CN102262078A - Method of atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, and its apparatus - Google Patents
Method of atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, and its apparatus Download PDFInfo
- Publication number
- CN102262078A CN102262078A CN2010101844339A CN201010184433A CN102262078A CN 102262078 A CN102262078 A CN 102262078A CN 2010101844339 A CN2010101844339 A CN 2010101844339A CN 201010184433 A CN201010184433 A CN 201010184433A CN 102262078 A CN102262078 A CN 102262078A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- atomic fluorescence
- morphological analysis
- fluorescence spectrophotometry
- online
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a method of an atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, the method comprises the following steps: (a) mixing a first arsenical sample and a first reducing agent under the temperature of 65-75 DEG C and performing a reduction of quinquivalent arsonium; (b) mixing a second arsenical sample and a second reducing agent, and determining the concentration of trivalent arsonium by the generated hydride after mixing; (c) mixing a solution obtained by reducing quinquivalent arsonium in the step (a) with the second reducing agent, and determining the concentration of total arsonium by the generated hydride after mixing. The invention also discloses an apparatus for using the method. According to the on-line pre-reduction of quinquivalent arsonium, the method of the invention is capable of effectively solving the interference problem between the valences, avoiding manual pre-treating processes in the off-line reduction and realizing an automatic and rapid analysis of arsenic shape.
Description
Technical field:
The present invention relates to the fluorescence spectrum morphological analysis field of element, trivalent arsenic and pentavalent arsenic morphological analysis method and device in particularly a kind of seawater, the online prereduction mode of use pentavalent arsenic realizes the quantitative test of trivalent arsenic and pentavalent arsenic.
Background technology:
China be one populous, land resources scarcity, and have the ocean big country of more than 300 ten thousand square kilometres of Precincts.Seawater is most valuable and the limited natural resource.Current, social economy develops rapidly along with the coastland, and oceanographic engineering construction and ocean development activity are frequent day by day, and a large amount of industrial waste waters and sanitary sewage are by channel discharge into seas such as river, the direct sewage draining exit of enterprise and municipal wastewater sewage draining exits.Metal pollution thing in the seawater, having become influences human survival and healthy significant problem.
The crucial ecological effect of metal pollutant depends primarily on the form of the metal pollutant that this material exists in environment, rather than its total amount.Along with people to the deepening continuously of minor metallic element polluting effect understanding, to the standard study on monitoring of corresponding trace metal contamination element from total quantitative determination synform attitude analysis directions development.
This area personage is well-known, the marine environment system comprises that seawater and rivers estuary and Lu Yuan go into the metal pollutant in the extra large sewage draining exit, can be starting point by water body, enter into formed " water body-water body biology-human body " food chain circulating system, make the constantly enrichment in the relevant sample in ocean of minor metallic element pollutant, cause that the biology and the whole mankind are injured, pathogenic even dead.Arsenic is monitoring elements important in seawater pollution and the marine environmental monitoring.Mainly there are arsenious acid (H3AsO3) and arsenic acid (H3AsO4) in the seawater, organic methyl arsenic of minute quantity is arranged in addition.The toxicity of arsenic has notable difference with the form difference, and the toxicity of inorganic arsenic is big than the toxicity of organo-arsenic.As (III) is the most malicious form of arsenic element, and the toxicity of As (V) etc. reduces successively.In " ocean water quality standard " and " marine monitoring standard " that the existing promulgation of China is carried out, although the standard determination method for major metal pollution element total concentrations such as As clearly stipulates not have the standard method of metal pollutant such as As, Hg morphological analysis in the seawater temporarily.Therefore; carry out the research of morphological analysis method such as arsenic in the marine environment system; can estimate the seawater pollution degree better; to further reinforcement with improve the monitoring of metal pollution thing in each marine environment system; the resource of protecting the marine environment, the infringement of preventing and remedying pollution, maintaining ecological balance; ensure health, promote society and economic sustainable development to have very far reaching significance.
At present, high performance liquid chromatography (HPLC) is to detect the most effective analytical approach of minor metallic element form with inductively coupled plasma spectrometry mass spectrum (ICP-MS) coupling technique, but because of it costs an arm and a leg, difficult universal in common laboratory.At home, when carrying out micro-morphological analysis such as marine environment system arsenic, hydride generation atomic fluorescence spectrometry is because of being easy to avoid the interference of matrix extensively to see bibliographical information.But because the hydride generation atomic fluorescence spectrometry reaction system needs certain acidity to satisfy the requirement that forms argon hydrogenation flame, making the interference that brings pentavalent arsenic inevitably when trivalent arsenic is analyzed carrying out finally influences the practical application of this method.
