CN112798706A - Method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salt of cultural relics - Google Patents
Method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salt of cultural relics Download PDFInfo
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- 150000001449 anionic compounds Chemical class 0.000 title claims abstract description 42
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- 238000000034 method Methods 0.000 title claims abstract description 22
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- 239000012224 working solution Substances 0.000 claims abstract description 27
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- 150000002500 ions Chemical class 0.000 claims abstract description 12
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- 239000000523 sample Substances 0.000 claims description 27
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- 239000010452 phosphate Substances 0.000 claims description 26
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- 238000001514 detection method Methods 0.000 claims description 23
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- 241000219193 Brassicaceae Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XQFRJNBWHJMXHO-RRKCRQDMSA-N IDUR Chemical compound C1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C(I)=C1 XQFRJNBWHJMXHO-RRKCRQDMSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 241001311547 Patina Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation using ion-exchange
Abstract
The invention relates to a method for simultaneously detecting various organic acid radicals and inorganic anions in harmful salt of a cultural relic, belonging to the technical field of preventive protection of the cultural relic. The method comprises the steps of preparing a standard working solution with gradient concentration by five standard products of formate, acetate, propionate, butyrate and valerate and a multi-element standard solution, sequentially detecting the standard working solution by adopting an ion chromatograph to obtain a chromatogram, and drawing a standard curve and fitting a standard curve equation by using peak areas of different organic acid radicals and anions to the concentrations of the organic acid and the anions in the standard working solution; detecting the crystalline salt aqueous solution sample under the same chromatographic condition, and calculating the concentrations of the organic acid radicals and the anions detected in the crystalline salt aqueous solution sample according to a standard curve equation; and calculating the mass fractions of the organic acid radicals and the anions in the crystallized salt according to the concentrations of the detected organic acid radicals and anions in the sample of the crystallized salt water solution. The method can be used for analyzing the environmental pollutant species causing the salt damage of the cultural relics.
Description
Technical Field
The invention relates to a method for simultaneously detecting various organic acid radicals and inorganic anions in harmful salt of a cultural relic, belonging to the technical field of preventive protection of the cultural relic.
Technical Field
Salt damage is one of the main causes of damage to immovable cultural relics (such as ancient cultural relics, stone cultural relics, murals and the like) or movable cultural relics (such as metal cultural relics, ceramic cultural relics and the like).
The harmful salts causing damage mainly comprise chloride, sulfate, nitrate and the like. Wherein, Na2SO4The salts widely regarded as the most damaging: it can cause the diseases of fracture of site, sandy soil, crisp soil powder, etc.; the stone cultural relics can be internally expanded and cracked, the external surface layer is polluted, and the integrity and the ornamental value of the stone cultural relics are damaged; and can also cause diseases such as herpes, powder layer armor, lamellar shedding, and base of crunchy crust on the surface of the mural. In comparison with other salts, Na2SO4The salt solution has higher saturation and is more sensitive to temperature; when Na is present2SO4When the salt is transferred to the surface of the cultural relic or the external environment changes (such as moisture reduction or temperature reduction), salt crystals are precipitated on the surface layer of the cultural relic, and then the salt crystals are repeatedly dissolved and crystallized. In this Na2SO4During the dissolution shrinkage-crystallization expansion process of the salt, the volume can be different by 4.18 times, so that huge mechanical pressure is generated to destroy the structure of the cultural relic.
The harm of the chloride salt to metal cultural relics and ceramic cultural relics is most obvious. For metal cultural relics bronze wares, chloride salts can induce "bronzing". The bronze disease isProgressive corrosion of copper alloy initiated by green patina cuprous chloride, bronze ware first receiving Cl-The cuprous chloride is generated by corrosion, and is contacted with oxygen under the condition of high humidity, the cuprous chloride is converted into basic cupric chloride and hydrochloric acid, and the copper is converted into the cuprous chloride when meeting the hydrochloric acid, so that the corrosion reaction is carried out repeatedly, and the corrosion product of the bronze ware is continuously expanded and deepened, so that the bronze ware is completely crisp and decomposed into powder. And for metallic cultural relics ironware, Cl-Can prevent the active wustite (gamma-FeOOH) generated on the surface of the ironware from being converted into the inactive goethite (alpha-FeOOH), and destroy the formation of a passive film on the surface of the ironware, so that the ironware is in an unstable state, thereby accelerating the corrosion of the ironware. For the pottery cultural relics, when NaCl, CaCl2Entering the pottery with high porosity, on one hand, the ceramic has a replacement reaction with metal minerals in the pottery, so that the internal structure of the pottery is changed, and the deterioration of the pottery is caused; on the other hand, the salt penetrates and accumulates in the gaps of the pottery to form a micro solution of soluble salt, and when the temperature and humidity in the environment are changed alternately, the repeated change of dissolution and crystallization occurs, thereby reducing the strength of the pottery, and causing the pottery to become loose and fragile.
