CN209560093U - The fast automatic analytical equipment of tritium in water - Google Patents

Abstract

The utility model discloses a kind of fast automatic analytical equipments of tritium in water, comprising: back purge system obtains back segment filter liquor by reverse osmosis membrane purification for obtaining water sample to be measured；Automatic liquid matching and conveying measuring system, for the back segment filter liquor of the first preset volume and the scintillation solution of the second preset volume to be injected into counting vial respectively, and counting vial fullys shake, back segment filter liquor and scintillation solution are uniformly mixed, to obtain sample to be tested, and spectrometer is dodged by liquid, count measurement is carried out to sample to be tested, to obtain the analysis result of tritium in water sample to be measured.The device carries out quick separating-purifying to water sample to be measured using reverse osmosis membrane separation technology and reaches the condition requirement for meeting liquid and dodging measurement, so as to effectively shorten time of analysis, improves the efficiency of analysis；Using large capacity counting vial measurement pattern, detection limit is effectively reduced, with the analysis of the tritium suitable for a variety of ambient waters, effectively improves the applicability of analysis, realizes the automated analysis of tritium, it is simple easily to realize.

Description

The fast automatic analytical equipment of tritium in water

Technical field

The utility model relates to nuclear energy and nuclear technology field of engineering technology, in particular to fast automatic point of tritium in a kind of water Analysis apparatus.

Background technique

Currently, meeting the common people to daily life to ensure that government department grasps National Water Environmental radiological safety situation comprehensively The informed requirement of water radiation safety is applied flexibly, the measurement work for carrying out waterborne radioactivity nucleic is particularly important.And Tritium measurement is to put The important component of penetrating property Nuclide measurement work, is also more and more taken seriously and pays close attention in recent years.

The relevant technologies, researcher are generally dedicated to realizing by improving electrolytic enrichment process to the effective of low-level tritium Analysis, no matter however how electrolytic enrichment device upgrades improvement, the time needed for electrolytic enrichment process also still needs to one day or more, sample The problem of product pre-treatment overlong time, is not solved effectively.In addition, although some improved electrolysis units are certain The automation of electrolytic enrichment process is realized in degree, but for tritium analytic process in entire water, still need to human attendance and hand Dynamic to operate, the working efficiency of tritium analysis is unable to get breakthrough always in water.Meanwhile in existing water there is analysis in tritium analysis method Overlong time or the excessively high problem of detection limit, it is difficult to meet the requirement analyzed tritium in ambient water.

Utility model content

The utility model is intended to solve at least some of the technical problems in related technologies.

For this purpose, a purpose of the utility model is to propose a kind of fast automatic analysis method of tritium in water, this method It can effectively shorten time of analysis, improve the efficiency of analysis, and detection limit can be effectively reduced, effectively improve analysis Applicability realizes the automated analysis of tritium, simple easily to realize.

Another purpose of the utility model is to propose a kind of fast automatic analytical equipment of tritium in water.

In order to achieve the above objectives, on the one hand the utility model proposes the fast automatic analysis method of tritium in a kind of water, packet It includes following steps: obtaining water sample to be measured, back segment filter liquor is obtained by reverse osmosis membrane purification；It is injected respectively into counting vial The back segment filter liquor of first preset volume and the scintillation solution of the second preset volume, and counting vial fullys shake and makes back segment filter liquor It is uniformly mixed with scintillation solution, to obtain sample to be tested；Spectrometer is dodged by liquid, count measurement is carried out to the sample to be tested, to obtain The analysis result of tritium in the water sample to be measured.

The fast automatic analysis method of tritium in the water of the utility model, using reverse osmosis membrane separation technology to water sample to be measured into The quick separating-purifying of row effectively shortens the pre-treatment time to reach the condition requirement for meeting liquid and dodging measurement, improves analysis Efficiency selects suitable liquid to dodge measurement method and carries out count measurement to sample, so as to which detection limit is effectively reduced, to be applicable in The analysis of tritium in a variety of ambient waters, effectively improves the applicability of analysis, realizes the automated analysis of tritium, simple easily to realize.

Further, in the back segment filter liquor and the second preset volume for injecting the first preset volume into counting vial respectively After scintillation solution, the bottle cap of the counting vial is screwed automatically, and make back segment filter liquor and scintillation solution counting vial fullys shake It is uniformly mixed after, wiping processing is carried out to the counting vial automatically.

Further, the volume of the counting vial is 100ml, and first preset volume and second preset volume are equal For 50ml.

Further, described to obtain water sample to be measured, back segment filter liquor is obtained by reverse osmosis membrane purification, is further wrapped It includes: being rinsed using water sample to be measured；The water sample to be measured is filtered by the reverse osmosis membrane separation, to obtain spare water sample, And exclude waste water；The spare water sample is filtered again by the reverse osmosis membrane, the back segment is obtained with purification and is filtered out Liquid；Empty remaining water sample to be measured.

Further, further includes: detect the conductivity value of the back segment filter liquor；Judge whether the conductivity value is less than Default conductivity value；If the conductivity value is less than the default conductivity value, it is pre- that first is injected into the counting vial If the back segment filter liquor of volume；If the conductivity value is more than or equal to the default conductivity value, by described anti- Permeable membrane purification back segment filter liquor again, until the conductivity value is less than the default conductivity value.

In order to achieve the above objectives, on the other hand the utility model proposes the fast automatic analytical equipment of tritium in a kind of water, Include: back purge system, for obtaining water sample to be measured, back segment filter liquor is obtained by reverse osmosis membrane purification；Automatic liquid matching With conveying measuring system, for respectively injecting the back segment filter liquor and the second preset volume of the first preset volume into counting vial Scintillation solution, and counting vial fullys shake, back segment filter liquor and scintillation solution are uniformly mixed, to obtain sample to be tested, and pass through liquid It dodges spectrometer and count measurement is carried out to the sample to be tested, to obtain the analysis result of tritium in the water sample to be measured.

The fast automatic analytical equipment of tritium in the water of the utility model, using reverse osmosis membrane separation technology to water sample to be measured into The quick separating-purifying of row effectively shortens the pre-treatment time to reach the condition requirement for meeting liquid and dodging measurement, improves analysis Efficiency, and the liquid sudden strain of a muscle measurement method that reselection is suitable for carries out count measurement to sample, so as to which detection limit is effectively reduced, With the analysis of the tritium suitable for a variety of ambient waters, the applicability of analysis is effectively improved, realizes the automated analysis of tritium, it is simple easily real It is existing.

Further, further includes: sample bottle automatic control system, in the default appearance of injection first into counting vial respectively After the scintillation solution of long-pending back segment filter liquor and the second preset volume, the bottle cap of the counting vial is screwed automatically, and sufficiently shaking Swing counting vial make back segment filter liquor and scintillation solution it is uniformly mixed after, wiping processing is carried out to the counting vial automatically.

Further, the volume of the counting vial is 100ml, and first preset volume and second preset volume are equal For 50ml.

Further, the back purge system includes: water sample wash module, for being rinsed using water sample to be measured；One Secondary filtering module to obtain spare water sample, and excludes useless for filtering the water sample to be measured by the reverse osmosis membrane separation Water；Sample preparation module proposes that obtaining back segment filters out for filtering again by the reverse osmosis membrane to the spare water sample with purification Liquid；Drain module, for emptying remaining water sample to be measured.

Further, further includes: detection module, for detecting the conductivity value of the back segment filter liquor；Judgment module is used In judging whether the conductivity value is less than default conductivity value；Processing module, it is described pre- for being less than in the conductivity value If when conductivity value, inject the back segment filter liquor of the first preset volume into counting vial, and be greater than in the conductivity value or When equal to the default conductivity value, by reverse osmosis membrane purification back segment filter liquor again, until the conductivity value is small In the default conductivity value.

The additional aspect of the utility model and advantage will be set forth in part in the description, partially will be from following description In become obvious, or recognized by the practice of the utility model.

Detailed description of the invention

The utility model is above-mentioned and/or additional aspect and advantage from the following description of the accompanying drawings of embodiments will Become obvious and be readily appreciated that, in which:

Fig. 1 is three standards of the relevant technologies about tritium analysis sample-pretreating method contrast schematic diagram in water；

Fig. 2 is the schematic diagram of the improved alkali formula electrolytic enrichment unit of the relevant technologies；

Fig. 3 is the schematic diagram of the improved alkali formula electrolytic enrichment device of the relevant technologies；

Fig. 4 is the relevant technologies solid polymerization film electrolysis principle schematic diagram；

Fig. 5 is tritium automatic electrolysis unit structure chart of the relevant technologies based on SPE；

The contrast schematic diagram of method after Fig. 6 is the relevant technologies conventional method and improves；

Fig. 7 is the structural schematic diagram of surabaya electrolysis installation of the relevant technologies based on proton exchange membrane；

Fig. 8 is the flow chart according to the fast automatic analysis method of tritium in the water of the utility model one embodiment；

Fig. 9 is according to tritium automatic analysis method workflow in the water based on RO film sample preparation of the utility model one embodiment Journey；

Figure 10 is the common household water filter structural framing schematic diagram of the relevant technologies；

Figure 11 is the RO UF membrane sample preparation device structural block diagram according to the utility model one embodiment；

Figure 12 is each link work flow diagram of RO UF membrane sample preparation device according to the utility model one embodiment；

Figure 13 is the liquid flashing counting measurement flow chart according to the utility model one embodiment；

Figure 14 is the RO film preparation conductivity variation tendency schematic diagram according to the utility model one embodiment；

Figure 15 is the background spectrum according to the utility model one embodiment；

Figure 16 is the standard specimen spectrogram according to the utility model one embodiment；

Figure 17 is to be changed according to the sensitivity figure of merit SFOM of the utility model one embodiment with water sample and scintillation solution proportion Variation tendency schematic diagram；

Figure 18 is according to this original pattern counting rate of the utility model one embodiment and the relation schematic diagram of time of measuring；

Figure 19 is according to the environmental water sample counting rate of the utility model one embodiment and the relation schematic diagram of time of measuring；

Figure 20 is according to the mark-on sample counting rate of the utility model one embodiment and the relation schematic diagram of time of measuring；

Figure 21 is the LB7 type scintillation counter quality control chart according to the utility model one embodiment；

Figure 22 is according to tritium concentration analysis of uncertainty in measurement schematic diagram in the water of the utility model one embodiment；

Figure 23 is the block diagram according to the fast automatic analytical equipment of tritium in the water of the utility model one embodiment.

Specific embodiment

The embodiments of the present invention are described below in detail, the example of embodiment is shown in the accompanying drawings, wherein from beginning to end Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached The embodiment of figure description is exemplary, it is intended to for explaining the utility model, and should not be understood as the limit to the utility model System.

It is first simple to introduce in the water for introducing the utility model embodiment before the fast automatic analysis method of tritium and device The once status of tritium and the relevant technologies status of analysis tritium.

The purpose of 1.1 the utility model embodiments be in the water based on RO film sample preparation tritium automatic analysis method it is feasible Property is studied.Experimental study is carried out to the comprehensive performance of RO film sample preparation device first under existence conditions, grasps its basic nature It can and suggest improvements to the problem of discovery；Secondly measurement process measurement of correlation mode is dodged to liquid and measuring condition carries out theory Research determines that suitable liquid dodges measurement method and condition on this basis by experimental verification；Finally in front research achievement it On, the experimental comparison that tritium is analyzed in water is carried out by the way of method comparison, to verify tritium acquired results in this method analysis water Accuracy, thus for this research method later practice and popularization reference and foundation are provided.

1.2, the basic situation of tritium

Tritium belongs to the isotope of hydrogen, have radioactivity, half-life period about 12.32.One is generated respectively after one triton decay It is a³He, anti-neutrino and ceiling capacity are no more than 18.6keV, the negative β particle of average energy about 5.7keV.

There are many existence forms of Environmental Tritium, is broadly divided into the HTO, gaseous HT and CH of liquid₃T and combination The OBT of state, wherein HTO occupies absolute leading position in the environment.The Transport And Transformation of tritium in the environment is mainly also with HTO's Form realizes that this has also embodied the importance that tritium analysis in water measures the research to Environmental Tritium.