Summary of the invention:
Technical matters to be solved by this invention provides trivalent arsenic and pentavalent arsenic online prereduction atomic fluorescence spectrophotometry morphological analysis method and device thereof in a kind of seawater, compare with pentavalent arsenic atomic fluorescence spectrophotometry morphological analysis method with trivalent arsenic in the common offline restore seawater, online prereduction by pentavalent arsenic, effectively solve the interference problem between valence state, avoid artificial pre-treatment process loaded down with trivial details in the offline restore and consuming time, realize arsenic morphology automatically and express-analysis.
For achieving the above object, the technical solution used in the present invention is as follows:
The atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic and the online prereduction of pentavalent arsenic, this method may further comprise the steps:
(a) contain the arsenic sample with first and under 65～75 degree temperature, mix the reduction of carrying out pentavalent arsenic with first reductive agent;
(b) contain the arsenic sample with second and mix, and carry out the trivalent arsenic concentration determination by the hydride that mixes the back generation with second reductive agent;
(c) solution after the pentavalent arsenic reduction is finished in the step (a) is mixed with second reductive agent, and carry out total arsenic concentration determination by the hydride that mixes the back generation.
Further, described first contains the arsenic sample and mixes acquisition with hydrochloric acid solution by the seawater sample that filters.
Further, described second contains the arsenic sample by the seawater sample that filters, and dilution obtains as thinning agent through aqueous citric acid solution.
Further, described first to contain the arsenic sample be the pentavalent arsenic standard solution, and described second to contain the arsenic sample be the trivalent arsenic standard solution.
Further, described first reductive agent is thiocarbamide-ascorbic acid solution.
Further, described second reductive agent is a solution of potassium borohydride.
Further, in described step (b) with (c), described mixing also comprises the hydrochloric acid solution as carrier, participates in hydrogenation simultaneously and produces hydrogen.
Further, carry out trivalent arsenic concentration determination and total arsenic concentration determination by atomic fluorescence spectrometry.
The atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic and the online prereduction of pentavalent arsenic comprises
One water bath with thermostatic control commingled system is used for the solution of solution mixing test tube is carried out thermostatic control;
One sequential injection hydrogenation generation systems, the solution that is used for importing by the sequential injection mode carry out hydrogenation and generate hydride gas;
One atomic fluorescence spectrophotometry detection system is used for carrying out element by the hydride that the atomic fluorescence spectrophotometry detection mode generates described sequential injection hydrogenation generation systems and detects;
The control of one system, data acquisition and analytic system are used for control sequence injection hydrogenation generation systems, and the testing result of atomic fluorescence spectrophotometry detection system is transferred to computing machine and handles;
Described water bath with thermostatic control commingled system is connected by pipeline with sequential injection hydrogenation generation systems; Described sequential injection hydrogenation generation systems and atomic fluorescence spectrophotometry detection system are connected by a pipeline that is used for the hydride gas that sequential injection hydrogenation generation systems generates is inputed to the atomic fluorescence spectrophotometry detection system.
Further, described water bath with thermostatic control commingled system comprises solution mixing test tube and the heating arrangement that is used to heat described solution mixing test tube.
Further, described sequential injection hydrogenation generation systems comprises hydrogenation generation systems pump valve parts, hydrogenation generation systems control circuit, hydrogenation generation systems internal control program, wherein hydrogenation generation systems pump valve parts comprise syringe pump, liquid storage pipe, multidigit selector valve, mixed block, gas-liquid separator, peristaltic pump, and each parts connects successively by connecting pipe; Described water bath with thermostatic control commingled system is connected to multidigit selector valve in the sequential injection hydrogenation generation systems by pipeline.
Further, the control of described system, data acquisition and analytic system comprise that one installs the computer system of seawater arsenium morphological analysis workstation software, and described seawater arsenium morphological analysis workstation software comprises sequential injection hydrogenation generation systems control function module, atomic fluorescence spectrophotometry detection system data acquisition function module and arsenium morphological analysis data processing function module.
Further, described pipeline is the vinyon pipeline.
Trivalent arsenic and pentavalent arsenic online prereduction atomic fluorescence spectrophotometry morphological analysis method and device thereof in a kind of seawater that provides are provided, marine environment condition characteristics and actual needs in conjunction with coastal modern international metropolises such as present domestic Shanghai, online reduction innovative technology is used in research, sequential injection technology and hydride generation atomic fluorescence spectrometry coupling, by brand-new program optimization design, by accurate control to reaction system acidity, and use online reduction mode, automatically control methods such as reduction process, effectively solve the interference problem between valence state, realize morphological analysis marine environment system metal pollutant arsenic element.The online prereduction of this automatic control system adopts the sequential injection analytical approach to combine with atomic fluorescence spectrometry, online prereduction process is dynamically controlled, and carry out sample pre-treatments and mensuration automatically, shorten analysis time greatly, reduce sample pre-treatments or enrichment difficulty, simultaneously can reduce experimental error at effective minimizing sample and related reagent consumption, the online prereduction of this automatic control system has that process is dynamically controlled, operation automation, rapidly and efficiently, effectively reduce advantages such as sample and related reagent consumption, more is applicable to the generally popularization of test in enormous quantities and method.