The formation of salt is closely related to the existence of the cultural relics or the storage environment. The temperature and humidity changes of the environment of immovable cultural relics or movable cultural relics (such as metal cultural relics and ceramic cultural relics) can cause the crystallization-dissolution-recrystallization process of soluble salt in the cultural relics, and further can cause serious diseases. In recent years, researches show that the salt damage condition of cultural relics, the cause of the salt damage, the salt damage degree and the like are greatly different due to different regions, natural environments or collection conditions.
The detection and analysis of the components of the crystalline salt (namely, the related data of the composition type and the phase form of the crystalline salt on the cultural relic) are combined with the existence of the cultural relic or the environmental condition of a storage ring, the migration of the salt in the cultural relic and the possibility of causing the salt damage are presumed, the types of the environmental pollutants causing the salt damage of the cultural relic are analyzed, the cause of the local salt damage is analyzed, a new basis is provided for preventing, delaying and predicting the occurrence of diseases, and a certain reference value is provided for the preventive protection of the cultural relic.
The traditional and current determination of fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate is generally carried out by titration. However, the titration method is complicated to operate, is not beneficial to the detection of a large number of samples, and has certain limitation on the samples with lower content; the color of the titration end point is difficult to distinguish, or if sediment is generated in the titration process, the titration end point is difficult to determine, interference ions are more, the error is larger, and the operation is troublesome; wherein, the silver, chromium and mercury plasma can cause secondary pollution to the environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for simultaneously detecting a plurality of organic acid radicals and inorganic anions in harmful salts of cultural relics, namely a method for simultaneously realizing environmental pollutants of crystal salts separated out from cultural relic diseases by adopting ion chromatography, wherein the environmental pollutants are caused by formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate, sulfate and the like, and has the characteristics of low cost, short detection time and high accuracy.
A method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salts of cultural relics comprises the following specific steps:
(1) preparing a standard working solution: five standard substances of formate, acetate, propionate, butyrate and valerate are added into ultrapure water for constant volume, and mixed acid standard stock solution is prepared; mixing the mixed acid standard stock solution with the multi-element standard solution, and then diluting with ultrapure water to obtain a series of standard working solutions with gradient concentrations; wherein the multielement standard solution contains fluorinion, chloride ion, bromide ion, nitrate radical, nitrite radical, phosphate radical and sulfate radical;
(2) sequentially detecting ion chromatograms of a series of concentrations of standard working solution and a blank control sample by an ion chromatograph, wherein chromatographic peaks in the chromatograms correspond to fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, nitrate, sulfate and phosphate according to peak emergence time, and respectively drawing a standard curve by using peak areas of fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, nitrate, sulfate and phosphate to the concentrations of fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, sulfate and phosphate in the standard working solution, wherein the correlation coefficient of a standard curve equation is not lower than 0.995;
(3) Collecting crystallized salt on the cultural relic, dissolving the crystallized salt in ultrapure water, and performing constant volume to obtain a crystallized salt water solution sample, wherein the crystallized salt water solution sample contains one or more anions selected from formate, acetate, propionate, butyrate, valerate, fluoride ions, chloride ions, bromide ions, nitrate, nitrite, phosphate and sulfate radicals; the type of environmental pollutants causing the precipitation of crystal salt from the cultural relic disease can be detected;
(4) detecting a crystal salt water solution sample and a blank control sample under the same chromatographic condition of the detection standard working solution in the step (2), detecting to obtain peak areas of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate, respectively calculating the concentration of the detected organic acid radical and/or inorganic anion in the crystal salt water solution sample according to a standard curve equation of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate, and calculating the mass fraction of the organic acid radical and/or inorganic anion in the crystal salt; analyzing environmental pollutants causing the cultural relic diseases to separate out crystal salt;
The gradient concentrations of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate in the standard working solution in the step (1) are respectively 5.0, 10.0, 15.0, 20.0, 25.0 and 30.0 mu g/ml, wherein the concentrations of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate in the standard working solution in each gradient concentration are equal;
the chromatographic detection conditions of the step (2) and the step (4) are as follows: the gradient concentration range of the detected standard working solution is 5-30 mug/mL, the leacheate is KOH solution with the concentration of 2-30mmol/L, the column temperature is 30 ℃, the ECD detector has the flow rate of 1.0-1.2 mL/min, the suppressor current is 90mA-144mA, and the sample injection amount is 25 ul;
further, when the elution program is 0-10.5min, the concentration of KOH eluent is 2 mmol/L; when the time is 10.5-29min, the concentration of the KOH leacheate is increased from 2mmol/L to 30 mmol/L; when the time is 29-34min, the concentration of KOH leacheate is 30 mmol/L; when the time is 34-35min, the concentration of KOH leacheate is 2 mmol/L;
the ultrapure water is used as a solvent of the crystallization salt, although carbon dioxide is very soluble in water, the detection of carbonate does not interfere with various organic acid radicals and inorganic anions to be analyzed.