1.3, tritium analysis measurement is summarized in water

1.3.1, the development course of Chinese tritium analysis measurement

In China, for tritium research early start the sixties in last century, the main purpose of original research tritium be in order to Ensure the radiological safety of nuclear facilities operation maintenance personnel；1970s, the analysis measurement work for tritium in natural environment are opened Begin to occur, thus be brought into schedule for the analysis measurement work of low-level environment tritium；To the eighties, China has carried out several times The analysis of tritium, monitoring are all incorporated into investigation content, the analysis measurement of Chinese tritium in national environmental radio activity level investigation work It is developed.In the 21st century, is as Chinese nuclear technology is using horizontal fast development, along with the public to environmental quality Growing interest, environmentally friendly supervision department and nuclear facilities unit of operation have carried out successively for tritium in the air around nuclear power station base Tritium in tritium (including river water, well water, pond water, seawater) and biology in (including precipitation, vapor), water body (tissue free water tritium, Organically combine tritium) analysis measure work.National 32 provincial radiation monitoring stations (including Qingdao City's radiation monitoring station) The measurement work of the analysis to tritium in local air (including precipitation, vapor) is carried out in succession.In addition, some colleges and universities, scientific research The units such as institutes also increasingly pay attention to the analysis measuring study to tritium.The introduction of increasingly advanced analysis measuring device and a large amount of Tritium analysis measurement practice so that Chinese tritium analysis measurement capability achieves quick development.

1.3.2 the method for tritium analysis measurement mainly has gas counting method, liquid scintillation counting and mass spectrography etc. in water, under Simple introduction is done in face of these types of method.

A, gas counting method.As the term suggests gas counting method gas and then is carried out again firstly the need of converting detected water sample to Measurement.CH is generally converted for detected water sample by chemically synthesized mode₄、C₂H₆Or C₃H₈Equal working gas, then by these Count measurement is carried out in working gas input proportional counter.The advantages of this method is detectivity height, some researches show that, Working gas selects C₃H₈In the case where, proportional counter tube can be promoted at double to the detectivity of tritium.Its shortcomings that, is also very bright Aobvious: detected water sample is converted to that gaseous process is cumbersome and the gas that generates is inflammable and explosive, and there are certain danger.

B, mass spectrography.Mass spectrography is also known as³Growth measurement method in He is to utilize decay constant of the mass spectrograph by measurement of tritium³He, then pass through a kind of anti-indirect measurement method for pushing away to obtain tritium.The principle of this method is removed first with vacuum outgas Initially it is dissolved in detected water sample³Then detected water sample is stored in a closed container (usually glass by He Ball) in, made by the sealed storage of a period of time (it is generally necessary to some months)³He accumulation.It is tested followed by mass spectrograph measurement What water sample generated during storage³He content is inferred to the content of tritium in sample in turn.Due to³He is seldom dissolved in organic compound, And gas phase is easily entered, therefore the technology is suitable for various samples, such as food, vegetation.This method it is main Advantage is can to drop to detection limit very low, therefore is adapted to the measurement to extremely low tritium concentration sample, document, which is shown, takes 20ml Water sample, integration time 3 months, then detection limit can drop to the level of 0.15Bq/L.This method another advantage is that The simplicity of operation, it is only necessary to which two operating process, i.e. degasification and measurement do not need the cumbersome step such as burnt, distill, be concentrated Suddenly, therefore this method can also preferably avoid laboratory pollution.The shortcomings that mass spectrography is that each measurement requires for a long time by force The Storage period of property processed.

C. liquid scintillation counting.Liquid scintillation counting is that up to the present technology is the most mature, is most widely used A kind of measurement of tritium method.The detection efficient of this method is high, and time of measuring is compared also more excellent for the two methods of front Gesture, the analysis work of tritium is all this measurement method used in overwhelming majority water at present.Therefore, it is necessary to this method into Row introduces.

Liquid scintillation counting has certain requirement to the degree of purity and tritium concentration of detected water sample.If the degree of purity of sample Not enough, containing more impurity, then it will increase the quenching degree of sample to reduce the detection efficient during count measurement；If sample The tritium concentration of product is lower, and the detection limit all in measurement method is all not detected hereinafter, then will appear big measurements Situation, thus can not achieve the effective monitoring to tritium.Therefore, selection liquid scintillation counting usually needs to carry out sample in advance Purification is handled with concentration.

(1) it purifies

The mode of purification can have distillation, film filtering and ion exchange column etc..Laboratory generallys use often both at home and abroad at present The mode of pressure distillation purifies sample, and this way of purification effect is good, but the time needed for the process distilled is relatively long, Generally at least need 2 to 3 hours.In addition, due to isotope effect, in accumulation distillation process the content of tritium there are gradient, because The distillate that this collects same area is extremely important, and the collection of distillate will also be limited simultaneously by conductivity, this is to evaporating The collection selection work belt of liquid carrys out certain difficulty out.

Film filtering separating-purifying mode filter film technology develop on the basis of gradually paid attention to, its principle with it is daily Water purifier working principle in family life is similar, i.e., by water by filter membrane so that impurities in water is stopped by filter membrane, absorption and from It is separated in water, to realize the effect of water quality purifying.

Filter membrane type multiplicity, its filter capacity of different types of filter membrane differs greatly, to membrane filtration technique applied to tritium point The result of study that analysis process carried out research shows: reverse osmosis (RO) membrane technology is a kind of alternative method.This method The advantages of be water sample separating-purifying process it is fast, automation that is easy to operate and being easily achieved purification process, but there is also use The problem of service life, needs periodically to replace filter membrane.

Once application was obtained in Tritium measure work in the separating-purifying mode of ion exchange column, and this separating-purifying mode can To obtain more pure surabaya, but because there is recycling rate of waterused difference, utilization rate is not high, is not described in detail here.

(2) concentration

The mode of concentration is mainly electrolysed.Its principle is to decompose to generate hydrogen and oxygen when being electrolysed by water, is utilized In hydrogen the content of tritium can lower than the property of tritium level in electrolyte, by electrolysis so that in final residue electrolyte tritium concentration It increases, to realize the concentration of detected water sample tritium.Traditional alkali formula electrolysis method substantially process is as follows: being steamed for the first time to water sample It evaporates in addition to sodium peroxide is added in distillate on the basis of impurity and organic matter, is then poured into electrolytic cell and carried out Electrolysis need to finally obtain distillate, also need to sample during this after long-time is electrolysed to sample second distillation to remove alkali Multiple weighing operation is carried out so that the cycles of concentration to sample calculates.1.3.3, both at home and abroad in water tritium analysis measurement status and Developing direction

Analysis measurement for tritium in water, the national standard that Chinese nineteen ninety implements use " air-distillation+electrolytic enrichment The analysis method of+liquid sudden strain of a muscle measurement "." test method of tritium level in drinking water " of American Society Testing and Materials (ASTM) and state " the air-distillation+liquid that " the measurement liquid scintillation counting of water quality tritium activity concentration " of border standardization body (ISO) then selects The analysis method of sudden strain of a muscle measurement ".The measurement method of three standards is close, but pretreatment process is respectively different.Their pre-treatment Journey comparison is as shown in Figure 1.

By comparison as it can be seen that three of the above pre-treating method all select under alkaline environment addition strong oxidizer to sample into Row distilation, wherein basic treatment is to remove the radioactivity that radioiodine, carbon etc. are easy to be distilled off with tritium Nucleic.In addition, can inevitably have the case where containing organic matter in environmental water sample, although these content of organics are few, easily With tritium be distilled off influence measurement process sample quenching degree, be added strong oxidizer can aoxidize these organic matters from And eliminate its interference to measurement result.

Because of Chinese national standard electrolytic enrichment process more than another two standard, in the water that can be measured after the concentration ratio of tritium The two is much lower, thus is more suitable for the analysis to low-level tritium.IAEA also suggests selecting " electrolytic enrichment pre-treatment in the world The method of+liquid flashing counting measurement " realizes that effective analysis to low-level tritium measures.However, it is contemplated that traditional alkali formula is electrolysed Method for concentration program is cumbersome, sample processing time is long and there are the danger of hydrogen detonation.For this purpose, mentioned in national standard, if instrument Sensitivity is sufficiently high, can not electrolytic enrichment, the upper spectrometer measurement directly after normal pressure distilation.In consideration of it, many laboratories In water in the analytic process of tritium, this pre-treatment is generallyd use by the analysis method of the tritium simplified.Experience have shown that existing Some liquid dodges on Spectrometer performance basis, and detection limit obtained by the analysis method using this tritium simplified generally exists 1Bq/L or so, this is still more inadequate for the Tritium measure of current Chinese environmental water sample.

In order to realize that the environmental water sample to low-level tritium more effectively analyzes measurement, researchers at home and abroad generally post expectation In improving or being promoted sample pretreatment process or device, conducted in-depth research in particular for electrolytic enrichment link.Pass through Effort, various new electrolytic enrichment methods are found, and some of new methods are promoted and have corresponding product to come out.

A. the improvement and application of traditional alkali formula electrolytic cell

Based on traditional alkali formula electrolysis principle, the structure at electrolysis yin-yang the two poles of the earth is improved, it is as follows to improve content: By cathode design at hollow lining, the structure of double-layer epispores, circulation cooling water between double-layer epispores interlayer, electrolyte is from yin The export of pole lower part；Anode interior equally uses hollow structure, and outer wall is disposed with stomata, and exhaust outlet is arranged in top and condenser pipe connects It connects, in order to which electrolytic process generates the export of gas.Improved electrolysis unit is big in terms of the rate of recovery of tritium and concentration efficiency There is improvement, but it fails to make progress in terms of safety, ease of handling and electrolysis time.Its electrolytic enrichment cellular construction Shown in as shown in Figure 2, several electrolytic enrichment units form the electrolytic enrichment device of a tritium, as shown in Figure 3.

B. application and development based on SPE electrolysis tech

SPE Chinese name is solid polymer electrolyte, the related content of SPE electrolysis tech and by verification experimental verification this The reliability and superiority of one technology.The principle of this method is to can be used as the characteristic of electrolyte, electrolytic process based on SPE film itself In, positive and negative catalysis electrode abuts against SPE film two sides, produces after catalyticing anode is decomposed by the detected water sample of air-distillation early period Raw hydrogen ion and oxonium ion, to realize the electrolysis to water sample.Near anode, oxonium ion issues negative electron to become oxygen Gas；Hydrogen ion passes through SPE film and reaches cathode and generate hydrogen in conjunction with negative electron near cathode.The oxygen and hydrogen quilt of generation The isolation of SPE film, is discharged from different pipelines, and solid polymerization film electrolysis principle is as shown in Figure 4.

Compared with traditional alkali formula electrolysis method, this SPE electrolysis tech has following three advantages: first is that it is safer, The hydrogen and oxygen that electrolytic process generates are come by SPE UF membrane, are not susceptible to the danger such as explosion.Second is that the promotion of concentration rate, SPE film, which is utilized, in this method well can be used as the characteristic of electrolyte, and electrolytic process does not need that alkaline reagent is added, therefore remains Object is few, and the enrichment factor of water has significant increase.Third is that process is simple, electrolysis time is short, and alkali on the one hand is added due to no before being electrolysed Property reagent, just without being evaporated in vacuo again after the completion of electrolysis, process is simplified；Another aspect SPE film resistance very little, film The electric current passed through between electrode is not easy to be saturated, so that high current electrolysis becomes feasible, to largely shorten electricity Solve the time.Because SPE electrolysis tech solves many unavoidable difficulties of traditional alkali formula electrolysis method, thus this technology once It is proposed is just widely studied and is used after promoted improvement by extensive investment.

In the related technology, another set of SPE film is electrolysed enrichment facility automatically, which has done two o'clock improvement: first is that electrolysis The surface of plasma membrane, which has been done, slightly to be handled, and the separating property that gas is generated to electrolytic process is improved；Second is that in order to detect electrolyte Liquid level is mounted with liquid level sensor, is automatically stopped electrolysis so that the device can according to need and collects sample, the apparatus structure See as shown in Figure 5.

Further, further the air-distillation purification process before electrolysis is replaced on the basis of SPE film electrolysis tech It is purified at RO UF membrane, to establish this tritium analysis method by " RO UF membrane+SPE electrolysis+liquid dodges measurement ".This side Method has the following excellent compared with the method for traditional " air-distillation+alkali formula electrolytic tank electrolysis+vacuum distillation+liquid dodges measurement " Gesture eliminates the addition of oxidant and alkaline reagent, time first is that replacing the air-distillation before electrolysis with RO UF membrane in program On foreshortened to 40 minutes or so by original 2~3 hours；Replace alkali formula electrolytic tank electrolysis second is that being electrolysed with SPE, by original on the time That comes foreshortens to 1~2 day for 7~10 days；Third is that addition of the new method because of not no alkaline reagent, no longer needs to carry out vacuum steaming after electrolysis It evaporates, eliminates original 2~3 hours vacuum distillation time.Two methods comparison is as shown in Figure 6.