Description of drawings:
Further specify the present invention below in conjunction with the drawings and specific embodiments.
Fig. 1 is the structural representation of apparatus of the present invention;
Fig. 2 is the graph of a relation between each system in apparatus of the present invention;
Fig. 3 is the typical curve comparison diagram of pentavalent arsenic offline restore and the online reduction of pentavalent arsenic;
Fig. 4 is trivalent arsenic concentration, total arsenic concentration test signal patterns.
Embodiment:
For technological means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with concrete diagram, further set forth embodiments of the present invention.
Fig. 2 is the graph of a relation between each system in the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic of the present invention and the online prereduction of pentavalent arsenic, this device comprises that one is used for the solution of solution mixing test tube is carried out thermostatically controlled water bath with thermostatic control commingled system 23, and described water bath with thermostatic control commingled system 23 comprises solution mixing test tube and is used to heat the heating arrangement of described solution mixing test tube; One solution that is used for importing by the sequential injection mode carries out the sequential injection hydrogenation generation systems 17 that hydrogenation generates hydride gas; One atomic fluorescence spectrophotometry detection system 24 is used for carrying out element by the hydride that the atomic fluorescence spectrophotometry detection mode generates described sequential injection hydrogenation generation systems and detects; The control of one system, data acquisition and analytic system 25, be used for control sequence injection hydrogenation generation systems, and the testing result of atomic fluorescence spectrophotometry detection system is transferred to computing machine and handles, be connected with described atomic fluorescence spectrophotometry 24 detection systems by data line; The control of described system, data acquisition and analytic system 25 comprise that one installs the computer system of seawater arsenium morphological analysis workstation software, and described seawater arsenium morphological analysis workstation software comprises sequential injection hydrogenation generation systems control function module, atomic fluorescence spectrophotometry detection system data acquisition function module and arsenium morphological analysis data processing function module.
Described water bath with thermostatic control commingled system 23 and sequential injection hydrogenation generation systems 17 are connected by pipeline; Described sequential injection hydrogenation generation systems 17 and atomic fluorescence spectrophotometry detection system 24 are connected by the pipeline that is used for the hydride gas that sequential injection hydrogenation generation systems 17 generates is inputed to atomic fluorescence spectrophotometry detection system 24.
Fig. 1 is the synoptic diagram of the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic of the present invention and the online prereduction of pentavalent arsenic, water bath with thermostatic control commingled system 23; The sequential injection hydrogenation generation systems 17 that comprises hydrogenation generation systems pump valve parts, hydrogenation generation systems control circuit, hydrogenation generation systems internal control program, wherein hydrogenation generation systems pump valve parts comprise syringe pump 8, liquid storage pipe 9, multidigit selector valve 10, mixed block 11, gas-liquid separator 12, peristaltic pump 13, and each parts connects successively by connecting pipe; And atomic fluorescence spectrophotometry detection system 24.Connection between each ingredient of sequential injection hydrogenation generation systems 17 is as follows: as shown in Figure 1, No. 2 positions of described syringe pump 8 are connected with an end of liquid storage pipe 9, the inlet of described multidigit selector valve 10 is connected with the other end of liquid storage pipe 9, an inlet in three inlets of its No. 1 position and mixed block 11 is connected, and the outlet of mixed block 11 is connected with the inlet of gas-liquid separator 12.
In addition, as shown in Figure 1, No. 4 positions of multidigit selector valve 10 are connected by a pipeline in described water bath with thermostatic control commingled system 23 and the sequential injection hydrogenation generation systems 17, and described pipeline can be selected the vinyon pipeline; Outlet in atomic fluorescence spectrophotometry detection system 24 and the sequential injection hydrogenation generation systems 17 in two outlets of gas-liquid separator 12 is connected by pipeline, and this pipeline can be selected the vinyon pipeline.
The atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic of the present invention and the online prereduction of pentavalent arsenic before adopting said method, at first, needs to prepare following reagent:
(1) concentration is 2% hydrochloric acid, the concentration of getting 50mL be the concentrated hydrochloric acid of 12mol/L in volumetric flask, water is settled to 1000mL.Hydrochloric acid is carrier fluid, participates in hydrogenation simultaneously and generates hydrogen.
(2) concentration is that 2% thiocarbamide and concentration are the mixed solution of 1% ascorbic acid, be diluted to 250mL after promptly taking by weighing the dissolving of (25.0 ± 0.1) g thiocarbamide and (12.5 ± 0.1) g ascorbic acid water, obtain 100g/L thiocarbamide-50g/L ascorbic acid mixed solution, as first reductive agent of pentavalent arsenic reduction.This reagent disposes before use.