The invention has the beneficial effects that:
(1) the method can measure one or more of various organic acid radicals and inorganic anions in the crystal salt on the cultural relic in the collection of cultural relics; weakly retained ions such as organic acids and strongly retained ions such as inorganic anions can be detected simultaneously without mutual interference. The detection range is 5.0-30.0 mu g/ml, and the method is suitable for analyzing environmental pollutants causing cultural relic diseases to separate out crystal salt;
(2) the method can adopt ultrapure water as a solvent of the crystallization salt, and has simple sample treatment and easy operation;
(3) the method can quantitatively calculate the mass fractions of the organic acid radicals and the inorganic anions in the crystalline salt.
Drawings
FIG. 1 is an ion chromatogram of various organic acid radicals and inorganic anions in a standard working solution of 20 ppm;
FIG. 2 is a standard curve of fluoride ion;
FIG. 3 is a standard curve for acetate;
FIG. 4 is a standard curve for chloride ion;
FIG. 5 is a standard curve for nitrate nitrogen.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salts of cultural relics comprises the following specific steps:
(1) Preparing a mixed acid standard stock solution (rho is 100 ug/mL): accurately measuring a formate standard solution (rho 1000ug/mL), an acetate standard solution (rho 1000ug/mL), a propionate standard solution (rho 1000ug/mL), a butyrate standard solution (rho 1000ug/mL) and a valerate standard solution (rho 50000ug/mL), measuring a proper amount, diluting with ultrapure water, and preparing into a mixed acid standard stock solution containing 100ug/mL of each of A, B, C, D and valerate, wherein the solution is prepared on site;
(2) accurately measuring mixed acid standard stock solution and multi-element standard solution respectively, mixing uniformly, diluting with ultrapure water to prepare a series of standard working solutions with gradient concentrations of 5.0, 10.0, 15.0, 20.0, 25.0 and 30.0 μ g/ml in sequence, and taking a blank reference sample as ultrapure water; wherein the multielement standard solution contains fluorinion, chloride ion, bromide ion, nitrate radical, nitrite radical, phosphate radical and sulfate radical;
(3) measuring 5.0, 10.0, 15.0, 20.0, 25.0 and 30.0 mu g/ml of standard working solution by an ion chromatograph in sequence to obtain ion chromatograms of five volatile organic acids; the components corresponding to chromatographic peaks in the chromatogram are as follows in sequence by time order: fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, nitrate, sulfate and phosphate (see figure 1), wherein a carbonate peak is detected at 23.744min in figure 1, and the carbonate peak does not interfere with detection of various organic acid radicals and inorganic anion components; repeatedly measuring the standard working solution with each concentration for more than 3 times, carrying out quantitative analysis on the detection data by adopting Chromeleon 7.2 software, respectively drawing standard curves of each organic acid and inorganic anion, and fitting the standard curves into a standard curve equation, wherein the correlation coefficient of the standard curve equation is not lower than 0.995; wherein, the detection conditions of the 5.0-30.0 mug/mL standard working solution and the blank control sample are as follows: performing gradient elution by using a KOH solution, wherein the concentration range of KOH eluent is 2-30mmol/L, the column temperature is 30 ℃, the flow rate of an ECD detector is 1.2mL/min, the current of an inhibitor is 90mA, and the sample injection amount is 25 ul; specifically, when the elution program is 0-10.5min, the concentration of KOH leacheate is 2 mmol/L; when the time is 10.5-29min, the concentration of the KOH leacheate is increased from 2mmol/L to 30 mmol/L; when the time is 29-34min, the concentration of KOH leacheate is 30 mmol/L; when the time is 34-35min, the concentration of KOH leacheate is 2 mmol/L;
The blank control sample is ultrapure water, the carbonate peak is detected at 23.744min in the ion chromatogram (the carbonate peak has no interference on the detection of various organic acid radicals and inorganic anion components), but no target organic acid radical and inorganic anion are detected, and the blank control sample is proved to contain no organic acid radical and inorganic anion component to be detected;