In the related technology, the automatic electrolysis unit of each self application is successively designed using SPE membrane technology.These devices are set It counts design just bright et al. with vegetarian rattan in principle and overall structure to be not much different, only done in terms of certain details respective It improves.

C. based on the electrolysis tech of proton exchange membrane

Proton exchange membrane gains great popularity in water electrolysis hydrogen producing industry, because it has can under the working environment of high current The ability of the electrolytic efficiency of superelevation is kept for a long time, this feature has proton exchange membrane very in the application of water electrolysis industry Good prospect.By the inspiration of water electrolysis hydrogen producing industry, proton exchange membrane is applied to the field of tritium in electrolytic enrichment water, and is set Count out the surabaya electrolytic enrichment equipment based on proton exchange membrane.The basic framework of the equipment and previously described SPE film, which are electrolysed, to be filled Set it is similar, it is maximum to be modified in that SPE film is substituted by proton exchange membrane, by the excellent performance of the latter, so that the equipment exists While having nearly all advantage of previously described SPE electrolysis unit, additionally it is possible to effectively solve existing for SPE electrolysis tech The big problem of concentration dead volume, electrolysis time also further foreshortens to 24 hours, thus has more superiority than the former.Specific example As shown in Figure 7.

1.3.4, however, from the point of view of by the status of tritium analysis in the above water, researcher is generally dedicated to being electrolysed by improving Concentration process realizes effective analysis to low-level tritium.No matter however how electrolytic enrichment device upgrades improvement, electrolytic enrichment Time needed for process also still needs to one day or more, and the too long problem of time for sample pretreatment is not solved effectively.Though in addition, Right some improved electrolysis units realize the automation of electrolytic enrichment process to a certain extent, but with regard to tritium in entire water For analytic process, still needs to human attendance and be manually operated.The working efficiency that tritium is analyzed in water is unable to get breakthrough always.

1.4, the purpose of the utility model embodiment be in the water based on RO film sample preparation tritium automatic analysis method can Row is studied.The main contents of research include the applicable water sample condition of RO film sample preparation device, the stabilization of module operational process, Reliability and operational process parameters performance indicator.The suitable liquid of research dodges measurement method, and to solve, detection limit is high to be asked Topic, and optimize every measuring condition parameter for the measurement method.Finally, by method compare, verifying this time research based on Tritium automatic analysis method precision of analysis in the water of RO film sample preparation.

It is based on above-mentioned reason, in order to solve the problems, such as that technology exists, the utility model embodiment proposes a kind of water The fast automatic analysis method and device of middle tritium.

Describe with reference to the accompanying drawings according to the utility model embodiment propose water in tritium fast automatic analysis method and Device describes the fast automatic analysis method of tritium in the water proposed according to the utility model embodiment with reference to the accompanying drawings first.

Fig. 8 is the flow chart of the fast automatic analysis method of tritium in the water of the utility model one embodiment.

As shown in figure 8, in the water tritium fast automatic analysis method the following steps are included:

In step sl, water sample to be measured is obtained, back segment filter liquor is obtained by reverse osmosis membrane purification.

It is understood that water sample to be measured is referred to as detected water sample, the method for the utility model embodiment it is preliminary Frame system is " RO film (reverse osmosis membrane) separates sample preparation+liquid flashing counting measurement ", as shown in figure 9, firstly, detected water sample enters RO UF membrane sample preparation device is entered RO film after being handled with premenstruum (premenstrua) coarse filtration and is cleaned purification, it is of course also possible to directly by anti- Permeable membrane purification obtains back segment filter liquor, and those skilled in the art can be configured according to practical situation, herein not It is specifically limited.

It should be pointed out that the workflow described above for this research process this method.During studying herein, The model machine for only producing RO UF membrane sample preparation, realizes the automatic processing of water sample, and rest part requires to manually complete.But This has no effect on the purpose studied herein the feasibility of tritium automatic analysis method in the water based on RO film sample preparation.Pass through this Secondary research while verifying this method feasibility, grasps correlation performance parameters and proposes to be correspondingly improved suggestion.On this basis Sample preparation module need to be only connected in a modular manner by technological design with measurement module, complete analysis process can be realized Automation.

Specifically, RO film, the entitled reverse osmosis membrane of Chinese, are the cores of this research sample preparation device, working principle is big It causes as follows: being respectively weak solution and concentrated solution at left and right sides of RO film, at the beginning, the solvent of weak solution passes through under the action of infiltration RO film flows to concentrated solution.After reaching balance, weak solution side liquid level will be less than concentrated solution side, and generate the (infiltration of a pressure difference Pressure).At this time concentrated solution side apply one be greater than the pressure of osmotic pressure after, the flow direction of solvent is by the side before being in reverse to To this process is as reverse osmosis.The selective penetrated property that this method relies on RO film to have makes solvent and solute point by solution From to achieve the purpose that purification.

The category of RO membrane technology relative maturity, film manufacturer and film is numerous, and manufacturer is for different application and makes There is the membrane component product of respectively corresponding model with condition.This project researching and designing personnel are in early period to the RO membrane element of a certain brand Part is investigated, it is thus understood that the condition and range of some each self applications of variety classes RO film of the brand is as shown in table 1.According to investigation Situation, the RO film sample preparation device of the utility model embodiment have selected a RO for being suitable for handling low salinity water of the brand Membrane component.Wherein, table 1 is the scope of application table of certain brand RO film different model membrane component.

Table 1

Further, in one embodiment of the utility model, water sample to be measured is obtained, passes through reverse osmosis membrane purification Back segment filter liquor is obtained, further comprises: being rinsed using water sample to be measured；Water sample to be measured is filtered by reverse osmosis membrane separation, To obtain spare water sample, and exclude waste water；Spare water sample is filtered again by reverse osmosis membrane, back segment filter is obtained with purification Liquid out；Empty remaining water sample to be measured.

It is understood that the utility model embodiment is using coarse filtration, treated that water sample to be measured is rinsed, so as to This analysis is interfered with effectively excluding last measurement residual, to effectively reduce error, improves the accuracy of analysis. Also, after water sample to be measured is prepared, timely emptying thus water sample to be measured, analyzed next time thus convenient.

In addition, RO UF membrane sample preparation device will be described in detail below.

2.1, sample preparation device is constituted

Current common family has been used for reference in the core of tritium RO UF membrane sample preparation device in the water of the utility model embodiment With the structural framing of water purifier.The generally built-in Pyatyi filtering of common household water filter, first, the third level be that PP cotton is filtered, second, Level V is active carbon filtering, and the fourth stage is the filtering of RO film.Common household water filter structural framing is as shown in Figure 10.

The RO film sample preparation device of the utility model embodiment is determined based on structural framing shown in Figure 10 using through investigation RO membrane component, then be aided with the main components such as water valve, liquid level sensor, water pump, flowmeter, designed after engineered available The RO UF membrane sample preparation device of Yu Shuizhong tritium analysis.The structural block diagram of the sample preparation device is as shown in Figure 11.

2.2, sample preparation workflow

The water sample treatment process of the device can be divided into sample water and rinse, primary filtering, sample preparation, drain four processes altogether. Wherein sample water flushing link rinses entire sample-preparing system using a large amount of water samples, caused by excluding the residual because of a upper sample as far as possible Interference to this sample；Water sample is flowed through RO film and carries out separating and filtering, the pure water generated after film filters by primary filtering link It is stored in spare in three holding barrels, waste water is expelled directly out；Sample preparation link will be stored in spare pure water in holding barrel import RO film into Capable filtration treatment again, takes its back segment filter liquor as final detected water sample；Last draining link is by this sample treatment Remaining water sample emptying, prepares in process apparatus to can handle next water sample at any time.In conjunction with RO UF membrane system in Figure 11 The structural block diagram of sampling device describes the specific workflow of each link as shown in figure 12.

The stopping of each link of Figure 12 relies primarily on the flowmeter of connection RO film pure water mouth to realize.Pre-set each link The limit current value of flowmeter is flowed through, once the pure water amount for flowing through flowmeter in operational process reaches preset limit value, pump 1 just stops Work is cut off into the water source of RO film, and the working link stops immediately after remaining process.

RO UF membrane sample preparation device design has " automatic " and " manual " two kinds of operating modes." automatic " mode can realize one Key starting, the degree of automation is relatively high, only need to click "start" button after, device can according to program setting, strictly in order according to The secondary sample water that enters rinses, primary filtering, sample preparation, empties work.Difference of " manual " mode compared to " automatic " mode is often The starting of one link requires manually implemented, and the degree of automation is relatively low, but this mode can select current institute as needed The working link needed, flexibility are relatively stronger.

In step s 2, the back segment filter liquor and the second preset volume of the first preset volume are injected into counting vial respectively Scintillation solution, and counting vial fullys shake and makes being uniformly mixed for back segment filter liquor and scintillation solution, to obtain sample to be tested.

It is understood that as shown in figure 9, the back segment filter liquor of certain volume by injection counting vial, the backward counting The scintillation solution of certain volume is injected in bottle and screws bottle cap, is uniformly mixed the filter liquor in bottle with scintillation solution through fulling shake.

Wherein, in one embodiment of the utility model, after the first preset volume is injected into counting vial respectively After the scintillation solution of section filter liquor and the second preset volume, the bottle cap of counting vial is screwed automatically, and make counting vial fullys shake Back segment filter liquor and scintillation solution it is uniformly mixed after, wiping processing is carried out to counting vial automatically.

Certainly, the utility model embodiment can also screw the bottle cap of counting vial by artificial mode, and through abundant Concussion is uniformly mixed the filter liquor in bottle with scintillation solution.After carrying out wiping processing to counting vial outer wall with alcohol swab, so as to Electrostatic interference is effectively reduced.

Wherein, in one embodiment of the utility model, the volume of counting vial is 100ml, the first preset volume and the Two preset volumes are 50ml.

It is understood that, to reduce detection limit, liquid dodges measurement because water sample pretreatment process does not carry out electrolytic enrichment 100ml capacity counting vial measurement pattern is selected, this can make detection limit be reduced to 0.4Bq/L or so, efficiently solve detection The excessively high problem of lower limit；The utility model embodiment when selecting 100ml capacity counting vial measurement pattern, adopt with scintillation solution by water sample It is than convenient with the volume proportion of 50:50；By the research to sample time of repose, when determining measurement by standard sample, to Test sample and this original pattern are successively placed in liquid and dodge spectrometer, only need to set suitable time of measuring, can measure immediately, without specially standing It is protected from light.

In step s3, spectrometer is dodged by liquid and count measurement is carried out to sample to be tested, to obtain point of tritium in water sample to be measured Analyse result.

It is understood that as shown in figure 9, being suitable for by the incoming liquid sudden strain of a muscle spectrometer of manufactured sample to be tested and as required setting Count measurement is carried out after measuring condition.

Spectrometer measuring device will be dodged to liquid below to describe in detail.

2.3 liquid dodge spectrometer measuring device

2.3.1 the working principle that liquid dodges measurement is fitted into same counting vial sufficiently approximately as: sample and scintillation solution Mixing, the β ray energy that sample generates is direct or indirect to be absorbed by the organic scintillator in scintillation solution, causes the molecule of the latter Be excited, the organic scintillator molecule being excited by launch outward it is photoelectronic in a manner of de excitation to returning to ground state, and launch Photoelectron received by photomultiplier tube after through nuclear power sub-control system be converted into count signal, be excited scintillator molecular emission Photoelectron number it is related with the β ray energy that sample generates, it is final to realize between count signal and β ray energy by conversion Corresponding relationship, to realize measurement to low energy β radiation sample.It, can be with because sample is sufficiently mixed with scintillation solution It is regarded as sample to be surrounded by scintillation solution, the β ray energy that the former emits can not be influenced by sample self-absorption and directly be shifted To scintillator, therefore, the measurement of 4 ∏ solid angles may be implemented on this theoretical method.During actual measurement, liquid flashing counting is surveyed Amount is often influenced by system quenching effect, it is therefore desirable to the suitable quenching school of actual conditions selection according to sample Correction method is to obtain accurate system detection efficient.

2.3.2 measuring system is constituted

A. liquid dodges spectrometer

As liquid dodges the increasingly mature of measuring technique, liquid dodges measuring device and has also obtained quick development, and device performance has It is obviously improved.Currently, the liquid generally used both at home and abroad, which dodges spectrometer, mainly the PE from the U.S., Japanese Aloka and sweet smell The series such as blue Hidex.