(3) concentration is 2% solution of potassium borohydride, promptly taking by weighing (10.0 ± 0.1) g potassium borohydride (KBH4) in the glass beaker that drying is crossed is dissolved in advance in the aqueous solution that is dissolved with (2.5 ± 0.1) g potassium hydroxide (KOH), be diluted with water to 500mL, acquisition concentration is 2% solution of potassium borohydride, as second reductive agent.This reagent is prepared before use.
(4) 0.1mol/L aqueous citric acid solution: take by weighing the single water citric acid of 21.0g, the water dissolving also is settled to 1000mL.Aqueous citric acid solution contains the agent of arsenic dilution of sample for obtaining second.
(5) 100.0 μ g/mL trivalent arsenic standard reserving solutions: accurately take by weighing (0.1320 ± 0.0001) g arsenic trioxide (As2O3) in the 50mL beaker, after the dissolving of 10mL 1mol/L sodium hydroxide solution, be adjusted to nearly neutrality with the 1mol/L dilute hydrochloric acid solution, move in the 1000mL volumetric flask and be settled to scale, mixing is preserved.
(6) 100.0 μ g/mL pentavalent arsenic standard reserving solutions: accurately take by weighing disodium hydrogen arsenate (Na2HAsO47H2O) (0.4165 ± 0.0001) g in the 50mL beaker, after the dissolving of adding low amounts of water, move into constant volume in the 1000mL volumetric flask.
(7) the 100.0 μ g/L trivalent arsenic standard solution of Shi Yonging: pipette 100 μ L trivalent arsenic standard reserving solutions (6) in 100mL glass volumetric flask, the water constant volume, shake up, the 100.0 μ g/L trivalent arsenic standard solution that configuration obtains can be used as second arsenic containing solution, and this reagent prepares before use.
(8) the 100.0 μ g/L pentavalent arsenic standard solution of Shi Yonging: pipette 100 μ L pentavalent arsenic standard reserving solutions (7) in 100mL glass volumetric flask, the water constant volume, shake up, the 100.0 μ g/L pentavalent arsenic standard solution that configuration obtains can be used as first arsenic containing solution, and this reagent prepares before use.
(9) artificial seawater preparation: take by weighing 26.726g sodium chloride (NaCl), 2.260g magnesium chloride (MgCl26H2O), 3.248g magnesium sulphate (MgSO47H2O), 1.153g lime chloride (CaCl2), 0.198g sodium bicarbonate (NaHCO3), 0.721g potassium chloride (KCl), after the water dissolving, change in the 1000mL volumetric flask respectively, water is settled to scale, shake up, the artificial seawater that configuration obtains is as seawater sample.In addition, to be top grade pure for preparation artificial seawater agents useful for same.
After above-mentioned seawater sample via hole diameter 0.45 μ m mixed cellulose ester microporous membrane filters, measure 15.00mL and place the 25mL volumetric flask, add the single water citric acid of (0.5253 ± 0.0001) g, the water dissolving and be settled to scale after fully shake up the solution that obtains, contain the arsenic sample as second.
After above-mentioned seawater sample via hole diameter 0.45 μ m mixed cellulose ester microporous membrane filters, measure 15.00mL and place the 25mL volumetric flask, adding 1.25mL concentration is 12mol/L concentrated hydrochloric acid (HCl), and the water dissolving also is settled to scale, fully shake up the solution that obtains, contain the arsenic sample as first.
The preparation of above all ingredients comprises that its concentration and dosage etc. are specific embodiments that is applicable to method and apparatus of the present invention, and the preparation of all ingredients of other suitable concns and dosage etc. is that those skilled in the art institute is expectable.In addition, above-mentioned seawater sample is artificial preparation, and the seawater sample that is used for the inventive method and device also can be selected the seawater sample of nature.
Secondly, as shown in fig. 1, each reagent of preparation disposed in the following manner puts in place:
With being placed on the concentration that is disposed in the reagent bottle is 2% hydrochloric acid 31 is connected to syringe pump by connecting pipe No. 1 position; To be connected to No. 5 positions of multidigit selector valve 10 as the prepared thiocarbamide-ascorbic acid mixed solution 32 of first reductive agent of pentavalent arsenic reduction by connecting pipe; Second arsenic containing solution 34 is connected with No. 3 positions of multidigit selector valve 10 by connecting pipe; First arsenic containing solution 35 is connected with No. 2 positions of multidigit selector valve 10 by connecting pipe; Be 2% solution of potassium borohydride 37 as the concentration of second reductive agent with three inlets of mixed block in an inlet be connected by connecting pipe, two inlets of other of described mixed block connect No. 1 position of argon gas 15 and multidigit selector valve respectively.One waste liquid outlet transporting of described gas-liquid separator 12 goes out waste liquid 36.
