CN102262078B - 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
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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, particularly trivalent arsenic and pentavalent arsenic morphological analysis method and device in a kind of seawater use the online prereduction mode of pentavalent arsenic, realize the quantitative test of trivalent arsenic and pentavalent arsenic.
Background technology:
China be one populous, land resources is deficient, and has the ocean big country of more than 300 ten thousand square kilometres of Precincts.Seawater is most valuable and limited natural resources.Current, social economy develops rapidly along with the coastland, and oceanographic engineering construction and ocean development activity are day by day frequent, 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 has become the significant problem that affects human survival and health.
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 monitoring research 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 enter 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 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 large 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.China is existing to promulgate in " the ocean water quality standard " and " marine monitoring standard " carried out, although for the standard determination method of the major metal pollution element total concentrations such as As clear, temporarily without the standard method of the metal pollutant such as As, Hg morphological analysis in the seawater.Therefore; carry out the research of the morphological analysis method such as arsenic in the marine environment system; can estimate better the seawater pollution degree; 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 expensive because of it, and is difficult universal in common laboratory.At home, when carrying out the Speciation Analysis of Trace Elements such as marine environment system arsenic, hydride generation atomic fluorescence spectrometry is because 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, so that in the interference of carrying out bringing inevitably pentavalent arsenic when trivalent arsenic is analyzed, finally affect the practical application of the 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 pretreatment 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, the 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 the first reductive agent;
(b) contain the arsenic sample with second and mix with the second reductive agent, and carry out the trivalent arsenic concentration determination by the hydride that mixes rear generation;
(c) solution after the pentavalent arsenic reduction is finished in the step (a) is mixed with the second reductive agent, and carry out total arsenic concentration determination by the hydride that mixes rear 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 the first reductive agent is thiourea and ascorbic acid solution.
Further, described the second reductive agent is solution of potassium borohydride.
Further, in described step (b) with (c), described mixing also comprises the hydrochloric acid solution as carrier, participates in simultaneously hydrogenation 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 is used for carrying out hydrogenation by the solution that the sequential injection mode imports and generates 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;
One system control, Data collecting and analysis 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 processes;
Described water bath with thermostatic control commingled system is connected pipeline with sequential injection hydrogenation generation systems and is connected; 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 is used for heating the heating arrangement of 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 Procedure, 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 collecting and analysis system comprise that one installs the computer system of Arsenic in Seawater morphological analysis workstation software, and described Arsenic in Seawater morphological analysis workstation software comprises the control of sequential injection hydrogenation generation systems functional module, atomic fluorescence spectrophotometry detection system data acquisition function module and arsenium morphological analysis data processing function module.
Further, described pipeline is polyvinyl plastic 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 the accurate control to reaction system acidity, and use online reduction mode, automatically control the methods such as reduction process, effectively solve the interference problem between valence state, realize the morphological analysis to marine environment system metal pollutant arsenic element.The online prereduction of this automatic control system adopts the Sequential Injection Analysis method to combine with atomic fluorescence spectrometry, online prereduction process dynamics is controlled, and automatically carry out sample pre-treatments and mensuration, greatly shorten analysis time, 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 dynamics is controlled, operation automation, rapidly and efficiently, effectively reduce the 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 for heating the heating arrangement of described solution mixing test tube; One is used for carrying out the sequential injection hydrogenation generation systems 17 that hydrogenation generates hydride gas by the solution that the sequential injection mode imports; 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 collecting and analysis 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 processes, be connected with described atomic fluorescence spectrophotometry 24 detection systems by data line; The control of described system, Data collecting and analysis system 25 comprise that one installs the computer system of Arsenic in Seawater morphological analysis workstation software, and described Arsenic in Seawater morphological analysis workstation software comprises the control of sequential injection hydrogenation generation systems functional 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 is connected with sequential injection hydrogenation generation systems and is connected by pipeline; Described sequential injection hydrogenation generation systems 17 is connected by the pipeline that inputs to atomic fluorescence spectrophotometry detection system 24 for the hydride gas that sequential injection hydrogenation generation systems 17 is generated with 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 Procedure, 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 entrance of described multidigit selector valve 10 is connected with the other end of liquid storage pipe 9, an entrance in three entrances of its No. 1 position and mixed block 11 is connected, and the outlet of mixed block 11 is connected with the entrance of gas-liquid separator 12.
In addition, as shown in Figure 1, No. 4 positions of described water bath with thermostatic control commingled system 23 and multidigit selector valve 10 during sequential injection hydrogenation generation systems is connected connect by a pipeline, and described pipeline can be selected polyvinyl plastic 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 polyvinyl plastic 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 simultaneously hydrogenation and generates hydrogen.
(2) concentration is that 2% thiocarbamide and concentration are the mixed solution of 1% ascorbic acid, be diluted to 250mL after namely 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 the first reductive agent of pentavalent arsenic reduction.This reagent disposes before use.
(3) concentration is 2% solution of potassium borohydride, namely 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 the 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 thinning agent of arsenic sample for acquisition 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, add a small amount of water-soluble solution after, move into constant volume in the 1000mL volumetric flask.
(7) the 100.0 μ g/L trivalent arsenic standard solution that use: pipette 100 μ L trivalent arsenic standard reserving solutions (6) in 100mL Glass capacity bottle, the water constant volume, shake up, the 100.0 μ g/L trivalent arsenic standard solution that configuration obtains can be used as the second arsenic containing solution, and this reagent prepares before use.