Although the manufacturer of liquid sudden strain of a muscle spectrometer and model are different, it to be used for basic principle, structural framing and the survey of Tritium measure Amount performance is not much different.Therefore, this research experiment measurement process selects LB7 type Low background liquid to dodge spectrometer and carries out counting survey Amount.The structure of the device is constituted and performance parameter is substantially as follows: by photomultiplier tube, (3, be mutually the panel detector structure 1. used Hexagonal angle is laid), the Anticoincidence shield detector and thick and heavy lead screen module composition in delayed coincidence counting circuit.Photoelectricity times Increase that pipe thermal noise is low, equipment high-voltage-stable, instrument shield effectiveness are good, this makes the device have the Tritium measure performance of high level； 2. use 4000 multichannel analyzer and automatically switch gain make the counter have high level resolution ratio；3. can be used The Quench Correction Methods of ESCR (External Standard Channel Ratio).One piece of activity is housed inside the counter About 740kBq's¹³³The source Ba is used before each count measurement¹³³The source Ba carries out gamma-radiation to sample to obtain the Compton of sample Spectrum, is analyzed by multichannel analyzer, will account for the spectrum road of tale 75% as quenching indication parameter (i.e. ESCR value).This quenching The correction range of bearing calibration is wide, is suitable for low-activity activity sample；4. except having the most common 20ml capacity of measurement Counting vial function outside, the counting vial of 100ml, 145ml capacity can also be measured, by increase sample size can make to measure As a result detection limit is lower.

B. scintillation solution

By previously described liquid flashing counting measuring principle it is found that scintillation solution acts as in entire liquid flashing counting measurement process The effect of one detector: it detects the β ray energy of sample sending and is absorbed, is converted into photoelectron.It is different types of Scintillation solution absorbs, the ability difference of conversion β ray energy, thus is suitable for the measurement of different samples.Therefore, according to tested The difference of sample selects the scintillation solution adaptable with it just to seem necessary.The utility model embodiment is to current utilization rate Two serial scintillation solutions of highest Optiphase HiSafe and Ultima Gold are investigated, it is thus understood that Optiphase The scintillation solution of HiSafe series has mainly used diisopropyl naphthalene (DIN) as scintillator, it be mainly characterized by do not reducing Safety obtains certain promotion in the case where scintillation solution performance.And Ultima Gold series belongs to slow scintillation solution, it is main special Point is that have high flash-point, detection efficient high and low malicious and not volatile.Table 2 lists the common sudden strain of a muscle of the two serial several moneys Bright liquid and its correlated performance feature.Wherein, table 2 is that several moneys often use scintillation solution correlated performance feature contrast table.

Table 2

LLT the and u LLT type scintillation solution of Ultima Gold series is all suitable for the sample measurement of environment low-level tritium, with Purpose phase one of the tritium automatic analysis method mainly for the analysis of tritium in ambient water in the water based on RO film sample preparation studied herein It causes.Wherein u LLT type ratio LLT type scintillation solution has lower background count, therefore selects in the experimentation of this research Ultima Gold u LLT type scintillation solution with ultralow background, control environment monitoring application.

C. counting vial

The β ray of electromagnetic radiation absorbs and is converted into photon by scintillator, and photon needs guiding through counting vial and gets to photoelectricity Multiplier tube.And the material of counting vial and its thickness etc. will cause directly to influence on the penetration capacity of photon, to influence survey The detection efficient of amount system.Common counting vial material has polyethylene, polytetrafluoroethylene (PTFE) or the meter containing polytetrafluorethylecoatings coatings Several bottles, low potash glass etc..Table 3 gives the respective advantage and disadvantage of counting vial and its applicable range of above a few money unlike materials. Wherein, table 3 is the comparison table of unlike material counting vial.

Table 3

Counting vial material	Advantage	Disadvantage	The scope of application
				Polyethylene	Detection limit is low, price is low	Poor transparency	High-volume Analysis of environmental samples
Polytetrafluoroethylene (PTFE)	Detection limit is low, transparency is high	Price is high	A small amount of sample, high-acruracy survey
				Low potash glass	Transparency is high	Background count is high	Generally it is chiefly used in14The measurement of C

Tritium automatic analysis method is on the one hand mainly for environment in the water based on RO film sample preparation of the utility model embodiment The analysis application of tritium in water；The automation of tritium analysis overall process in water finally can be achieved in another aspect this method, can be used for large quantities of Measure the analysis of sample.In conjunction with table 3, the utility model embodiment selects the counting vial of polyethylene material, certainly, those skilled in the art Member can select the counting vial of other materials according to actual needs, herein only as an example, being not specifically limited.

2.3.3 count measurement process

As shown in figure 13, water sample after the processing of RO UF membrane sample preparation device purification, is obtaining meeting liquid sudden strain of a muscle measurement The filter liquor of condition.Filter liquor and scintillation solution are injected into counting vial by a certain percentage, screwing bottle cap and fulling shake mixes the two Uniformly and with alcohol swab wiping counting vial outer wall to reduce electrostatic interference.Then sample to be tested is passed to liquid to dodge in spectrometer, by wanting It asks and starts to measure after setting measuring condition.

To sum up, tritium automatic analysis method is in the water based on RO film sample preparation with " RO UF membrane sample preparation+liquid dodges spectrometer and counts survey Amount " is frame.RO membrane separation technique, which is mainly utilized, can carry out quick separating-purifying to water sample processed to reach symbol Close the requirement that liquid dodges measuring condition.Then it selects a kind of suitable liquid to dodge measurement method and count measurement is carried out to sample, with effective Reduce detection limit, to solve existing method presently, there are time for sample pretreatment is too long and measurement detection limit is high asks Topic, the final effective analysis realized to tritium in ambient water.

Above-described embodiment describes the fast automatic analysis method of tritium in water in detail, will pass through another embodiment pair below The fast automatic analysis method of tritium is introduced in water, and in the present embodiment, automatic measurement conductivity uses results of conductivity measurement Control sample crosses film number.

Further, in one embodiment of the utility model, further includes: the conductivity value of detection back segment filter liquor； Judge whether conductivity value is less than default conductivity value；If conductivity value is less than default conductivity value, infused into counting vial Enter the back segment filter liquor of the first preset volume；If conductivity value is more than or equal to default conductivity value, by reverse osmosis Film purification back segment filter liquor again, until conductivity value is less than default conductivity value.

It is understood that it be easy to cause reverse osmosis membrane to block when default conductivity value is arranged higher, and default conductivity When value setting valence is low, the back segment filter for meeting liquid sudden strain of a muscle measurement request can be prepared by needing multipass reverse osmosis membrane purification Liquid out, therefore, those skilled in the art need to need to be arranged the occurrence for presetting conductivity value according to actual use, so as to In the case where guaranteeing to be prepared the back segment filter liquor for meeting liquid sudden strain of a muscle measurement, also effectively control sample crosses reverse osmosis membrane number, To effectively improve the access times of reverse osmosis membrane, cost is reduced.The utility model embodiment is not done specific by taking 5 μ s/cm as an example It limits.

Specifically, below will be to will combine conductivity that RO film sample preparation device comprehensive performance is described in detail.

3.1, the RO film sample preparation device model machine design, produced, what is faced first is following problem: first is that the system The applicable water sample ambit of sampling device, tentatively grasping which kind of water sample is just suitable for carrying out sample preparation using the device；Second is that making Time needed for carrying out one sample of sample size situation and preparation that sample preparation needs to prepare with the device；Third is that the device The problem of with the presence or absence of tritium residual, or when need to consider that tritium residual will cause influence to sample analysis result； Fourth is that the case where RO film sample preparation device service life, substantially grasp the device and need to carry out RO film after preparing how many times sample Replacement.This chapter will be operated from above four problems by a large amount of actual motion, be verified and tentatively be grasped the RO film point Comprehensive performance from sample preparation device provides safeguard for effective operation of entire analysis method.It below will be from the following aspects pair Sample preparation device is further elaborated.

3.2, the applicable water sample range research of sample preparation device

The task of the sample preparation device is to be filtered purification to detected water sample using RO film, and purified water sample meets liquid The count measurement that machine on scintillation solution directly carries out tritium can be added by dodging measuring condition.But it is limited by RO film process water sample ability, Not all water sample is all suitable for being handled with the sample preparation device.Therefore, it is outstanding to grasp the applicable water sample range of the sample preparation device It is important.

For convenient for carrying out effective evaluation to water sample range from the angle of quantization, introducing conductivity and turbidity herein, the two are general It reads.Wherein conductivity is to evaluate the salt content in water sample, important indicator and liquid flashing counting method containing ion and impurity component etc. Can tritium examination final sample be surveyed enter the index that liquid sudden strain of a muscle spectrometer measures.And turbidity be evaluation water in it is various it is inorganic with have The suspended matter of machine is to the obstruction degree of light, and the big water sample of turbidity easily results in blockage and damages to RO film, to seriously affect RO The use of film sample preparation device.

The water sample range test research process being applicable in RO film sample preparation device is as follows:

1) surface water, underground water, the water sources such as enough various environmental water samples, including rivers, reservoir is acquired as required to drink Ground water and rainwater, tap water etc.；

2) measurement of conductivity and turbidity is carried out to the environmental water sample of each acquisition, and records measurement data in detail；

3) it is protection RO film sample preparation device, manual filtering early period is carried out to visually obvious muddy water sample.Method is as follows: adopting With suction type filtering device, the interior bilayer diameter that is laid with carries out the water sample of obvious muddiness for the 102 middling speed type qualitative filter papers of 18cm Early period filters to obtain relatively limpid filtrate.

4) conductivity and turbidimetry are carried out to the opposite clear filtrate after premenstruum (premenstrua) manual filtration again, and recorded in detail Measurement data；

5) enough environmental water samples are accessed into RO film sample preparation device water inlet, according to " automatic sample " of 2.2.3 section description Mode carries out separating-purifying processing to water sample.

6) whether low the measurement for carrying out conductivity after " automatic sample " to obtained filter liquor, observe its conductivity value In 5 μ s/cm.If so, stopping sample preparation and recording the conductivity value of current filtrate；If it is not, " manual mode " is then selected, it is right The environmental water sample carries out multiple " filtering+sample preparation " operation.After obtaining enough filter liquors, filter liquor is carried out again " filtering+ Sample preparation " operation, obtains secondary treatment filtrate, measures and records its conductivity value.

It will be respectively necessary for being listed in respectively through the water sample and its experimental result of RO film sample preparation device single treatment and reprocessing Table 4 and table 5.

Table 4

Table 5

By table 4 and table 5 as it can be seen that the initial conductivity of the environmental water sample for the utility model embodiment is from several μ s/cm To thousands of μ s/cm, conductivity value distribution is relatively extensive, has good representativeness；The turbidity of most environmental water samples All in 1.00NTU hereinafter, only few several visually obvious muddy its turbidity of water sample are greater than 1.00NTU, but by letter Its turbidity value is also all reduced to 1.00NTU or less after single coarse filtration early period.This experimental result is shown: initial conductivity is in Between 6.98~919 μ s/cm, and conductivity is lower than the environmental water sample of 1.00NTU, after RO film sample preparation device single treatment The purpose that filter liquor conductivity is lower than 5 μ s/cm can be realized；And for initial conductivity be in 1124~1744 μ s/cm it Between, after part of turbid water sample premenstruum (premenstrua) coarse filtration processing makes haze reduction to 1.00NTU or less, utilize RO film sample preparation device Need to be handled twice can make filter liquor conductivity be reduced to 5 μ s/cm or less.

In general, primarily determine the RO UF membrane sample preparation device to turbidity lower than 1.00NTU, conductance by this experiment Rate has good treatment effect in 900 μ s/cm environmental water samples below.And by experiment as it can be seen that most of environmental water samples are symbols This requirement is closed, therefore the water sample range that the device is applicable in is satisfactory.Due to limited conditions, this experiment only selects The environmental water sample of Tianjin, sample type and quantity are relatively fewer, also need to acquire more differences in China in next step The environmental water sample of type carries out similar experiment, to further determine that the applicable water sample ambit of the RO film device.

3.3, sample making course consumption sample amount and time-consuming research

3.3.1, sample making course consumes sample amount situation

It is further every to the sample preparation device after tentatively having grasped RO UF membrane sample preparation device and being applicable in water sample ambit The sample size that a sample substantially needs to consume is prepared to be counted and grasped.