Then, put in place and connect pipeline in related reagent configuration, open after the seawater arsenium morphological analysis workstation software of the computing machine that is connected with the atomic fluorescence spectrophotometry detection system and use, carry out the atomic fluorescence spectrophotometry morphological analysis of trivalent arsenic and the online prereduction of pentavalent arsenic.
The first step: first contains the introducing and the online prereduction of arsenic sample 35.The hydrogenation generation systems internal control programmed control multidigit selector valve 10 of sequential injection hydrogenation generation systems 17 forwards No. 2 positions to and draws 4.8ml first by syringe pump 8 and contains arsenic sample 35, multidigit selector valve 10 forwards No. 5 positions to and draws 1.2ml thiocarbamide-ascorbic acid solutions 32 to liquid storage pipe 9 by syringe pump 8 then, then the solution of twice suction is injected together the solution mixing test tube of water bath with thermostatic control commingled system 23, the temperature of water bath with thermostatic control commingled system 23 is set in 65～75 degree temperature ranges Celsius, preferably 70 spend, and this moment, mixed solution began fast restore.
Second step: second contains the trivalent arsenic concentration determination of arsenic sample 34.After the first step finished, mixed solution began fast restore, because reduction needs 3 minutes at least fully, so wait in this section the time period of reduction, can carry out trivalent arsenic and measure, to save Measuring Time.Sequential injection hydrogenation generation systems 17 is carried out following action:
1. drawing 3ml concentration by syringe pump 8 earlier is 2% hydrochloric acid 31;
2. multidigit selector valve 10 forwards No. 3 positions to and draws 1.5ml second by syringe pump 8 and contains arsenic sample 34;
3. multidigit selector valve 10 forwards the position to No. 1, syringe pump 8 is got the solution that sucks, the beginning sample introduction, simultaneously as the solution of potassium borohydride 7 of second reductive agent through peristaltic pump 13 wriggling sample introductions, argon gas 15, solution of potassium borohydride 37, sample mix solution hybrid reaction in mixed block 11;
4. the hydride of 24 pairs of gas-liquid separators of atomic fluorescence spectrophotometry detection system, 12 outputs is tested, and waste liquid 36 is discharged through peristaltic pump 13, coordinates control by seawater arsenium morphological analysis workstation software simultaneously and carries out the trivalent arsenic concentration determination;
5. according to 1-4 program replication three times.This replication number of times is determined according to the degree of accuracy of desired data by the operator.
The 3rd step: total arsenic concentration determination, promptly carry out total arsenic concentration determination to the mixed solution in the step 1 water bath with thermostatic control commingled system 23.Behind second EOS, the trivalent arsenic concentration determination finishes, and the mixed solution in the commingled system of water bath with thermostatic control simultaneously 23 has also reached reduction fully, can carry out the mensuration of total arsenic concentration.Sequential injection hydrogenation generation systems 17 is carried out following action:
1. drawing 3ml concentration by syringe pump 8 earlier is 2% hydrochloric acid 31;
2. multidigit selector valve 10 forwards No. 4 positions to and is drawn the mixed solution 1.5ml of reduction fully in the mixing test tube of water bath with thermostatic control commingled systems 23 by syringe pump 8;
3. multidigit selector valve 10 forwards the position to No. 1, and syringe pump 8 is got the solution that sucks, the beginning sample introduction, and solution of potassium borohydride 37 is through peristaltic pump 13 wriggling sample introductions, argon gas 15, solution of potassium borohydride 37, sample mix solution hybrid reaction in mixed block 11 simultaneously.
4. the hydride of 24 pairs of gas-liquid separators of atomic fluorescence spectrophotometry detection system, 12 outputs is tested, and waste liquid 36 is discharged through peristaltic pump 13, coordinates control by control program simultaneously and carries out total arsenic concentration determination;
5. go on foot replication three times according to 1-4.This replication number of times is equally also determined according to the degree of accuracy of desired data by the operator.
Fig. 3 is the typical curve comparison diagram of pentavalent arsenic offline restore and the online reduction of pentavalent arsenic, pentavalent arsenic offline restore typical curve equation is y=0.1979x+0.1853 among the figure, the online reduction typical curve of pentavalent arsenic equation is y=0.1925x+0.1883, the deviation of two kinds of methods is SD=[0.1979-(0.1979+0.1925)/2]/(0.1979+0.1925)/and 2=0.35%, show that the pentavalent arsenic offline restore is consistent with the actual effect of the online reduction of pentavalent arsenic.
