CN103940758A - Method for detection of lead ions in water - Google Patents
Method for detection of lead ions in water Download PDFInfo
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- CN103940758A CN103940758A CN201310337492.9A CN201310337492A CN103940758A CN 103940758 A CN103940758 A CN 103940758A CN 201310337492 A CN201310337492 A CN 201310337492A CN 103940758 A CN103940758 A CN 103940758A
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Abstract
The invention provides a method for detection of lead ions in water. The method comprises the following steps: measuring to take a masking agent solution, a chromogenic agent solution and a buffer solution; sequentially adding the masking agent solution, the chromogenic agent solution and the buffer solution in a to-be-detected water sample, mixing uniformly, and thus obtaining a detection sample; and measuring an absorbance value of the detection sample by adopting a spectrophotometer, and calculating out the content of lead in the to-be-detected water sample, wherein the mass volume ratio of a chromogenic agent to water in the chromogenic agent solution is (0.05-5 g):1 L, the chromogenic agent is xylenol orange, the buffer solution is an acid hexamethylenetetramine buffer solution, and the masking agent solution contains a masking agent, water and hydrochloric acid. Due to addition of concentrated hydrochloric acid in the masking agent solution, a reagent can be better preserved under a condition of not affecting the pH value of the reagent, reagent waste is facilitated to be reduced, and resources are saved.
Description
Technical field
The present invention relates to on-line monitoring technique field, more particularly, relate to a kind of monitoring of lead ion.
Background technology
Lead is a kind of important raw material of industry, is easy to form alloy, plasticity is good, corrosion-resistant and can form the characteristics such as colored compound owing to having, and has research widely and application in fields such as metallurgy, chemical industry, material science.Plumbous (II) is also a kind of toxic heavy metal that can accumulate simultaneously, has non-biodegradable, can in environment, exist for a long time.The enrichment of plumbous (II) can produce toxic and side effect to each tissue of human body, causes the damage of nervous system, hemopoietic system, digestive system, kidney and enzyme system, especially very harmful to infant and preschool child's intelligent development.In recent years, along with developing rapidly of China's material industry and auto industry, in environment, lead content is in continuous increase, and lead contamination forms comparatively serious threat to environment for human survival and health.Plumbous primary pollution source is the waste water of the discharges such as accumulator, smelting, five metals, machinery, coating and electroplating industry.Qian Shi China implements one of index of total emission volumn control.Therefore, accurately monitor water quality lead ion content significant.
At present, the colorimetric estimation of lead ion is adopted to dithizone method mostly, need extracting operation, comparatively loaded down with trivial details, and in the conventional method, use poisonous extractant and screening agent, not only harmful, and contaminated environment.And while being applied to on-line monitoring, because process is loaded down with trivial details, the difference of extraction degree, can bring considerable influence to result.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.
For this reason, one object of the present invention is to propose a kind of method with detecting lead ion in water quality.
The method for detection of lead ion in water according to the embodiment of the present invention, comprises the following steps:
Measure screening agent solution, chromogenic reagent solution and damping fluid; In water sample to be detected, add successively described screening agent solution, chromogenic reagent solution and damping fluid and mix, obtaining test samples; And the absorbance of test samples described in use spectrophotometer measurement, and calculate the lead content in described water sample to be detected, wherein, in described chromogenic reagent solution, the mass volume ratio of developer and water is (0.05 ~ 5g): 1L, described developer is xylenol orange, described damping fluid is acid hexamethylenetetramine buffer solution, in described screening agent solution, contains screening agent, water and hydrochloric acid.
The present invention adds concentrated hydrochloric acid in screening agent solution, can under the condition that does not affect reagent pH value, better preserve reagent, is conducive to reduce reagent waste, has saved resource.
Wherein, described screening agent can in sodium citrate, disodium ethylene diamine tetraacetate, 1,10-ferrosin, oxammonium hydrochloride any one or multiple, wherein, especially preferred 1,10-ferrosin.Through the inventor's large quantity research discovery, these screening agents can both be sheltered heavy metal well, thereby can effectively improve plumbous selectivity.