Inevitably there is certain pure waste water ratio because of the working mechanism of film itself in RO UF membrane sample preparation device.This Outside, the interference for being the complete sample of pre-treatment that eliminates as much as to sample below, sample preparation device design increase sample water washing ring Section.The sample size of required consumption is bigger when therefore, using device progress water sample processing.Specifically to grasp RO UF membrane The sample size situation of required consumption when sample preparation device handles water sample, herein in the following ways to each water sample of RO film device at Each link water consumption of reason process, wastewater flow rate and production sample amount situation are recorded and are counted:

1) water sample to be processed is filled with the plastic barrel that volume is 25L, then bucket is placed on electronic scale, record the device During processing water sample each link start with finish time electronic scale numerical value, the concrete water quality of each link consumption is obtained through converting；

2) selecting volume is the beaker access of the 10L device in processing each link of water sample process, through discharge outlet 1, draining Mouth 2 and the wastewater flow rate of gap (as shown in Figure 11) discharge, and make a record；

3) selecting volume is the beaker access of the 3L device in processing each link of water sample process, is abandoned liquid mouth (see Figure 11 It is shown) sample size of discharge, and it makes a record.

Secondary processing environment water samples according to said method tens of to the device and the originally water consumption of each link of water sample, discharge waste water Amount and production sample amount are all recorded.The data of record are collated, summarize and be listed in shown in table 6.

Table 6

By upper table data as it can be seen that the process for needing to consume water sample, which concentrates on sample water, rinses and once filter link, and two The concrete water quality of link consumption is substantially suitable；Four processes can all have waste water generation, and the waste water that wherein sample water flushing link is discharged is about For one times or so for once filtering link discharge waste water, the wastewater flow rate that two links of sample preparation and emptying generate is not much different；Sample Generation process occurs in sample preparation link.All in all, this research sample preparation overall process of RO UF membrane sample preparation device consumes Concrete water quality range is 11.0~15.3L, mean consumption 12.9L；The wastewater flow rate range of overall process discharge is 9.5~13.8L, average Waste water 11.4L is discharged；The sample size of generation is fixed on 1.5L, generally takes the 100ml of latter end or so sample stand-by.Accordingly, it is proposed that When prepared by the water sample for carrying out tritium analysis in water using the device, for the sake of insurance, the water sample for preparing 16L or so is to compare conjunction Suitable.

It should be noted that being the case where only needing RO film device single treatment above.When encountering at special needs repeat The sample of reason is needed on this basis if the higher water samples of initial conductivity some in table 3.2 using " manual " sample preparation mode, weight Multiple 3~4 " primary filtering+sample preparation " links are to collect enough pure water through device single treatment.Then by device water inlet In the above pure water collected of merging, then 1 " primary filtering+sample preparation+emptying " link is carried out, water sample can be made to meet measurement and wanted It asks.So need the concrete water quality consumed and will increase to 32~39L or so.

3.3.2, sample making course time-consuming situation

Tritium analysis method all has that sample preparation procedure takes long time in existing water.It forgoing describes using biography The alkali formula electrolytic enrichment method sample preparation of system need to consume a week even more than ten days time；Electrolytic enrichment device after improvement It needs one day time-consuming or more；And time-consuming is needed at least because saving the air-distillation sample preparation method that electrolytic enrichment process is greatlied simplify It 2~3 hours, is distilled if you need to repeat, then spent time will be increased to 12~16 hours or so.The base of the utility model embodiment Water sample is purified by film filtering in the sample preparation device of RO UF membrane, advantage should be theoretically had more in time-consuming.

The time situation of required consumption when to grasp RO UF membrane sample preparation device processing sample, herein to entire research process In the tens of secondary water sample treatment processes of the device recorded in the time-consuming situation of each link, the data of record are collated, summarize It is listed in shown in table 7.

Table 7

The above experimental result is shown, when carrying out water sample processing using the RO UF membrane sample preparation device, entire treatment process institute Time-consuming range is 35~52 minutes, and average time-consuming needs 41 minutes.It is wherein time-consuming longest for sample water flushing link, the link Spent time accounts for 60% or more of entire sample making course.Specific each link time-consuming situation approximately as: sample water flushing link is time-consuming It is range 19~40 minutes, average 26 minutes time-consuming；Primary filtering link time-consuming range 3~12 minutes, it is average 5 minutes time-consuming；System It is sample link time-consuming range 4~7 minutes, average 5 minutes time-consuming；Last emptying link time-consuming range 3~6 minutes, average time-consuming 5 Minute.

It equally, is the case where only needing RO film sample preparation device single treatment above.The sample that special needs are reprocessed Product, need on this basis utilize " manual " mode increase by 3~4 times " primary filtering+sample preparation " operation and 1 time " once filter+ Sample preparation+emptying " operation, required time increase accordingly by 85~95 minutes or so.

By conclusions as it can be seen that the sample preparation device based on RO UF membrane the studied herein sample preparation that tritium is analyzed in water For process compares the method for making sample that tritium is analyzed in existing water, have a clear superiority in spent time.

3.4, the research of RO film sample preparation device tritium remaining influence

The problem of inevitably bringing contamination using RO UF membrane sample preparation device, i.e. sample are through the filtering point of RO film device After purification, the impurity in the sample, which inevitably understands some, can be stopped in the device, after next sample enters the device, A part of impurity stopped before in the device may can be mixed into the sample to pollute it.And the tritium in water is very This process may be participated in, this will cause directly to influence on the analysis result of tritium in sample.

In this regard, the RO UF membrane sample preparation device that this research uses devises the sample water cleaning procedure of long period.It is expected that leading to The interference of sample carryover impurity before in excessive bulk, prolonged sample water flushed zone walking apparatus.To verify having for this measure Effect property, grasps the anti-tritium remaining influence ability of the RO UF membrane sample preparation device, has carried out tritium residue test below herein.

1) laboratory originally water sample tritium analysis measurement

" automatic sample " mode is selected using RO UF membrane sample preparation device, originally water sample is filtered at purification to laboratory Reason.It takes latter end filter liquor of the 50ml conductivity lower than 5 μ s/cm to contain in 100ml counting vial, 50ml flashing is then injected into bottle Liquid, counting vial, which fullys shake, to be uniformly mixed the two and wipes bottle outer wall with alcohol swab.Then sample to be tested merging liquid is dodged into spectrum In instrument and suitable time of measuring is set, after standing in spectrometer after sample, being protected from light 12 hours, starts to measure and record measurement knot Fruit.

Repeat above step, prepare three laboratories originally water sample and carry out tritium counting rate measurement, measurement result is made For tritium counting rate horizontal reference value in this laboratory tap water.Measurement data is shown in Table 8.

Table 8

Sample number into spectrum	Time of measuring (min)	ESCR value	Counting rate (cpm)
				Tap water 1	1000	11.22	4.243
Tap water 2	1000	11.21	4.402
				Tap water 3	1000	11.24	4.397
Average value			4.347

2) configuration of tritium mark-on sample

The laboratory tap water that electronic scale weighs 20kg is contained spare in 25L bucket.The liquid-transfering gun for the use of range being 1mL The tritium standard solution that 0.2mL initial concentration is 1009Bq/g is pipetted, then weighs up this using the electronic balance that precision is 0.1mg The tritium standard solution quality pipetted is 0.2002g.Both make in spare tap water before weighed tritium standard solution is poured into It is sufficiently mixed the tritium mark-on sample for being configured to that tritium concentration is about 10Bq/L.

3) the tritium retention analysis measurement of mark-on sample

By method in step 1), using RO UF membrane sample preparation device, it is about to configured tritium concentration in 2) step first The mark-on sample of 10Bq/L is handled and is prepared into mark-on sample to be measured, then continuously prepares multiple laboratories originally water sample, successively Number is C₁、C₂、C₃... all liquid that are placed in together to test sample prepared are finally dodged progress tritium counting rate survey in spectrometer by .. It measures and records measurement result.

4) the tritium retention analysis measurement of various concentration tritium mark-on sample

By step 2), 3) in method, configuring in order tritium concentration is about 50Bq/L and the mark-on sample of 100Bq/L, is then carried out Sample preparation and tritium residue test measure, and record to test result.This time tritium residue test the results are shown in Table shown in 9.

Table 9

Above-mentioned test result is shown: the RO UF membrane sample preparation device is handling the mark-on sample that tritium concentration is about 10Bq/L Afterwards, originally the tritium counting rate of water sample is referred to laboratory tap water tritium counting rate in table 3.5 in continuous 4 laboratories immediately after Value is suitable.And after having handled tritium concentration and being about 50Bq/L and the mark-on sample of 100Bq/L, preceding several laboratories immediately after are certainly Carrying out the tritium counting rate of water sample, than before there is the phenomenon that increasing in laboratory tap water tritium counting rate reference value, until the 3rd or the 4th Its tritium counting rate of a sample is horizontal before being just gradually restored to.

Accordingly, it can tentatively be concluded that for water sample of the tritium concentration lower than 10Bq/L, use the RO film It separates after sample preparation device carries out water sample processing, without considering the influence because of device tritium residue problem to sample handled by later；But When the tritium concentration of water sample processed is higher than 10Bq/L, tritium residue problem should arouse attention.Specific influence degree optionally and It is fixed, it is generally available the ambient water of tritium counting rate level known to locality or the multiple sample preparation of tap water is rinsed, until what is be processed works as The tritium counting rate of ground ambient water or tap water is restored to initial level, which can continue investment normal use.

For normal environmental water sample, tritium concentration is substantially all in 10Bq/L hereinafter, therefore using the RO film point When from sample preparation device processing environment water sample, the remaining influence of sample preparation device tritium can be ignored substantially.

3.5, RO film sample preparation device service life case study

The service life of device is an important technical indicator, for non-disposable use equipment, even if it makes With process again facilitate, other performance it is superior again, if service life is too short, which is also difficult to be promoted the use of.Therefore, understand Service life situation of the RO UF membrane sample preparation device for tritium analysis sample making course in water, makes the popularization of this method next step With particularly significant.

For RO UF membrane sample preparation device, the part for being used for deciding factor from the service life is RO film.With The increase of RO film process concrete water quality, the surface of film by gradually by the impurity in water block or because friction effect, film surface quilt Impurities in water damage, eventually leading to the device reduces the detergent power of water.When use, the device carries out water sample processing, acquisition Filter liquor is difficult to realize conductivity lower than 5 μ s/cm, thus when no longer meet that tritium analyzes measurement request in water, it is necessary to it is right RO film in device is replaced.

Before this research experiment, device research staff is being designed the RO UF membrane sample preparation device and limber up period Between, the originally water sample processing test (be wherein no lack of plus the originally water sample of salt is tested) up to more than 40 times had once been carried out to it.Debugging After, in the case where no replacement RO film, using the device, to the environmental water sample of acquisition and originally, water sample has carried out this Research experiment.In experimentation, complete water sample per treatment to RO film device has all carried out measurement and the record of conductivity, and according to The trend that this conductivity for delineating sample prepared by the device prepares the variation of sample number with it is as shown in figure 14.It is horizontal in figure Coordinate is this research experiment sample preparation number, and ordinate is the conductivity value for having prepared sample.

As seen from Figure 14, generally speaking with the increase of RO UF membrane sample preparation device processing sample number, after processing The trend slowly risen is presented in water sample conductivity.There is obvious liter in the conductivity of wherein the 17th time, 27 times, 31 times processing water sample High situation, being checked, this increases the first of the underground water, drinking water source 5 and the river 1 that are corresponding in turn in table 5 extremely three times Secondary processing result, it is seen that this abnormal increase is excessively high caused by water sample initial conductivity processed.Since the 33rd time, it What the conductivity of continuous 4 water samples was all stable afterwards is maintained at 6 μ s/cm or more, through looking into, this 4 water samples be use for laboratory originally Water.Therefore, it can be confirmed that the RO film process concrete water quality has reached its own limit value, it need to be replaced.

So far, which designs more than 40 originally water sample processing and this experimental stage in debugging stage before it experienced More than 30 environmental water samples and originally water sample processing after, reached it and used the phase in longevity.It should be pointed out that RO film makes Be with the service life with the water sample water quality that it is handled it is directly related, the water sample water quality of RO film process is better, service life also will more It is long.

RO film used is this time tested, it includes due to adding salt that front and back completes more than 70 water sample preparations altogether among these The originally water sample and the higher environmental water sample of self-conductance rate for having high conductivity.It is ensured that ensuring to enter RO film The water sample of sample preparation device is meeting under the applicable environmental water sample range of condition of the device, which analyzes sample preparation for tritium in water Service life will be not less than 70 times.