Fig. 4 is trivalent arsenic concentration, total arsenic concentration test signal patterns, and 26 is three measurement pattern of trivalent arsenic concentration among the figure, and 27 is three measurement pattern of total arsenic concentration.Thus, trivalent arsenic concentration in seawater sample or the trivalent arsenic standard solution can be determined, and by the mensuration of total arsenic concentration in total solution, pentavalent arsenic concentration=total arsenic concentration-trivalent arsenic concentration, and the pentavalent arsenic concentration in acquisition seawater sample or the pentavalent arsenic standard solution.The present invention is when first contains the concentration determination of arsenic sample pentavalent arsenic, do not need to contain the pentavalent arsenic sample introduction after thiocarbamide-ascorbic acid mixing prereduction reagent is converted into trivalent arsenic that exists in the arsenic sample with first in advance, but when measuring beginning direct injected, utilize sequential injection hydrogenation generation systems and water bath with thermostatic control commingled system that sample is carried out online quick prereduction, and then utilize solution after sequential injection hydrogenation generation systems is introduced reduction, directly carry out hydrogenation, and measure by the atomic fluorescence spectrophotometry detection system.The present invention uses the online prereduction mode of pentavalent arsenic, has realized the quantitative test of trivalent arsenic and pentavalent arsenic.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention not only is restricted to the described embodiments; that describes in the foregoing description and the instructions just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (13)
1. the atomic fluorescence spectrophotometry morphological analysis method of trivalent arsenic and the online prereduction of pentavalent arsenic, this method may further comprise the steps:
(a) contain the arsenic sample with first and under 65～75 degree temperature, mix the reduction of carrying out pentavalent arsenic with first reductive agent;
(b) contain the arsenic sample with second and mix, and carry out the trivalent arsenic concentration determination by the hydride that mixes the back generation with second reductive agent;
(c) solution after the pentavalent arsenic reduction is finished in the step (a) is mixed with second reductive agent, and carry out total arsenic concentration determination by the hydride that mixes the back generation.
2. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic is characterized in that: described first contains the arsenic sample mixes acquisition by the seawater sample that filters with hydrochloric acid solution.
3. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic is characterized in that: described second contains the arsenic sample by the seawater sample that filters, and dilution obtains as thinning agent through aqueous citric acid solution.
4. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic is characterized in that: described first to contain the arsenic sample be the pentavalent arsenic standard solution, and described second to contain the arsenic sample be the trivalent arsenic standard solution.
5. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic is characterized in that: described first reductive agent is thiocarbamide-ascorbic acid solution.
6. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic is characterized in that: described second reductive agent is a solution of potassium borohydride.
7. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic, it is characterized in that: in described step (b) with (c), described mixing also comprises the hydrochloric acid solution as carrier, participates in hydrogenation simultaneously and produces hydrogen.
8. the atomic fluorescence spectrophotometry morphological analysis method of a kind of trivalent arsenic according to claim 1 and the online prereduction of pentavalent arsenic is characterized in that: carry out trivalent arsenic concentration determination and total arsenic concentration determination by atomic fluorescence spectrometry.
9. the atomic fluorescence spectrophotometry morphological analysis means of trivalent arsenic and the online prereduction of pentavalent arsenic is characterized in that, comprises
One water bath with thermostatic control commingled system is used for the solution of solution mixing test tube is carried out thermostatic control;
One sequential injection hydrogenation generation systems, the solution that is used for importing by the sequential injection mode carry out hydrogenation and generate hydride gas;
One atomic fluorescence spectrophotometry detection system is used for carrying out element by the hydride that the atomic fluorescence spectrophotometry detection mode generates described sequential injection hydrogenation generation systems and detects;
The control of one system, data acquisition and analytic system are used for control sequence injection hydrogenation generation systems, and the testing result of atomic fluorescence spectrophotometry detection system is transferred to computing machine and handles;
Described water bath with thermostatic control commingled system is connected by pipeline with sequential injection hydrogenation generation systems; Described sequential injection hydrogenation generation systems and atomic fluorescence spectrophotometry detection system are connected by a pipeline that is used for the hydride gas that sequential injection hydrogenation generation systems generates is inputed to the atomic fluorescence spectrophotometry detection system.
10. the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic according to claim 9 and the online prereduction of pentavalent arsenic, it is characterized in that described water bath with thermostatic control commingled system comprises solution mixing test tube and is used to heat the heating arrangement of described solution mixing test tube.
11. the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic according to claim 9 and the online prereduction of pentavalent arsenic, it is characterized in that, described sequential injection hydrogenation generation systems comprises hydrogenation generation systems pump valve parts, hydrogenation generation systems control circuit, hydrogenation generation systems internal control program, wherein hydrogenation generation systems pump valve parts comprise syringe pump, liquid storage pipe, multidigit selector valve, mixed block, gas-liquid separator, peristaltic pump, and each parts connects successively by connecting pipe; Described water bath with thermostatic control commingled system is connected to multidigit selector valve in the sequential injection hydrogenation generation systems by pipeline.
12. the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic according to claim 9 and the online prereduction of pentavalent arsenic, it is characterized in that, the control of described system, data acquisition and analytic system comprise that one installs the computer system of seawater arsenium morphological analysis workstation software, and described seawater arsenium morphological analysis workstation software comprises sequential injection hydrogenation generation systems control function module, atomic fluorescence spectrophotometry detection system data acquisition function module and arsenium morphological analysis data processing function module.