detecting 5.0-30.0 μ g/mL standard working solution to obtain standard curves of fluoride ion, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, nitrate, sulfate and phosphate respectively, wherein the standard curve of fluoride ion is shown in FIG. 2, and the standard curve equation is shown in formula (1); the standard curve of acetate is shown in FIG. 3, and the standard curve equation is shown in formula (2); the standard curve of the chloride ions is shown in figure 4, and the standard curve equation is shown in formula (3); the standard curve of nitrate radical is shown in figure 5, and the standard curve equation is shown in formula (4); retention time, standard curve equation and linear range of various organic acid radicals and inorganic anions are shown in table 1, and correlation coefficients of all standard curves are higher than 0.995 and meet the requirements of detection standards;
y＝0.3937x+0.1742 (1)
y＝0.0733x+0.2059 (2)
y＝0.2676x-0.0783 (3)
y＝0.1451x-0.0997 (4)
TABLE 1 Retention time, Standard Curve equation, Linear Range and detection Limit for various organic acid radicals and inorganic anions
(4) Collecting crystal salt on cultural relics in a collection, weighing a proper amount of crystal salt solid, dissolving the crystal salt solid in a proper amount of ultrapure water, filtering the solution by using a 0.45um needle type filter and transferring the solution into a volumetric flask; adding a proper amount of water to dissolve the solid, filtering and transferring the solid into a volumetric flask for three times, and finally fixing the volume in the volumetric flask to obtain a crystallized saline solution sample; wherein the sample of the aqueous crystalline salt solution comprises one or more anions selected from formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate, and sulfate; the type of environmental pollutants causing the precipitation of crystal salt from the cultural relic disease can be detected;
(5) detecting a crystalline salt aqueous solution sample and a blank control sample under the same chromatographic condition of a detection standard working solution as the standard working solution, detecting peak areas of obtained formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate, respectively calculating the concentrations of detected organic acid radicals and inorganic anions in the crystalline salt aqueous solution sample according to a standard curve equation of the formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate, quantitatively calculating the mass fractions of the organic acid radicals and the inorganic anions in the crystalline salt, and analyzing environmental pollutants causing cultural relic diseases to separate out the crystalline salt;
(6) Performing quantitative analysis on the detection data by adopting Chromeleon 7.2 software, and calculating the concentrations of organic acid radicals and inorganic anions contained in the crystal salt water solution sample; a control blank sample of the crystallized salt aqueous solution sample is ultrapure water, the crystallized salt aqueous solution sample and the ultrapure water also have a carbonate peak at 23.744min, the carbonate peak has no interference on the detection of various organic acid radicals and inorganic anion components, no target organic acid radicals and inorganic anions are detected in the ultrapure water, and the blank control sample is proved to contain no organic acid radicals and inorganic anion components to be detected;
(7) quantitatively calculating the mass fractions of the organic acid radicals and the inorganic anions in the crystallized salt according to the detection results of the concentrations of various organic acid radicals and inorganic anions in the known crystallized salt water solution sample, and referring to formula (5);
in the formula:
omega-mass fraction of certain organic acid radical or inorganic anion in the crystalline salt,%;
m-mass of the crystalline salt weighed when preparing the sample of the aqueous solution of crystalline salt, mg;
c is the concentration of certain organic acid radical or inorganic anion in the sample of the crystallized salt water solution, mu g/ml;
v-volume of sample of crystalline saline solution, ml.