To sum up, by the above experimental study, the RO UF membrane sample preparation device is tentatively grasped for tritium analysis sample preparation in water The comprehensive performance parameter of journey is as follows: 1. the device is lower than 1.00NTU to turbidity, and initial conductivity is in 900 μ s/cm environment below Water sample has good treatment effect, only needs single treatment that can complete sample preparation；2. handle such environmental water sample using the device The sample size needed is relatively large, need to averagely consume sample about 13L, for the sake of assurance, it is proposed for preparing water sample before each sample preparation 16L or so；3. spent time is average when handling such environmental water sample using the device only needs 40 minutes or so, in existing water Tritium analysis method is compared and is had a clear superiority；4. the device is when processing meets the environmental water sample of conditions above, the use of device Service life is not less than 70 times；5. when processing environment water sample normal using the device, without considering between the sample of front and back because tritium is remaining Problem has an impact analysis result, but after processing complete has the water sample of higher tritium concentration (10Bq/L or more), tritium residual is asked Topic need to arouse attention.

Further, the optimization of determination and measuring condition to measurement method is described in detail below.

4.1, two conflicting problems that tritium analysis work mainly faces in current water have been previously noted: or before sample The treatment process used time is too long or detection limit is excessively high.The 3rd chapter has been verified that the system based on RO UF membrane of this time research herein Quadrat method can be such that the sample pretreatment process used time greatly shortens.How this chapter will make under detection from the angle research of count measurement Limit the method being effectively reduced.

The detection limit calculation formula of tritium is as follows:

In formula: N_bIndicate background sample counting rate, min^-1；

E indicates detection efficient, %；

V indicates sample amount, ml；

t_bIndicate the time of measuring of this original pattern, min；

By above formula as it can be seen that the principal element for influencing detection limit has following two in the case where detection system determines relatively Point: first is that the influence of measurement method, such as sample size number, quenching correction method determination；Second is that the selection of background water And its length of time of measuring.In addition, also needing to consider to carry out measuring condition excellent in the case where the above parameters all determine Change, such as stands the optimization for being protected from light the time before the optimization of energy window, the optimization of water sample and scintillation solution proportion, sample measurement.

In the following, the discussion that will conduct a research respectively in terms of above-mentioned two, to determine that one kind is suitable for based on RO film The liquid for separating sample preparation dodges measurement method and optimal count measurement condition.

4.2, the determination of measurement method

4.2.1 the selection of sample size

By formula 1 as it can be seen that the number of sample amount will cause to directly affect to detection limit.It is determined in counting vial capacity In the case where constant, the change of sample size this means that scintillation solution volume change, and scintillation solution is excessive or very few, is all not suitable for In the measurement of sample.Experience have shown that the volume ratio of sample and scintillation solution is between 8:12 and 10 for the counting vial of 20ml capacity: It is than convenient between 10.But the sample volume variation in this range influences the change of detection limit little.

Therefore, it is necessary to break through the limitation of counting vial total capacity.Theoretically, sample size is bigger, the detection limit value of acquisition It will be lower.In the case where ensuring sample and scintillation solution suitable proportion, with the increase of counting vial capacity, sample size also increases therewith Add, but background counting rate N_bAnd the detection efficient E of instrument tritium also will change therewith, and the range changed is unclear, Want to show that detection limit is relatively difficult with the increased detailed situation of change of sample size by theoretical calculation.So only passing through reality Suitable sample size is found in border measurement.

It forgoing describes LB7 type Low background liquid and dodges the counting vial that spectrometer has tri- kinds of different capabilities of 20ml, 100ml, 145ml Measure function.Here, we first select 20lm and 100ml capacity counting vial to carry out the control experiment of detection limit, experimental procedure It is as follows:

1) it selects two sets of identical laboratory atmospheric distillation plants to same a collection of background water, is carried out according to standard practice Air-distillation.Distillation process is preferably slow, in order to which single flash can obtain the distillate that conductivity is lower than 5 μ s/cm.

2) the qualified distillate that the distillation of two covering devices obtains is mixed, total 130ml.Then four are divided into liquid-transfering gun Part, wherein two parts of 10ml are respectively charged into 20ml capacity counting vial, two parts of 50ml are respectively charged into 100ml capacity counting vial.It is surplus Remaining distillate discards；

3) distillate for respectively selecting portion 10ml and 50ml is added suitable tritium standard solution configuration thereto respectively and survives Similar tritium standard specimen is spent, another set distillate is as this original pattern；

4) it sequentially adds into four counting vials and is flashed with the isometric Ultima Gold u LLT type of contained distillate Liquid carries out sample mark with signature pen after screwing bottle cap on bottle cap, and concussion is allowed to uniformly mixed；

5) after alcohol wipe outer wall, sample is put into LB7 Low background liquid and dodges spectrometer.All by the time of measuring of all samples It is set as 100 minute/time of single measurement, duplicate measurements 11 times.After sample stands in spectrometer and is protected from light 12 hours, that is, carry out tritium meter Number measurement, measurement result, which is computed, arranges rank rear in table 10.

Table 10

Table 10 shows that the corresponding detection limit of 20ml capacity counting vial is in 1Bq/L or more, the detection of 100ml capacity counting vial Lower limit is lower than 0.4Bq/L.

According to " Chinese quality of radioactive environment report in 2016 " and " state key supervision cores in 2016 and radiating facility week Enclose the report of radiation environment supervisory monitoring ", tritium concentration range is 0.28~2.7Bq/L in the Some City precipitation of China in 2016, The tritium concentration of most precipitation is in 1Bq/L or so；It is 0.41 that tritium concentration range in point dewatering is compareed around most of nuclear power ~2.7Bq/L.There is data to show, the source of China's environment surface water, the water such as Ru Jiang, river and reservoir is derived mainly from precipitation.

Therefore, 100ml capacity counting vial measurement pattern of the detection limit lower than 0.4Bq/L is can satisfy substantially to China's ring The requirement that tritium is effectively analyzed in the water of border；20ml capacity counting vial measurement pattern is because detection limit is too high, in 1Bq/L or more, Therefore it should not select；If predictably selecting the counting vial of 145ml capacity, detection limit can be further decreased, but be counted The increase of several bottles of capacity also brings along the problem of scintillation solution dosage increase, and scintillation solution is toxic and reluctant.Therefore, comprehensive It closes and considers, selecting applicable 100ml capacity counting vial measurement pattern is that comparison is reasonable.

4.2.2 the selection of Quench Correction Methods

Quenching is to influence one of the maximum interference factor of liquid flashing counting measurement result.Strictly, sample is different, quenches journey Degree is different, and measurement efficiency is not also identical.The basic goal of quenching correction is the liquid flashing counting measurement efficiency of determining sample, Thus detection limit value is affected indirectly whether quenching calibration accuracy.There are many available Quench Correction Methods, such as: internal standard method, External standard method, sample channels ratio(SCR) method, sample Spectral index method, isotope quenching method etc..It is mainly internal standard method that utilization rate is highest at present, outer Mark method and relative measurement method.

A. internal standard method

Internal standard method begins to be applied to Tritium measure process very early, and substantially steps are as follows: sample being placed in liquid first It dodges in spectrometer and measures, the tritium standard liquid of known activity is added after measurement in sample, and measure again.By measuring again As a result the known activity that tritium standard liquid is added is combined, measurement efficiency can be obtained by being computed, which is that can be considered the survey of sample Amount efficiency.The variation of quenching degree can be ignored before and after this method requires sample that tritium standard liquid is added, therefore it is required that The concentration of tritium standard liquid is higher, and the volume change that standard liquid front and back sample is added is little.

B. external standard method

External standard method is relatively complicated, it is to dodge gamma ray radiator built-in in spectrometer using liquid to shine sample It penetrates, obtains a Compton scattering spectrum, the different sample of quenching degree, distribution of the Compton scattering spectrum in multiple tracks is different, I.e. road ratio is different, this road ratio is the quenching degree for reflecting sample, can be referred to as quenching coefficient.Principle accordingly, can The tritium standard specimen of the different known activity of one group of quenching degree of configured in advance, available one group of quenching system after liquid dodges spectrometer measurement The data of the corresponding measurement efficiency of number, become required Quench correction curve after being fitted.When measuring sample later, it is known that its Quenching coefficient can obtain its measurement efficiency according to the Quench correction curve of fitting.There is configured quenching series source in external standard method The problem whether being applicable in sample to be tested, and the configuration process for quenching serial source is relatively cumbersome.

C. relative measurement method

Relative measurement method is similar with internal standard method from principle, the difference is that this method does not need to add sample The measurement twice of front and back is marked, but is prepared using identical method for making sample to test sample, this original pattern and standard sample, then will Three is placed in liquid together and dodges count measurement in spectrometer.Since sample preparation methods are identical, it is believed that the quenching degree one of three It causes, therefore the detection efficient of the standard sample of known activity is the detection efficient to test sample.This method is at present in radiation environment It is widely adopted in monitoring.

Comprehensively consider, relative measurement method is selected to carry out the quenching correction of sample herein.To ensure to test sample and this original pattern, mark The quenching degree of quasi- sample is consistent, and is obtained in advance with the source the γ irradiation built in spectrometer to test sample, this original pattern and standard sample The quenching coefficient of three.Theoretically, when the quenching coefficient similar of sample, they dodge the counting on spectrometer in same liquid Efficiency should also be similar, there is pertinent literature^[24,25]Verifying was carried out to this theory by up to a hundred actual measurements.

Using same method multiple tritium standard specimens are carried out with the experiment of quenching coefficient and the measurement of tritium counting rate herein, then According to resulting tritium standard specimen counting rate is measured, it is computed and show that it measures activity, the practical activity in conjunction with known to tritium standard specimen Obtain the counting efficiency of different tritium standard specimens.Experimental result is shown in Table shown in 11.

Table 11

By table 11 as it can be seen that the tritium standard specimen of different activity, as long as quenching coefficient similar, their counting efficiency difference would not It is too big.The reliability of the quenching correction method of relative measurement is demonstrated again.

4.3, the determination of background water and sample-out count time

4.3.1 the selection of background water

Being related to nuclear activity by the mankind is influenced, and real tritium-free water is seldom even not present in global range at present.And this Bottom water has direct influence to sample final measurement and detection limit, therefore particularly significant.In actual measurement, Wo Menchang Select the alap environmental water sample of tritium counting rate convenient for obtaining as background water sample.

To select suitable background water sample, once to certain two provincial radiation stations background water sample and Tianjin two at Sampling of ground water carries out the measurement of tritium counting rate, and measurement result is shown in Table 12.

Table 12

It is shown according to table 12, the minimum background water sample for radiation station 2 of tritium count rate measurement, is secondly Tianjin underground Water 2, and the two measurement result is not much different.In view of the comfort level that water sample obtains, Tianjin underground water 2 is had finally chosen Background water sample as the analysis of this laboratory tritium.

4.3.2, the selection of sample-out count time

Formula 1 is as it can be seen that the time of measuring of this original pattern constitutes direct influence to detection limit.When this original pattern counting rate is stablized Afterwards, with the extension of time of measuring, background counting rate is relatively constant, and detection efficient is also relatively constant, and sample volume and background Time of measuring is unrelated.So, it is believed that sample-out count time and detection limit are at evolution inverse relation.Theoretically obtain, this Bottom time of measuring can change detection limit, but it is limited to change ability.

Tritium analysis requires at 1000 minutes or more the time of measuring of this original pattern in general current water.Comprehensively consider, herein This original pattern time of measuring is set as 1000 minutes by selection.

4.4, the optimization of measuring condition

After measurement method determines, measurement result can need to be caused centainly on the basis of the measurement method to some The measuring condition of influence optimizes.Such as the optimization of the optimization of energy meter number interval, water sample and scintillation solution proportion and to test sample Product stand the optimization etc. for being protected from light the time.

4.4.1, the optimization of energy meter number interval

The variation of energy meter number interval to a certain extent can impact detection limit, for reasonable selection energy meter For number interval to improve detection limit as far as possible, spy introduces the concept of quality factor (FOM).People are by Liquid Scintillation Count Efficiency Square quality factor is defined as with the ratio of background counting rate^[26].For specific sample, when quality factor takes most When big value, the optimal selection of its energy meter number interval is corresponded to.Quality factor formula is as shown in Equation 2:

In formula: N_bIndicate background counting rate, min^-1；

E indicates that detection efficient, calculation formula are as shown in formula 3:

In formula: N_sIndicate standard sample counting rate, min^-1；

D indicate standard sample in per minute tritium decays, min^-1。

For the maximum value for finding and determining quality factor, following experiment has been carried out:

1) take high purity water of the 50ml conductivity less than 5 μ s/cm and 50ml Ultima Gold u LLT type scintillation solution in Sample to be tested is made after concussion mixes them thoroughly in 100ml polyethylene counting vial；

2) it is put into LB7 type liquid after wiping counting vial outer wall with alcohol swab to dodge in spectrometer, sets 100 for time of measuring Minute/time, duplicate measurements 11 times, correction method selects " ESCR ".After sample standing is protected from light 12 hours, start to measure.By this Measurement result is as background values；

3) after sample-out count, sample is taken out, the tritium standard solution that activity is 197Bq is wherein being added, is being shaken through concussion It is even that tritium standard specimen is made；

4) the tritium standard specimen counting vial outer wall made of alcohol swab wiping previous step, is then put into LB7 type liquid and dodges spectrometer In, 10 minutes/time are set by time of measuring, duplicate measurements 11 times, correction method selects " ESCR ".12 are protected from light to sample standing After hour, start to measure.