13. the atomic fluorescence spectrophotometry morphological analysis means according to claim 9 or 11 described a kind of trivalent arsenics and the online prereduction of pentavalent arsenic is characterized in that described pipeline is the vinyon pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010184433 CN102262078B (en) | 2010-05-25 | 2010-05-25 | Method of atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, and its apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010184433 CN102262078B (en) | 2010-05-25 | 2010-05-25 | Method of atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, and its apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102262078A true CN102262078A (en) | 2011-11-30 |
| CN102262078B CN102262078B (en) | 2013-04-10 |
Family
ID=45008789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010184433 Expired - Fee Related CN102262078B (en) | 2010-05-25 | 2010-05-25 | Method of atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, and its apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102262078B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103207170A (en) * | 2013-04-19 | 2013-07-17 | 华北电力大学（保定） | Method for analyzing and determining arsenic form in liquid food seasoning |
| CN103424390A (en) * | 2013-08-05 | 2013-12-04 | 福建省邵武市永晶化工有限公司 | Measurement method for arsenic content in hydrofluoric acid |
| CN103808698A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Method for measuring arsenic content in propylene |
| CN104316499A (en) * | 2014-08-11 | 2015-01-28 | 广西大学 | A method of indirectly measuring gold in seawater by adoption of an atomic fluorescence spectrophotometer |
| CN107037115A (en) * | 2017-04-17 | 2017-08-11 | 中国科学院海洋研究所 | A kind of ICP MS hydride sampling system and its method for detecting hydride |
| CN109085144A (en) * | 2018-06-27 | 2018-12-25 | 华北电力大学（保定） | Valence state is divided to survey arsenic method based on stabilizer and fluorescence intensity coordinative role |
| CN110398489A (en) * | 2019-07-05 | 2019-11-01 | 中南大学 | A method for determining the valence state of arsenic in copper smelting electrostatic precipitator dust |
| CN111239105A (en) * | 2020-02-20 | 2020-06-05 | 南京信息工程大学 | Spectrum monitoring system for sewage real-time monitoring |
| CN112326571A (en) * | 2020-10-28 | 2021-02-05 | 中国科学院生态环境研究中心 | A method for quantitative detection of pentavalent arsenic in water samples |
| CN114965843A (en) * | 2022-05-11 | 2022-08-30 | 浙江树人学院 | Ion chromatograph for multi-channel detection and use method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502467B (en) * | 2014-11-20 | 2016-08-31 | 华中科技大学 | A kind of assay method of arsenic valence state |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089230A (en) * | 1989-03-15 | 1992-02-18 | Takara Shuzo Co. | Reagent reactor apparatus |
| CN2502273Y (en) * | 2001-11-23 | 2002-07-24 | 北京吉大小天鹅仪器有限公司 | Sequential sample injection device for atomic fluorescence spectrograph |
| US20040151622A1 (en) * | 2002-12-31 | 2004-08-05 | Chun-Mao Tseng | Ultra-trace automatic mercury species analyzer |
| CN101135643A (en) * | 2007-10-17 | 2008-03-05 | 东北大学 | Miniaturized atomic fluorescence detection device |
| CN201697878U (en) * | 2010-05-25 | 2011-01-05 | 上海光谱仪器有限公司 | Atomic fluorescence spectrometry morphological analysis device for online prereduction of trivalent arsenic and pentavalent arsenic |
-
2010
- 2010-05-25 CN CN 201010184433 patent/CN102262078B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089230A (en) * | 1989-03-15 | 1992-02-18 | Takara Shuzo Co. | Reagent reactor apparatus |
| CN2502273Y (en) * | 2001-11-23 | 2002-07-24 | 北京吉大小天鹅仪器有限公司 | Sequential sample injection device for atomic fluorescence spectrograph |
| US20040151622A1 (en) * | 2002-12-31 | 2004-08-05 | Chun-Mao Tseng | Ultra-trace automatic mercury species analyzer |
| CN101135643A (en) * | 2007-10-17 | 2008-03-05 | 东北大学 | Miniaturized atomic fluorescence detection device |
| CN201697878U (en) * | 2010-05-25 | 2011-01-05 | 上海光谱仪器有限公司 | Atomic fluorescence spectrometry morphological analysis device for online prereduction of trivalent arsenic and pentavalent arsenic |
Non-Patent Citations (1)
| Title |
|---|
| N.V. SEMENOVA, ETC: "Sequential injection analysis system for total inorganic arsenic determination by hydride generation-atomic fluorescence spectrometry", 《ANALYTICA CHIMICA ACTA》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103808698A (en) * | 2012-11-14 | 2014-05-21 | 中国石油天然气股份有限公司 | Method for measuring arsenic content in propylene |
| CN103808698B (en) * | 2012-11-14 | 2016-06-08 | 中国石油天然气股份有限公司 | Method for measuring arsenic content in propylene |