In addition, preferably, described pack is (0.5 ~ 5g) with the mass volume ratio of screening agent and water in screening agent solution: (0.5 ~ 3) L; Further preferably, described pack is (0.5 ~ 2g) with the mass volume ratio of screening agent and water in screening agent solution: (0.5 ~ 2) L; Especially preferably, described pack is 1.5g:1L with the mass volume ratio of screening agent and water in screening agent solution.
Preferably, the concentrated hydrochloric acid that the described pack that is 1000ml in total amount is 37% by the mass concentration that has added 0.5 ~ 5ml in screening agent solution.If the addition of hydrochloric acid is too much, the easy pH value of medium during impact test, and if the addition of hydrochloric acid is too low, be difficult to play the effect of the stability of increase screening agent solution.
Preferably, use plumbous standard water solution value and described screening agent solution, chromogenic reagent solution and damping fluid to mix and measure absorbance, to draw lead solution standard absorbance curve, and by the absorbance of described test samples and described standard absorbance curve are compared to calculate the lead content in described water sample to be detected.
Preferably, the volume ratio of described water sample to be detected and screening agent solution, chromogenic reagent solution and damping fluid is (5 ~ 15): (1 ~ 2): (1 ~ 2): (1 ~ 2).
Preferably, the volume ratio of described screening agent solution, chromogenic reagent solution and damping fluid is (1 ~ 2): (1 ~ 2): (1 ~ 2).
Preferably, the volume ratio of described screening agent solution, chromogenic reagent solution and damping fluid is 1:1:1.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Embodiment
Describe embodiments of the invention below in detail.It should be noted that, the embodiment the following describes is exemplary, is intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
first, screening agent solution and preparation method thereof for pack is described.
According to the pack of the embodiment of the present invention with containing screening agent, water and hydrochloric acid in screening agent solution.
The present invention adds concentrated hydrochloric acid in screening agent solution, can under the condition that does not affect reagent pH value, better preserve reagent, is conducive to reduce reagent waste, has saved resource.
Wherein, described screening agent can in sodium citrate, disodium ethylene diamine tetraacetate, 1,10-ferrosin, oxammonium hydrochloride any one or multiple, wherein, especially preferred 1,10-ferrosin.Through the inventor's large quantity research discovery, these screening agents can both be sheltered heavy metal well, thereby can effectively improve plumbous selectivity.
In addition, preferably, described pack is (0.5 ~ 5g) with the mass volume ratio of screening agent and water in screening agent solution: (0.5 ~ 3) L; Further preferably, described pack is (0.5 ~ 2g) with the mass volume ratio of screening agent and water in screening agent solution: (0.5 ~ 2) L; Especially preferably, described pack is 1.5g:1L with the mass volume ratio of screening agent and water in screening agent solution.
Preferably, the concentrated hydrochloric acid that the described pack that is 1000ml in total amount is 37% by the mass concentration that has added 0.5 ~ 5ml in screening agent solution.If the addition of hydrochloric acid is too much, the easy pH value of medium during impact test, and if the addition of hydrochloric acid is too low, be difficult to play the effect of the stability of increase screening agent solution.
, it should be noted that herein, both can in prefabricated industry, add 37% concentrated hydrochloric acid, also can add as the case may be the hydrochloric acid of variable concentrations, as long as reset most after appearance, the concentration of described hydrochloric acid meets above-mentioned scope.
Preparation method according to the pack of the embodiment of the present invention with screening agent solution, comprises the steps:
A) take screening agent;
B) described screening agent is dissolved in to pure water, obtains prefabricated solution; And
C) in described prefabricated solution, add hydrochloric acid, obtain described pack screening agent solution.
Wherein, preferably, described pack is with in screening agent solution, and described pack is (0.5 ~ 5g) with the mass volume ratio of screening agent and water in screening agent solution: (0.5 ~ 3) L; Further preferably, described pack is (0.5 ~ 2g) with the mass volume ratio of screening agent and water in screening agent solution: (0.5 ~ 2) L; Especially preferably, described pack is 1.5g:1L with the mass volume ratio of screening agent and water in screening agent solution.
next, describe pack for detection of lead ion in water quality and preparation method thereof.