Figure 15 and Figure 16 is respectively that background spectrum and standard specimen compose spectrogram.

LB7 type liquid dodges the entire window energy range of spectrometer Tritium measure by 0 to 200keV, is divided into 4000, per together Corresponding energy 0.05keV.Correctly to find and determining optimal energy meter number interval, need to count peak it is high and low can both ends by Secondary card road records the tritium counting rate of every secondary card road corresponding standard specimen and background, is then calculated every time using formula 2 and formula 3 The corresponding FOM value in card road.The maximum value of FOM is found, energy section corresponding to card road is optimal energy meter number interval. The FOM Data-Statistics situation of each energy meter number interval is shown in Table 13.

Table 13

Upper table is shown, when energy meter number interval takes 1.00~4.70keV, it is 142.42 that maximum value, which occurs, in quality factor, Corresponding detection limit is also minimum, is 0.4107Bq/L.Thereby determine that the energy window that the liquid is dodged spectrometer Tritium measure is set as 1.00~4.70keV.

Spectrometer parameter setting method is as follows: selecting " other (FREE) " first in the nucleic column of the primary condition page, so The minimum (L.L.) of power spectrum window is set as 1.000 in the FREE power spectrum window setting of the measuring condition page afterwards, highest limit (U.L.) 4.700 are set as, " ok " is clicked and saves setting.

4.4.2 the optimization of water sample and scintillation solution proportion

Suitable water sample and scintillation solution matches, and is more advantageous to the effective analysis for realizing tritium in water.To find optimal water sample With scintillation solution volume proportion, the concept of sensitivity figure of merit SFOM, the sensitivity figure of merit are further introduced on the basis of quality factor For the product of quality factor and sample volume square.

In formula: V indicates the volume of detected water sample, ml；Remaining parameter meaning is identical as formula 2,3.

Optimal sample volume is corresponded to when SFOM is maximized, i.e., optimal water sample and scintillation solution match ratio.For Maximum SFOM value is found, is proceeded as follows:

1) use high purity water as detected water sample, by it with Ultima Gold u LLT type scintillation solution respectively according to 70:30, The volume proportion of 65:35,60:40,55:45,50:50,45:55,40:60,35:65,30:70 are packed into 100ml polyethylene and count In bottle, after concussion shakes up, the sample to be tested of one group of difference sample and scintillation solution proportion is made.

2) all of above sample to be tested counting vial outer wall is wiped to eliminate electrostatic interference with alcohol swab, then successively put it Enter LB7 type liquid to dodge in spectrometer.100 minutes/time are set by measuring condition, duplicate measurements 11 times, correction method selects " ESCR ", After sample stands in spectrometer and is protected from light 12 hours, start to measure, measures the data obtained as background values；

3) it is taken out after sample measurement, the tritium that about 0.2g initial concentration is 1009Bq/g is successively added in each sample Standard solution, concussion shake up rear to be measured；

4) with alcohol swab wipe outer wall after place a sample into again liquid dodge spectrometer in, except by time of measuring be changed to 10 minutes/ Secondly, being consistent in other measuring conditions and 2) step.This time measurement data is mark-on sample measured value；

5) it arranges and measures the data obtained twice, it is corresponding with scintillation solution proportion that different water samples are calculated via correlation formula Detection efficient and SFOM value, are listed in table 14.

Table 14

According to table 14, the trend that sensitivity figure of merit SFOM changes with sample and scintillation solution proportion and changed is drawn out, is such as schemed Shown in 17.

It is above-mentioned the results showed that 1. with the decline of water sample and scintillation solution proportion ratio, the ESCR value of matched sample with Raising, i.e. the quenching degree of sample reducing.But the ESCR value variation before and after same sample mark-on is less, illustrates sample mark-on The quenching degree of front and back is substantially suitable, ensure that the consistency of detection efficient before and after same sample mark-on；2. the detection of sample is imitated Rate matches the decline of ratio with scintillation solution with water sample and gradually rises, this is because the increase of scintillation solution volume, leads to detected sample The light conversion ratio of product increases, and the received optical signal of photomultiplier tube increases, so that detection efficient increases；3. the sensitivity figure of merit SFOM is in downward trend after first rising with the decline of water sample and scintillation solution proportion ratio, this is because with the reduction of water sample, Detection efficient dramatically increases, and background counting rate is relatively stable, thus SFOM value increases.Later, water sample is further reduced, detection Efficiency increase slows down, and when the contribution that detection efficient increases is not enough to make up the contribution of volume of water sample reduction, SFOM value is It is on a declining curve.Figure 17 intuitively shows this variation tendency, and clearly shows that in sample and scintillation solution proportion be 50: SFOM value is maximum when 50.Accordingly, it is determined that the experiment measurement part of this research selects the water sample and scintillation solution of 50:50 Proportion mode.

4.4.3 it stands and is protected from light and the optimization of time of measuring

Rigid configured sample generally requires the standing of a period of time before measuring and is protected from light processing, this is because if surveying immediately Amount, measured result are often bigger than normal.The reason of causing this phenomenon is the rigid configured sample mistake stable there are a quenching Journey is generally protected from light to eliminate this influence by standing.But specific stand is protected from light the time currently without final conclusion, most of provincial The selection of Radiation monitoring mechanism laboratory is protected from light 12 hours even 24 hours.Also there is document suggestion sample lower for tritium concentration quiet It sets and is protected from light 6 hours or more the measurement that is just available on the machine, and sample higher for tritium concentration, then the time is protected from light without too long of standing.

To determine that the standing for being suitable for this research method is protected from light the time, promotes this method tritium and analyze working efficiency, carry out Following experiment:

1) production and measurement of this original pattern: fresh background water sample is acquired, is distilled with atmospheric distillation, takes middle section Distillate 50ml of the conductivity lower than 5 μ s/cm is added in 100ml counting vial, and 50ml scintillation solution is then added, and concussion, which shakes up, to be used in combination After alcohol wipe counting vial outer wall, it is immediately placed in liquid sudden strain of a muscle spectrometer and starts to measure, time of measuring is 100 minutes/time, duplicate measurements 18 times.It is as shown in figure 18 that each measurement result with time of measuring situation of change is depicted as column diagram；

2) production and measurement of environmental water sample: selecting a certain environmental water sample, using with the identical method of step 1) into Row sample preparation and measurement.Measurement result is as shown in figure 19 with time of measuring variation column diagram；

3) production and measurement of mark-on sample: this original pattern is made by step 1) first, is then injected thereto a certain amount of Tritium titer, be configured to the mark-on sample that concentration is about 100Bq/L, be put into after wiping liquid dodge spectrometer in immediately begin to measure, Time of measuring be 60 minutes/time, duplicate measurements 24 times.Measurement result is as shown in figure 20 with time of measuring variation column diagram.

Figure 18, Figure 19 show that sample meter early period digit rate is higher, but over time, counting rate gradually under Drop, final entirety tend towards stability.The difference is that counting rate, which reaches, stablizes required time difference.The extremely low background of tritium concentration Sample, after about 500 minutes, counting rate tends towards stability；The lower environment sample of tritium concentration, after about 300 minutes, counting rate is It tends towards stability.And as seen from Figure 20, the higher mark-on sample (about 100Bq/L) of tritium concentration, counting rate tends towards stability at the beginning of measurement, It is protected from light substantially without standing.Whether it is every to dodge spectrometer using LB7 type liquid in addition, recognizing that sample is stood by experiment usually or not There is obvious higher phenomenon in the ESCR value of first data of secondary measurement, usually do first measurement data give up thus Processing.

In consideration of it, in conjunction with this research select relative measurement Quench Correction Methods the characteristics of, use the research method When carrying out sample measurement, after test sample configures and finishes, can successively it be set by standard sample (about 100Bq/L), to test sample, this original pattern Enter liquid to dodge spectrometer and measure immediately.Wherein, the time of measuring suggestion of standard sample is set as 60 minutes/time, and duplicate measurements 11 times；To The time of measuring suggestion of test sample and this original pattern is set as 100 minutes/time, and duplicate measurements 11 times.Data handling procedure, each sample First measurement data be not included in statistics calculating process.Whole process is protected from light processing without deliberately standing.

To sum up, by the above experimental study, the liquid flashing counting measurement method for being suitable for this research method and measurement item are determined Part is as follows: 1. for detection limit is effectively reduced, selecting the measurement pattern of 100ml capacity counting vial and the quenching school of relative measurement Correction method is that comparison is reasonable；2. selection convenient for acquisition and relatively low my the unit laboratory of counting rate at present Tianjin A certain underground water is set as 1000 minutes as background water sample, all original pattern time of measuring；3. in terms of the optimization of measuring condition, Select the energy meter number interval of 1.00~4.70keV；Water sample and scintillation solution press the volume proportion of 50:50；When count measurement, it is not necessarily to It specially stands and is protected from light, liquid can be sequentially placed in by standard sample (about 100Bq/L), to test sample, this original pattern and dodges spectrometer and measures immediately, The time of measuring of Plays sample is set as 60 minutes/time, and duplicate measurements 11 times；Time of measuring to test sample and this original pattern is respectively provided with For 100 minutes/time, duplicate measurements 11 times, first measurement data of each sample is not included in statistics calculating process.

The fast automatic analysis method of tritium in water will be further elaborated by way of specific embodiment below.

5.1 above-described embodiments are carried out to RO UF membrane sample preparation device comprehensive performance and liquid flashing counting measurement method and condition Research determines and optimization, ultimately forms and the relatively complete of tritium automatic analysis method in the water based on RO film sample preparation has been determined Frame system.

The purpose of any analysis method, be finally provided to obtain it is accurate, reliably analyze measurement result.In order to originally grinding Study carefully method in water tritium analysis result on accuracy verified, this chapter by using method compare by the way of respectively to different The mark-on sample of environmental water sample and various concentration carries out the matching measurement of tritium, and by analyzing comparison result, determination is originally ground It is whether accurate in measurement result to study carefully method.

5.2 Experimental comparison

5.2.1 comparison method

In the water based on RO film sample preparation of the utility model embodiment tritium automatic analysis method compared to existing method and Speech, one of main feature are RO film sample making course.And measurement process has then still continued to use liquid and has dodged measuring technique, although in order to Detection limit is reduced, although with the counting vial of 100ml capacity instead of currently used 20ml capacity counting vial, it is entire to measure Process is without too big change.In order to guarantee the comparativity of experimental result, this time comparing will set about from sample preparation link, adopt respectively Various environmental water samples and various concentration are added with two kinds of method for making sample of RO UF membrane of currently used air-distillation and this research Standard specimen carries out sample preparation, and the liquid then determined using this dodges measurement method from condition to two kinds of different method for making sample systems Standby sample measures comparison.

A. air-distillation sample preparation

Air-distillation sample preparation operating process approximately as:

1) potassium permanganate for weighing 0.25g or so natrium carbonicum calcinatum and 0.125g or so in the balance, sequentially adds 500ml's In distilling flask, the detected water sample of about 300ml is injected into bottle, and ground glass stopper is covered tightly after shaking up and is connect with serpentine condenser It is good, it opens electrothermal furnace and controls temperature, distill the sample in distilling flask slowly in the case where not boiling acutely；

2) conductivity for collecting about 70ml is spare lower than the middle section distillate of 5 μ s/cm, needs if conductivity is higher than 5 μ s/cm It repeatedly collects enough distillates and carries out second distillation, until conductivity lower than until 5 μ s/cm；

3) liquid-transfering gun for being 10ml with range pipettes the spare distillate injection 100ml polyethylene of 50ml in five times and counts In bottle, 50ml Ultima Gold u LLT type scintillation solution is then added, concussion, which shakes up, is made sample to be tested；

4) fresh background water is acquired, 1) manufactures two samples to the process of 3) step in the method, wherein a sample It being added in product and passes through diluted tritium titer, concussion is configured to the tritium standard sample that tritium activity is about 5Bq or so after shaking up, another Not plus the sample of tritium standard liquid is as this original pattern.