Example 2: testing of crystalline salt on the back of the Han sheep Tianxia Oroban
The appearance of the crystallized salt on the back of the Wadang mustards in Han sheep is bright white down feather-like crystals and is light; weighing 0.0261g of solid, dissolving in ultrapure water, filtering with 0.45um needle filter, and transferring into volumetric flask; adding a proper amount of water to dissolve the solid, filtering and transferring the solid into a volumetric flask for three times; finally, the volume of the solution in the volumetric flask is determined to be 25ml, and a crystal salt water solution sample is obtained; detecting a crystal salt aqueous solution sample and blank ultrapure water by using the same chromatographic conditions as in example 1; the measured values of the concentrations of various organic acid groups and inorganic anions in the sample of the aqueous solution of the crystalline salt in this example are shown in Table 3;
TABLE 3 concentration measurements (. mu.g/ml) of various organic acid groups and inorganic anions in samples of aqueous solutions of crystalline salts
Note ND indicates no detection;
the mass fractions of various organic acid groups and inorganic anions in the crystalline salt are calculated by adopting the formula (5) in the example 1, and are shown in a table 4;
TABLE 4 Mass fractions (%) of various organic acid groups and inorganic anions in the crystalline salts
Note ND indicates no detection;
as can be seen from Table 4, the sample of the crystalline salt aqueous solution contains acetate, chloride and nitrate, and the bright white down-like crystalline salt on the back surface of the article of vadang contains 23.56% by mass of acetate, 6.11% by mass of chloride and 17.81% by mass of nitrate as calculated by the formula (5) in example 1; in addition, the main component of the crystalline salt was found to be C by XRD analysis 6H9Ca3ClN2O12·7H2O, assuming that the amount of the substance is 1mol, the mass fractions (%) of acetate, chloride and nitrate contained therein calculated from the molecular formulae are 30.41%, 6.01% and 21.31%, respectively; the species of acetate, chloride and nitrate radical detected by the two analysis methods are consistent, the calculation results of the mass fraction are basically approximate, and the deviation of the mass fraction possibly comes from the content of crystal water and trace impurities insoluble in ultrapure water; therefore, the method for detecting the mass fractions of various organic acid radicals and inorganic anions in the crystalline salt by ion chromatography is reliable. The detection result shows that the types of the environmental pollutants causing the precipitation of the crystal salt from the cultural relic disease mainly comprise acetic acid, chloride ions and nitrogen oxide in the ambient air; the detection and analysis of the components and the content of the crystalline salt provide a new basis for preventing, delaying and predicting the occurrence of diseases by knowing the types of environmental pollutants causing the salt damage of the cultural relics and analyzing the causes of the local salt damage, and have reference value for the preventive protection of the cultural relics.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salts of cultural relics is characterized by comprising the following specific steps:
(1) preparing a standard working solution: five standard substances of formate, acetate, propionate, butyrate and valerate are added into ultrapure water for constant volume, and mixed acid standard stock solution is prepared; mixing the mixed acid standard stock solution with the multi-element standard solution, and then diluting with ultrapure water to obtain a series of standard working solutions with gradient concentrations; wherein the multielement standard solution contains fluorinion, chloride ion, bromide ion, nitrate radical, nitrite radical, phosphate radical and sulfate radical;
(2) sequentially detecting ion chromatograms of a series of concentrations of standard working solution and a blank control sample by an ion chromatograph, wherein chromatographic peaks in the chromatograms correspond to fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, nitrate, sulfate and phosphate according to peak emergence time, and respectively drawing a standard curve by using peak areas of fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, nitrate, sulfate and phosphate to the concentrations of fluoride, acetate, propionate, formate, butyrate, valerate, chloride, nitrite, bromide, sulfate and phosphate in the standard working solution, wherein the correlation coefficient of a standard curve equation is not lower than 0.995;
(3) Collecting crystallized salt on the cultural relic, dissolving the crystallized salt in ultrapure water, and performing constant volume to obtain a crystallized salt water solution sample, wherein the crystallized salt water solution sample contains one or more anions selected from formate, acetate, propionate, butyrate, valerate, fluoride ions, chloride ions, bromide ions, nitrate, nitrite, phosphate and sulfate radicals;
(4) and (3) detecting the sample of the crystalline salt aqueous solution and a blank control sample under the same chromatographic condition of the detection standard working solution in the step (2), detecting to obtain peak areas of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate, respectively calculating the concentration of the detected organic acid radical and/or inorganic anion in the sample of the crystalline salt aqueous solution according to a standard curve equation of the formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate, and calculating the mass fraction of the organic acid radical and/or inorganic anion in the crystalline salt.