According to the pack for detection of lead ion in water quality of the present invention, comprise screening agent solution, chromogenic reagent solution and damping fluid.
Wherein, described screening agent solution is the screening agent solution according to above-mentioned arbitrary embodiment, does not repeat them here.
In addition, the screening agent solution of the embodiment of the present invention is suitable for combining with xylenol orange chromogenic reagent solution, porphin series solution, Fluorone reagent series chromogenic reagent solution, peacock green chromogenic reagent solution and azo chromogenic reagent solution, for detecting lead ion in water quality.
below, for inhomogeneity chromogenic reagent solution, its composition and configuration method is described respectively.
xylenol orange (XO)
Xylenol orange is a kind of very important spectrophotometric color reagent in microanalysis, and in phosphoric acid 2 acetic acid 2 borate buffer solutions of pH 6. 0, xylenol orange forms 1: 1 stable red complex with lead, causes the enhancing of absorbance.
XO chemical name is 3,3 '-bis-[N, N-bis-(ethyloic) amino methyl]-o-cresol sulfonphthalein, is a kind of sulfonephthalein ammonia carboxylic metallochromic indicator the most conventional in metallic ion analytic process.
XO has different chelating system (Chelating System) to exist under different acid-base conditions, therefore when metallic ion and XO formation chelate, also can carry out in a different manner chelating.
In p H=1~6 o'clock, in aqueous solution, XO molecule is mainly with H
5l
-and H
4l
2-existing, should be H in the main existence form of p H=6 o'clock XO
4l
2-, H
5l
-and H
4l
2-.
The absorbance of solution to be measured raises and increases with p H value, considers sensitivity and the reagent of measuring
The impact of the blank factors such as light absorption value, finally selects that p H=6. 0 is suitable reaction condition.
In addition, using phosphoric acid-acetic acid-borate buffer solution (pH 6. 0).This buffer solution forms by phosphoric acid, boric acid and acetic acid mixed preparing that concentration is 0. 04 mol/L, during use, with 0. 2 mol/L NaOH solution, is adjusted to pH 6. 0 on acidometer.
b) porphin series
Porphyrin reagent is because its special optical property becomes a kind of very promising organicvisualization reagent.As organicvisualization reagent, porphyrin has the sensitivity of superelevation, and its molar absorptivity is up to 1 * 10
5~6 * 10
5l mol
-1cm
-1, therefore, the research that the porphyrin reagent of usining is measured heavy metal ion as developer has caused numerous scientific workers' extensive concern.In the present invention, utilize porphyrin easily to generate the chemical characteristic of 1: 1 high stability complex with plumbous (II), porphyrin reagent is applied to detect the lead content in water quality.
In described chromogenic reagent solution, the mass volume ratio of developer and solvent is (0.05 ~ 5g): 1L, and described developer is porphin series, and described solvent is (N, N-dimethyl formamide).
In addition, described porphin series comprises: four (4-methoxyphenyl) porphyrin, four (4 chloro-3 sodium sulfonate phenyl) porphyrin, four (2,5-difluorophenyl) porphyrin, four (3-hydroxy phenyl) porphyrin, four (2,5-difluorophenyl) porphyrin, four (the bromo-4-hydroxy benzenes of 3,5-bis-) porphyrin, four (4-sulfonic benzo) porphyrin, P tetra-(4-pyridine) porphyrin etc.Wherein, above-mentioned porphin series can be used separately, also can multiple merging use.
In addition, in described chromogenic reagent solution, can also contain catalyzer, described catalyzer comprises at least one in oxammonium hydrochloride salt, oxine, sodium fluoride-Citrate-ethylene diamine, phenanthroline, ascorbic acid.
In addition, when using porphin series solution, can use borate buffer solution, and medium pH is adjusted under weak basic condition, for example chromogenic reaction is carried out in left and right, pH9 ~ 10.5.
c) Fluorone reagent series developer
Fluorones reagent is a kind of common metallic ion developer, utilize fluorone reagent to carry out the conditional request of lead (II) assay simple, under alkaline medium, room temperature, just can complete rapidly the complexing chromogenic reaction of lead (II) and phenylfluorone reagent, color development system is stable, and adds surfactant to have stronger sensitization to system.