(8) the 100.0 μ g/L pentavalent arsenic standard solution that use: pipette 100 μ L pentavalent arsenic standard reserving solutions (7) in 100mL Glass capacity bottle, the water constant volume, shake up, the 100.0 μ g/L pentavalent arsenic standard solution that configuration obtains can be used as the 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.
More than the preparation of various reagent, comprise that its concentration and dosage etc. are specific embodiments that is applicable to method and apparatus of the present invention, the preparation of the various reagent 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:
Be 2% hydrochloric acid 31 is connected to syringe pump by connecting pipe No. 1 position with being placed on the concentration that disposes in the reagent bottle; To be connected to as the prepared thiourea and ascorbic acid mixed solution 32 of the first reductive agent of pentavalent arsenic reduction No. 5 positions of multidigit selector valve 10 by connecting pipe; The second arsenic containing solution 34 is connected with No. 3 positions of multidigit selector valve 10 by connecting pipe; The 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 the second reductive agent with three entrances of mixed block in an entrance be connected by connecting pipe, two entrances of other of described mixed block connect respectively No. 1 position of argon gas 15 and multidigit selector valve.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 Arsenic in Seawater 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 introducing and the online prereduction of arsenic sample 35.The hydrogenation generation systems Internal Control Procedure 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, then multidigit selector valve 10 forwards No. 5 positions to and draws 1.2ml thiourea and ascorbic acid solution 32 to liquid storage pipe 9 by syringe pump 8, 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 Setting of water bath with thermostatic control commingled system 23 is 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 first 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 the 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 Arsenic in Seawater 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, namely carry out total arsenic concentration determination to the mixed solution in the step 1 water bath with thermostatic control commingled system 23.After second step finished, the trivalent arsenic concentration determination finished, and the mixed solution in the simultaneously water bath with thermostatic control commingled system 23 has also reached fully reduction, 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 first is 2% hydrochloric acid 31;
2. multidigit selector valve 10 forwards No. 4 positions to and is drawn the fully mixed solution 1.5ml of reduction 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, it is y=0.1925x+0.1883 that pentavalent arsenic reduces the typical curve equation online, 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 fast prereduction, and then utilize solution after sequential injection hydrogenation generation systems is introduced reduction, directly carry out hydrogenation, and measured 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 above-described embodiment 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 (10)
1. the atomic fluorescence spectrophotometry morphological analysis method of a trivalent arsenic and the online prereduction of pentavalent arsenic, the 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 the first reductive agent;
(b) contain the arsenic sample with second and mix with the second reductive agent, and carry out the trivalent arsenic concentration determination by the hydride that mixes rear generation;
(c) solution after the pentavalent arsenic reduction is finished in the step (a) is mixed with the second reductive agent, and carry out total arsenic concentration determination by the hydride that mixes rear generation;
Described first contains the arsenic sample mixes acquisition by the seawater sample that filters with hydrochloric acid solution, described second contains the arsenic sample by the seawater sample that filters, and dilution obtains as thinning agent through aqueous citric acid solution;
Perhaps 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.
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, it is characterized in that: described the first reductive agent is thiourea and ascorbic 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, it is characterized in that: described the second reductive agent is solution of potassium borohydride.
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, it is characterized in that: in described step (b) with (c), described mixing also comprises the hydrochloric acid solution as carrier, participates in simultaneously hydrogenation and produces hydrogen.
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: carry out trivalent arsenic concentration determination and total arsenic concentration determination by atomic fluorescence spectrometry.
6. realize the as claimed in claim 1 analytical equipment of the atomic fluorescence spectrophotometry morphological analysis method of trivalent arsenic and the online prereduction of pentavalent arsenic for one kind, it is characterized in that, comprise
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 is used for containing the arsenic sample by the sequential injection mode with first when above-mentioned steps (a) and imports to mentioned solution mixing test tube with the first reductive agent; Be used for when above-mentioned steps (b) importing second by the sequential injection mode and contain the arsenic sample and the second reductive agent carries out hydrogenation; The solution that is used for drawing when above-mentioned steps (c) after the reduction of mentioned solution mixing test tube is finished carries out hydrogenation;
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;
One system control, Data collecting and analysis 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 processes;
Described water bath with thermostatic control commingled system is connected pipeline with sequential injection hydrogenation generation systems and is connected; 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.
7. the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic according to claim 6 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 for heating the heating arrangement of described solution mixing test tube.
8. the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic according to claim 6 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 Procedure, 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.
9. the atomic fluorescence spectrophotometry morphological analysis means of a kind of trivalent arsenic according to claim 6 and the online prereduction of pentavalent arsenic, it is characterized in that, the control of described system, Data collecting and analysis system comprise that one installs the computer system of Arsenic in Seawater morphological analysis workstation software, and described Arsenic in Seawater morphological analysis workstation software comprises the control of sequential injection hydrogenation generation systems functional module, atomic fluorescence spectrophotometry detection system data acquisition function module and arsenium morphological analysis data processing function module.
10. according to claim 6 or the atomic fluorescence spectrophotometry morphological analysis means of 8 described a kind of trivalent arsenics and the online prereduction of pentavalent arsenic, it is characterized in that described pipeline is polyvinyl plastic pipeline.
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| 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 |
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| CN104502467A (en) * | 2014-11-20 | 2015-04-08 | 华中科技大学 | Determination method of arsenic valence |
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