局检验检疫技术中心 | Analysis method of heavy metals in textiles |
| CN103728170A (en) * | 2014-01-07 | 2014-04-16 | 中华人民共和国北京出入境检验检疫局 | Proficiency testing sample used for measuring contents of extractable heavy metal lead and chromium of textile and preparation method of sample |
| CN104807727A (en) * | 2014-12-22 | 2015-07-29 | 中华人民共和国象山出入境检验检疫局 | Method for detecting migration quantity of benzophenone compounds in textiles |
| CN106872454A (en) * | 2017-01-13 | 2017-06-20 | 上海市质量监督检验技术研究院 | The screening technique of total lead content in a kind of textile |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103389317A (en) * | 2013-07-28 | 2013-11-13 | 浙江出入境检验检疫局检验检疫技术中心 | Analysis method of heavy metals in textiles |
| CN103389317B (en) * | 2013-07-28 | 2015-11-25 | 浙江出入境检验检疫局检验检疫技术中心 | A kind of Analysis of Heavy Metal method in textile |
| CN103728170A (en) * | 2014-01-07 | 2014-04-16 | 中华人民共和国北京出入境检验检疫局 | Proficiency testing sample used for measuring contents of extractable heavy metal lead and chromium of textile and preparation method of sample |
| CN103728170B (en) * | 2014-01-07 | 2015-10-28 | 中华人民共和国北京出入境检验检疫局 | Proficiency testing sample of and chrome determination plumbous for textile extractable heavy metal and preparation method thereof |
| CN104807727A (en) * | 2014-12-22 | 2015-07-29 | 中华人民共和国象山出入境检验检疫局 | Method for detecting migration quantity of benzophenone compounds in textiles |
| CN104807727B (en) * | 2014-12-22 | 2018-08-28 | 中华人民共和国象山出入境检验检疫局 | The detection method of benzophenone compound the amount of migration in a kind of textile |
| CN106872454A (en) * | 2017-01-13 | 2017-06-20 | 上海市质量监督检验技术研究院 | The screening technique of total lead content in a kind of textile |
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