For example, can in borate buffer medium, utilize plumbous (II) and DBH-PF cetyl trimethyl ammonium bromide (CTMAB) exist the lower principle that forms red complex measure water quality in the content of lead (II).Can also be in the medium solution that p H value is 12.5~13.3, the complex anion of Pb (II) and phenylfluorone and the kation that cetyl trimethyl ammonium bromide ionizes out form hyacinthine ternary complex, can be in 0~8.0 μ g/ 25mL concentration range Accurate Determining micro lead (II) content.
As Fluorone reagent series developer, can enumerate 5/-2 nitro salicyl fluorone, trimethoxy fluorone, adjacent chloro phenylfluorone (
σ-cPF), O-Nitrophenylfluorone fluorone (
σ-nPF) etc.Wherein, above-mentioned Fluorone reagent series developer can be used separately, also can multiple merging use.
In addition, in described chromogenic reagent solution, the mass volume ratio of developer and water is (0.05 ~ 5g): 1L).
In addition, when using Fluorone reagent series developer, can use borate buffer solution, and medium pH is adjusted under weak basic condition, for example chromogenic reaction is carried out in left and right, pH9 ~ 10.5.
d) peacock green
Pb
2+can form complex with MG-KI, the absorbance of complex and Pb
2+concentration is relevant.Research shows, pH 4. 0 o'clock, Pb2+-MG-KI at room temperature can form rapidly stable complex, complex in the absorbance at 618nm place with Pb
2+concentration increases and declines, plumbous concentration 0. 4-2. 8mg/ L
Scope and negative absorbance are good linear relationship, and molar absorptivity is 6. 5 * 10
4lmol
-1cm
-1.relative deviation is 2. 5 % (n=11).The method is highly sensitive, and favorable reproducibility is easy and simple to handle, analysis speed is fast, is suitable for the Fast Measurement of industrial wastewater.
Described damping fluid can be acid hexamethylenetetramine buffer solution.
e) azo developer
Under strong acidic condition, plumbous (II) can make Azo-reagents fade, and absorbance and lead (II) concentration are linear dependence within the specific limits.
Conventional Azo-reagents has that Arsenazo, azo chlorine are Phosphorus, azochlorosulfonate class, azo sulphur class etc., wherein conventional with Arsenazo.
Because color development system need be carried out under strong acidic condition, therefore utilize the selectivity of arsennazo group reagents mensuration plumbous (II) stronger, this is conducive to useless trace lead in water (II) and measures.For example, the chromogenic reaction of Dibromo-p-chloro carboxyazo arsine and micro lead (II), this method selectivity can allow by force the interfering ions such as a large amount of copper, zinc, aluminium to exist; The dibromo of take is developer to methyl bromide azo sulphur (DB-MBSA), at 638 nm wavelength places, measure plumbous (II) content, method antijamming capability is strong, except Ca (II) and Ba (II), other ions all do not produce interference, and can adopt potassium iodide-methyl isobutyl ketone (KI-MI-B K) extraction to eliminate interference for Ca (II) and Ba (II) interfering ion.
finally, the method for detection of lead ion in water is described.
Use the pack of above-mentioned any embodiment, can be used for detecting the content of the lead ion in water quality.
The method for detection of lead ion in water according to the embodiment of the present invention, comprises the following steps:
Measure screening agent solution, chromogenic reagent solution and damping fluid;
In water sample to be detected, add successively described screening agent solution, chromogenic reagent solution and damping fluid and mix, obtaining test samples; And
The absorbance of test samples described in use spectrophotometer measurement, and calculate the lead content in described water sample to be detected.
Use plumbous standard water solution value and described screening agent solution, chromogenic reagent solution and damping fluid to mix and measure absorbance, to draw lead solution standard absorbance curve, and by the absorbance of described test samples and described standard absorbance curve are compared to calculate the lead content in described water sample to be detected.