2. The method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salts of cultural relics according to claim 1, which is characterized in that: the gradient concentrations of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate in the standard working solution in the step (1) are respectively 5.0, 10.0, 15.0, 20.0, 25.0 and 30.0 mu g/ml, wherein the concentrations of formate, acetate, propionate, butyrate, valerate, fluoride, chloride, bromide, nitrate, nitrite, phosphate and sulfate in the standard working solution with each gradient concentration are equal.
3. The method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salts of cultural relics according to claim 1, which is characterized in that: the chromatographic detection conditions of the step (2) and the step (4) are as follows: the gradient concentration range of the detected standard working solution is 5-30 mug/mL, the leacheate is KOH solution with the concentration of 2-30mmol/L, the column temperature is 30 ℃, the ECD detector has the flow rate of 1.0-1.2 mL/min, the suppressor current is 90mA-144mA, and the sample injection amount is 25 ul.
4. The method for simultaneously detecting multiple organic acid radicals and inorganic anions in harmful salts of cultural relics according to claim 3, which is characterized in that: when the elution program is 0-10.5min, the concentration of KOH leacheate is 2 mmol/L; when the time is 10.5-29min, the concentration of the KOH leacheate is increased from 2mmol/L to 30 mmol/L; when the time is 29-34min, the concentration of KOH leacheate is 30 mmol/L; the KOH leacheate concentration is 2mmol/L when the time is 34-35 min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101825618A (en) * | 2010-05-18 | 2010-09-08 | 上海博物馆 | Rapid detection method of volatile acid in exhibited materials collected by museum based on passive sampling |
| CN102128885A (en) * | 2010-12-08 | 2011-07-20 | 广东中烟工业有限责任公司 | Method for quickly and simultaneously detecting 16 inorganic anions and organic acids in tobacco |
| CN104090039A (en) * | 2014-07-08 | 2014-10-08 | 青海大学 | Method for simultaneously determining inorganic anions and organic acid radical ions in salt lake brine |
| JP2014202570A (en) * | 2013-04-04 | 2014-10-27 | 大日本住友製薬株式会社 | Separation method of organic acid ions and/or inorganic acid ions |
| CN106053627A (en) * | 2016-05-12 | 2016-10-26 | 中华人民共和国日照出入境检验检疫局 | Method for simultaneously detecting 26 organic acids and inorganic negative ions in juice |
| CN106841440A (en) * | 2017-01-20 | 2017-06-13 | 山东省分析测试中心 | The detection method of organic acid in a kind of environment |
-
2020
- 2020-12-29 CN CN202011595891.1A patent/CN112798706A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101825618A (en) * | 2010-05-18 | 2010-09-08 | 上海博物馆 | Rapid detection method of volatile acid in exhibited materials collected by museum based on passive sampling |
| CN102128885A (en) * | 2010-12-08 | 2011-07-20 | 广东中烟工业有限责任公司 | Method for quickly and simultaneously detecting 16 inorganic anions and organic acids in tobacco |
| JP2014202570A (en) * | 2013-04-04 | 2014-10-27 | 大日本住友製薬株式会社 | Separation method of organic acid ions and/or inorganic acid ions |
| CN104090039A (en) * | 2014-07-08 | 2014-10-08 | 青海大学 | Method for simultaneously determining inorganic anions and organic acid radical ions in salt lake brine |
| CN106053627A (en) * | 2016-05-12 | 2016-10-26 | 中华人民共和国日照出入境检验检疫局 | Method for simultaneously detecting 26 organic acids and inorganic negative ions in juice |
| CN106841440A (en) * | 2017-01-20 | 2017-06-13 | 山东省分析测试中心 | The detection method of organic acid in a kind of environment |
Non-Patent Citations (2)
| Title |
|---|
| 杨小林等: "离子色谱(IC)在文物保护中的应用", 《中国文物保护技术协会第四次学术年会论文集 哲学与人文科学辑》 * |
| 谭伟等: "水中常见阴离子和有机酸的离子色谱分析方法研究", 《化学世界》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114264769A (en) * | 2021-12-23 | 2022-04-01 | 江阴江化微电子材料股份有限公司 | Component concentration detection method of electronic-grade mixed acid system |
| CN114264769B (en) * | 2021-12-23 | 2024-02-20 | 江阴江化微电子材料股份有限公司 | Component concentration detection method of electronic grade mixed acid system |
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