| CN103207170A (en) * | 2013-04-19 | 2013-07-17 | 华北电力大学（保定） | Method for analyzing and determining arsenic form in liquid food seasoning |
| CN103207170B (en) * | 2013-04-19 | 2016-01-20 | 华北电力大学（保定） | A kind of method analyzing arsenic morphology in mensuration food liquid condiment |
| CN103424390A (en) * | 2013-08-05 | 2013-12-04 | 福建省邵武市永晶化工有限公司 | Measurement method for arsenic content in hydrofluoric acid |
| CN104316499A (en) * | 2014-08-11 | 2015-01-28 | 广西大学 | A method of indirectly measuring gold in seawater by adoption of an atomic fluorescence spectrophotometer |
| CN107037115A (en) * | 2017-04-17 | 2017-08-11 | 中国科学院海洋研究所 | A kind of ICP MS hydride sampling system and its method for detecting hydride |
| CN107037115B (en) * | 2017-04-17 | 2023-11-07 | 中国科学院海洋研究所 | An ICP-MS hydride sampling system and a method for detecting hydride |
| CN109085144A (en) * | 2018-06-27 | 2018-12-25 | 华北电力大学（保定） | Valence state is divided to survey arsenic method based on stabilizer and fluorescence intensity coordinative role |
| CN110398489A (en) * | 2019-07-05 | 2019-11-01 | 中南大学 | A method for determining the valence state of arsenic in copper smelting electrostatic precipitator dust |
| CN111239105A (en) * | 2020-02-20 | 2020-06-05 | 南京信息工程大学 | Spectrum monitoring system for sewage real-time monitoring |
| CN111239105B (en) * | 2020-02-20 | 2023-01-24 | 南京信息工程大学 | Spectrum monitoring system for sewage real-time monitoring |
| CN112326571A (en) * | 2020-10-28 | 2021-02-05 | 中国科学院生态环境研究中心 | A method for quantitative detection of pentavalent arsenic in water samples |
| CN114965843A (en) * | 2022-05-11 | 2022-08-30 | 浙江树人学院 | Ion chromatograph for multi-channel detection and use method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102262078B (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102262078B (en) | Method of atomic fluorescence spectrometry shape analysis by on-line pre-reducing trivalent arsonium and quinquivalent arsonium, and its apparatus | |
| CN101769863B (en) | Low-detection-lower-limit total arsenic online analyzer and analysis method thereof | |
| CN201697878U (en) | Atomic fluorescence spectrometry morphological analysis device for online prereduction of trivalent arsenic and pentavalent arsenic | |
| CN102375068B (en) | Full-automatic nutrient salt analyzer and analysis method thereof | |
| CN201527400U (en) | Ammonia nitrogen on-line monitor | |
| CN108318618A (en) | One kind being suitable for the high chlorine root sanitary sewage COD rapid detection methods of production platform | |
| CN106872388A (en) | A kind of assay method of super chemical oxygen demand of high-chloride wastewater | |
| CN102519922B (en) | An atomic fluorescence device and its measurement method for simultaneous determination of multiple elements | |
| CN106841466A (en) | A kind of liquid chromatogram pre-column derivatization for detecting water glyphosate | |
| CN102207466A (en) | Rapid test kit for benzoyl peroxide (banned additive) in flour and preparation method thereof | |
| CN113960153A (en) | ICP-MS (inductively coupled plasma-mass spectrometry) detection method for 12 elements in serum | |
| CN101241067A (en) | Total organic carbon and total nitrogen joint measuring instrument | |
| CN101101264A (en) | Automatic Analysis Method of Sulfide in Seawater | |
| Liu et al. | Automated determination of nitrite in aqueous samples with an improved integrated flow loop analyzer | |
| CN101696938B (en) | Method for online monitoring of copper ions in water through flow injection | |
| CN106290213A (en) | The detection method of polymer concentration in a kind of Produced Liquid handling process being suitable to offshore oilfield | |
| CN104181319A (en) | Cadmium column reduction detection device for full-automatic chemical analyzer | |
| CN105223143B (en) | A kind of method of pressure break liquid hold-up in measure oilfield sewage | |
| Frank et al. | A fast sequential injection analysis system for the simultaneous determination of ammonia and phosphate | |
| CN103940758A (en) | Method for detection of lead ions in water | |
| CN206960462U (en) | A kind of seawater quality optics on-line monitoring system | |
| CN201765236U (en) | Full-automatic nutritive salt analyzer | |
| CN105954250A (en) | Novel method for measuring arsenic in urine | |
| CN110007036A (en) | The detection of different arsenic morphologies in environment water based on HPLC-ICP-MS joint technology | |
| CN205981835U (en) | Processor before chemical analysis sample is synthesized |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130410 |