Preferably, the volume ratio of described water sample to be detected and screening agent solution, chromogenic reagent solution and damping fluid is (5 ~ 15): (1 ~ 2): (1 ~ 2): (1 ~ 2); Further preferably, the volume ratio of described screening agent solution, chromogenic reagent solution and damping fluid is (1 ~ 2): (1 ~ 2): (1 ~ 2); The volume ratio of especially preferred described screening agent solution, chromogenic reagent solution and damping fluid is 1:1:1.
With in prior art, must compare with abstraction technique, according to detection method of the present invention, avoided harm and the environmental pollution of using the contour toxic organic solvent extraction of methenyl choloride to bring, easy fast, measurement result is accurate, more friendly to environment.
Below, by preferred embodiment, describe in detail according to the pack of the embodiment of the present invention and use the detection method of this pack.
Wherein, take developer as xylenol orange, buffer agent solution as phosphoric acid-acetic acid-borate buffer solution, screening agent as 1,10-ferrosin be that example describes detection method.Situation for using the pack of other embodiment, except the composition difference of pack, can adopt identical method to detect, and description is omitted herein.
Embodiment 1
For monitoring the raw materials of the pack of lead ion, be: concentrated hydrochloric acid and pure water that the acid hexamethylenetetramine that the xylenol orange that 1,10-ferrosin that purity is AR, purity are AR, purity are AR, mass concentration are 37%.
The preparation of screening agent solution: take a certain amount of acid hexamethylenetetramine buffer solution, add a small amount of pure water to dissolve, in 1000ml volumetric flask, add 1.5ml concentrated hydrochloric acid, use pure water constant volume, mix standby.Wherein, in described screening agent solution, the mass volume ratio of screening agent and water is 1.5g:1L.
The preparation of chromogenic reagent solution: accurately take a certain amount of xylenol orange and be dissolved in pure water, be stirred to completely and dissolve, then add pure water, be settled to 1000ml, mix, be kept in brown volumetric flask standbyly, the mass volume ratio of described developer and pure water is 1.5g:1L.
The preparation of buffer solution: take a certain amount of phosphoric acid-acetic acid-boric acid and be dissolved in pure water, add acid that pH is adjusted to 6, shake up, then add pure water, be settled to 1000ml, shake up, standby.
The drafting of typical curve: accurately pipette plumbous standard solution that 0,5,10,15,20,25,30,35,40,45,50 ml concentration are 20mg/L in 100ml volumetric flask, add 1ml screening agent, solution is fully mixed, after adding 1 ml developer, solution is fully mixed, add again 1ml damping fluid, fully shake up, after a few minutes, take reagent blank as reference, 30 mm cuvettes, absorbance is measured at certain wavelength place, and drawing standard curve.
Embodiment 2
By a certain amount of target actual water sample that adds of Tianrui's online water quality lead ion monitor automatic sucking, automatic sucking screening agent solution successively again, chromogenic reagent solution, buffer soln, by automatic mixing, after 5 minutes, take reagent blank as reference, and the cuvette of 30 mm light paths, measures absorbance at 535nm wavelength place, the result of measuring for six times is respectively 1.548,1.597,1.604,1.626,1.580,1.615, and relative standard deviation RSD is 1.7%.
From the present embodiment, the pack monitoring lead ion of monitoring lead ion prepared by employing the present invention, measured result precision, accuracy are all fine, have solved due to residual the brought error of auto injection pipeline.
Embodiment 3
By a certain amount of actual water sample of Tianrui's online water quality lead ion monitor automatic sucking, automatic sucking screening agent solution successively again, chromogenic reagent solution, buffer soln, by automatic mixing, after 10 minutes, take reagent blank as reference, and the cuvette of 30mm light path, measures absorbance at 535nm wavelength place, the result of measuring for six times is respectively 0.092,0.086,0.088,0.084,0.084,0.088,0.088, and relative standard deviation is 0.0028.
From the present embodiment, adopt agents useful for same of the present invention and water sample that proportioning is surveyed to detect lower limit and be low to moderate 0.1mg/L, reach GB requirement.
In the description of this instructions, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention in the situation that not departing from principle of the present invention and aim, modification, replacement and modification.
From the present embodiment, adopt agents useful for same of the present invention and water sample that proportioning is surveyed to detect lower limit and be low to moderate 0.1mg/L, reach GB requirement.
In the description of this instructions, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention in the situation that not departing from principle of the present invention and aim, modification, replacement and modification.
Claims (11)
1. for detection of a method for lead ion in water, comprise the following steps:
Measure screening agent solution, chromogenic reagent solution and damping fluid;
In water sample to be detected, add successively described screening agent solution, chromogenic reagent solution and damping fluid and mix, obtaining test samples; And
The absorbance of test samples described in use spectrophotometer measurement, and calculate the lead content in described water sample to be detected, wherein,
In described chromogenic reagent solution, the mass volume ratio of developer and water is (0.05 ~ 5g): 1L, and described developer is xylenol orange,
Described damping fluid is acid hexamethylenetetramine buffer solution,
In described screening agent solution, contain screening agent, water and hydrochloric acid.
2. method according to claim 1, is characterized in that, in described screening agent solution, the mass volume ratio of screening agent and water is (0.5 ~ 5g): (0.5 ~ 3) L.
3. method according to claim 2, is characterized in that, in described screening agent solution, the mass volume ratio of screening agent and water is (0.5 ~ 2g): (0.5 ~ 2) L.
4. method according to claim 2, is characterized in that, in described screening agent solution, the mass volume ratio of screening agent and water is 1.5g:1L.
5. method according to claim 1, is characterized in that, the concentrated hydrochloric acid that the mass concentration that has added 0.5 ~ 5ml in the described screening agent solution that is 1000ml in total amount is 37%.
6. method according to claim 1, is characterized in that, described screening agent be in sodium citrate, disodium ethylene diamine tetraacetate, 1,10-ferrosin, oxammonium hydrochloride any one or multiple.
7. method according to claim 1, is characterized in that, described screening agent is 1,10-ferrosin.
8. method according to claim 1, it is characterized in that, use plumbous standard water solution value and described screening agent solution, chromogenic reagent solution and damping fluid to mix and measure absorbance, to draw lead solution standard absorbance curve, and by the absorbance of described test samples and described standard absorbance curve are compared to calculate the lead content in described water sample to be detected.
9. method according to claim 1, is characterized in that, the volume ratio of described water sample to be detected and screening agent solution, chromogenic reagent solution and damping fluid is (5 ~ 15): (1 ~ 2): (1 ~ 2): (1 ~ 2).
10. method according to claim 1, is characterized in that, the volume ratio of described screening agent solution, chromogenic reagent solution and damping fluid is (1 ~ 2): (1 ~ 2): (1 ~ 2).
11. methods according to claim 1, is characterized in that, the volume ratio of described screening agent solution, chromogenic reagent solution and damping fluid is 1:1:1.
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Cited By (3)
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CN104634751A (en) * | 2015-01-30 | 2015-05-20 | 胡孟 | Pre-packaging reagent for detecting content of lead ions in water |
CN108593638A (en) * | 2018-08-13 | 2018-09-28 | 广州安诺科技股份有限公司 | A method of heavy metal lead in the fresh egg of detection |
CN112997076A (en) * | 2018-11-05 | 2021-06-18 | 哈希公司 | Digestion of lead (0) and subsequent colorimetric detection of lead (II) |
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2013
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104634751A (en) * | 2015-01-30 | 2015-05-20 | 胡孟 | Pre-packaging reagent for detecting content of lead ions in water |
CN104634751B (en) * | 2015-01-30 | 2018-05-01 | 胡孟 | Detect the pre-packaged reagent of lead ion content in water |
CN108593638A (en) * | 2018-08-13 | 2018-09-28 | 广州安诺科技股份有限公司 | A method of heavy metal lead in the fresh egg of detection |
CN108593638B (en) * | 2018-08-13 | 2020-10-27 | 广州安诺科技股份有限公司 | Method for detecting heavy metal lead in fresh eggs |
CN112997076A (en) * | 2018-11-05 | 2021-06-18 | 哈希公司 | Digestion of lead (0) and subsequent colorimetric detection of lead (II) |
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Application publication date: 20140723 |