B.RO UF membrane sample preparation

RO UF membrane sample preparation operating process approximately as:

1) water sample (about 16L) for acquiring enough volumes is connected in the water inlet merging sample water of RO UF membrane sample preparation device Installation's power source clicks " starting " at " automatic mode " interface, and sample preparation device starts to be filtered water sample purification；

2) about 70ml filter liquor is taken out from sample tap after to be filtered and measures conductivity, if its conductivity is lower than 5 μ s/ Cm is then retained for use, if its conductivity is higher than 5 μ s/cm, enough filter liquors need to be collected from sample tap and carry out film again Filtration treatment is lower than 5 μ s/cm until the conductivity of final filter liquor；

3) liquid-transfering gun for being 10ml with range pipettes the spare filter liquor injection 100ml polyethylene of 50ml in five times and counts In bottle, 50ml Ultima Gold u LLT type scintillation solution is then added, concussion, which shakes up, is made sample to be tested；

4) 1) the fresh background water sample for acquiring enough volumes, manufactures two samples, In to the process of 3) step in the method It is added in one of sample and passes through diluted tritium titer, concussion is configured to the tritium mark that tritium activity is about 5Bq or so after shaking up Quasi- sample, another does not add the sample of tritium standard liquid as this original pattern.

It should be noted is that regardless of with which kind of method sample preparation, this original pattern and standard sample all be can be reused. In measurement process, as long as keeping normal relatively stable at the beginning of the quenching coefficient and counting rate of the two and sample preparation, they are can ?.Until measurement finds that quenching coefficient or counting rate occurs significant change, just needs to prepare again.

C. liquid dodges measurement and compares

After the completion of sample preparation, carry out matching measurement according to the following steps:

1) with the counting vial outer wall of the above prepared two groups of samples of alcohol swab wiping to eliminate electrostatic interference, then by two A standard sample, two to test sample, two this original patterns sequentially simultaneously be placed in LB7 type Low background liquid dodge spectrometer in；

2) the Tritium measure window of spectrometer is set as to the energy meter number interval of 1.00~4.70keV；When the measurement of standard sample Between be set as 60 minutes/time, the time of measuring to test sample and this original pattern is set as 100 minutes/time, each sample duplicate measurements 11 Secondary, correction method selects then " ESCR ", then starts to measure.First measurement data of each sample is not included in calculating process.

5.2.2, environmental water sample ratio

Comprehensively to verify this research method as far as possible to the reliability of various environmental water samples, Tianjin linchpin has been selected herein A variety of environmental water samples such as river, reservoir water, potable water source district water and rainwater in area carry out this control experiment.Due to RO Concrete water quality needed for UF membrane sample preparation device is relatively more, this sub-sampling acquires water sample 50L in each point.Because concrete water quality is big, It is difficult to find suitable glass container and preservation is sealed to the water sample of acquisition, tritium is sent out in tritium and ambient enviroment in water sample to reduce Raw exchange, entire sample collection process are conducted batch-wise, it is ensured that each water sample acquired back can be handled as early as possible.Specifically Preparation and measurement procedure are carried out in strict accordance with the description in 5.2.1 trifle.The raw measurement data of comparison is shown in Table 15, table 16 respectively And shown in table 17.Wherein, table 15 is rivers, tritium concentration matching measurement tables of data in reservoir water, and table 16 is in potable water source district water Tritium concentration matching measurement tables of data；Table 17 is tritium concentration matching measurement tables of data in rainwater.

Table 15

Note: " * " mark indicates that sample passes through pre-treatment twice in table.

Table 16

Note: " * " mark indicates that sample passes through pre-treatment twice in table.

Table 17

5.2.3 mark-on sample compares

Further to verify this research method to the reliability of the water sample measurement result polluted there may be tritium, spy is configured with Tritium concentration is respectively three groups of mark-on samples of 9.68Bq/L, 50.5Bq/L, 104Bq/L, then according to 5.2.1 trifle process, successively This three groups of mark-on samples are carried out with the control experiment of tritium analysis.It is every compared one group of mark-on sample after, all with laboratory tap water to RO Film sample preparation device is cleaned, until through the device treated originally water sample tritium counting rate be restored to initial level.Mark-on sample Matching measurement initial data is shown in Table 18.

Table 18

5.2.4 quality assurance

Data to guarantee this experiment acquisition are accurate and reliable, and whole experiment process is all in the quality certification system frame of our unit It is executed under frame.Key instrument equipment and reagent consumptive material used in experimentation are shown in Table 19.

Table 19

Wherein, tritium standard solution can trace to the source to German certification and accreditation committee Dakks, and liquid dodges the instrument such as spectrometer, electronic balance Device equipment is through metrological service's assay approval, and within validity period.The configuration of instrument producer is utilized during entire experiment Non- this original pattern of quenching carries out irregular confirmatory measurement, sees Figure 21 by the quality control chart that measurement result draws out liquid sudden strain of a muscle spectrometer It is shown.

As seen from Figure 21, during entire experiment, the non-quenching background counting rate of LB7 type scintillation counter is at mean value In 3 times of Standard deviation-Ranges, Spectrometer performance is relatively stable, meets quality control related request.

5.3, data processing

5.3.1 the calculating of tritium concentration and detection limit

Tritium activity concentration calculation is shown in formula 5 in water, and formula 1 is shown in detection limit calculating.

In formula: C indicates the activity concentration of tritium in detected water sample, Bq/L；

N_cIndicate detected water sample counting rate, min^-1；

N_bIndicate background sample counting rate, min^-1；

E indicates detection efficient, %；

V indicates sample amount, ml；

6×10^-2For unit conversion coefficient.

5.3.2 the evaluation of uncertainty

It is all inevitably to there is error between obtained result and true value by measuring, because of measuring condition unreasonably Wanting and practical true value can not determine, so the size of error is often also difficult to determine.For this purpose, International Metrology Commission (CIPM) It is recommended that the result with uncertainty substitution error to indicate experiment.Uncertainty has comprehensively considered all factors for causing error The degree that final experimental result is had an impact.

A. standard substance, measurer and the instrument being related to

(1) tritium standard substance: U=3.0%, k take 2；

(2) the ultralow background liquid of LB7 type dodges spectrometer；

(3) 10ml liquid-transfering gun: the limits of error (MPE_P) it is ± 0.06ml, according to being uniformly distributed, k value

(4) BSA224S type electronic balance: the limits of error (MPE_B) it is ± 0.5mg, according to being uniformly distributed, k value

B. the foundation of mathematical model

The mathematical model of this research method uncertainty of measurement is established according to formula 5-1.

C. the source analysis of uncertainty

The measurement of tritium concentration is by the decay of detected sample, the fluctuation of background, the uncertainty of standard substance and instrument in water Device measures the combined influence of the factors such as uncertainty.According to relevant criterion combination formula 5-1, tritium concentration uncertainty of measurement in water Analysis is as shown in Figure 22.

As seen from Figure 22, the uncertainty source of the two methods analysis result this time compared is consistent, it is anticipated that The range of uncertainty difference that two methods analyze result is not too large.

D. the evaluation of partial uncertainty

(1) the uncertainty u of sample measurement₁:

In formula: Nc indicates sample meter digit rate, min-1；

N_bIndicate background counting rate, min^-1；

t_cIndicate sample time of measuring, min；

t_bIndicate sample-out count time, min.

(2) the uncertainty u that instrument efficiency calibration generates₂, as shown in Figure 22, the uncertainty that efficiency calibration generates is main From following three aspects.

First is that the uncertainty u of tritium standard specimen measurement₂₁:

In formula: N_sIndicate tritium standard sample meter digit rate, min^-1；

N_bIndicate background counting rate, min^-1；

t_sIndicate tritium standard sample time of measuring, min；

t_bIndicate sample-out count time, min.

Second is that tritium standard specimen concentration uncertainty u₂₂, tritium standard specimen is diluted by the tritium standard substance bought to be got.Mainly by tritium mark Quasi- material concentration uncertainty u₂₂₁, tritium standard substance weigh uncertainty u₂₂₂、

Tritium standard substance dilutes uncertainty u₂₂₃It constitutes.

u₂₂₁、u₂₂₂、u₂₂₃Calculation formula enumerate respectively it is as follows:

In formula: U₂₂₁For the expanded uncertainty provided in tritium standard substance certificate, k takes 2.

In formula: MPE_BIndicate the electronic balance limits of error, mg；

M expression weighs tritium standard substance quality, mg；

K takesAccording to being uniformly distributed.

In formula: MPE_BIndicate the electronic balance limits of error, mg；

M expression is weighed for diluted tritium-free water quality, mg；

K takesAccording to being uniformly distributed.

Third is that tritium standard liquid weighs the uncertainty u of generation₂₃:

In formula: MPE_BIndicate the electronic balance limits of error, mg；

M indicates to weigh the quality of tritium standard liquid, mg；

K takesAccording to being uniformly distributed.

(3) liquid-transfering gun pipettes the uncertainty u of analysis sample₃:

In formula: MPE_PIndicate the limits of error of 10ml liquid-transfering gun, ml；

V indicates to pipette the volume of sample, ml；

K takesAccording to being uniformly distributed；

It represents 10ml liquid-transfering gun point 5 times and pipettes the synthesis that total 50ml sample causes uncertainty.

E. the evaluation of Composite Seismogram

F. the calculating of expanded uncertainty

U=ku_c (16)

K generally takes 2 in formula.

5.3.3 Appreciation gist

According to relevant criterion requirement, this paper selection ratio value En is evaluated experimental result is compared.En value indicates normalizing The error of change, calculation formula are as follows:

In formula: the tritium concentration that tritium analysis method measurement obtains in water of the LAB expression based on RO film sample preparation is as a result, Bq/L；

REF indicates the tritium concentration of air-distillation method measurement as a result, Bq/L；

U_LABIndicate that (confidence level is for the uncertainty of tritium analysis method measurement result in the water based on RO film sample preparation 95%), Bq/L；

U_REFIndicate the uncertainty (confidence level 95%) of air-distillation method measurement result, Bq/L.

When the absolute value of En value is not more than 1, i.e., | En | it is satisfied that≤1 Shi Ze represents comparison result, and experiment measured result is can Within the scope of receiving.And | En | value is smaller, indicates that comparison result is closer, effect is better.

5.4, experimental result and analysis

5.4.1 environmental water sample comparison result and analysis

By the environmental water sample control experiment raw measurement data of table 15, table 16 and table 17, the data described according to 5.3 trifles Processing method after collated, calculating, show that the comparison result of environmental water sample is listed in table 20, table 21 and table 22.

Table 20

Table 21

Table 22

Above-mentioned comparison result is shown: 1. from the point of view of measurement result, in addition to except Ninghe north, water head site is not detected, and remaining all the points The environmental water sample of position, the tritium concentration range obtained through the analysis of air-distillation sample preparation method is 0.55~2.27Bq/L, through RO UF membrane The tritium concentration range that sample preparation method analysis obtains is 0.69~2.11Bq/L, is in tritium concentration in current China's natural environmental water Within normal range (NR), analysis result is reliable；2. for comparison result, the range of uncertainty of atmospheric distillation measurement is The range of uncertainty of 10.93%~39.53%, RO UF membrane sample preparation method measurement is 11.59%~31.65%, the two difference Less.Two methods are 2.61%~25.45% to the relative deviation absolute value range of tritium comparison result in ambient water, are all existed Within 30%, the absolute value range of rate value En is 0.06~0.79, | En | < 1, comparison measurement results can receive.

In addition, two kinds of analysis methods show that tritium concentration is lower than detection limit in the water head site water of Ninghe north in table 21, through looking into It learns that Ninghe north water source belongs to and buries type groundwater source, tritium concentration is low in water, therefore fails to detect.In table 22, rainwater 1 and rain Two rainwater samples that water 2 is acquired from the different times of same point, but two kinds of analysis methods are all shown in rainwater 1 and rainwater 2 Tritium concentration difference is larger.Through analyzing, this may be as caused by the collection process difference of two rainwater samples.Wherein, rainwater 1 From in the rainfall of multiple small rainfall, the sample collection time is long, the degree that the rainwater sample of collection is exchanged with ambient enviroment generation tritium compared with Greatly.And rainwater 2 increases rainwater-collecting equipment from heavy rain, and in advance, therefore the sample collection time is short, the rain of collection The degree that water is exchanged with ambient enviroment generation tritium is small.

5.4.2, tritium mark-on sample comparison result and analysis

By the mark-on sample control experiment raw measurement data of table 19, after collated, calculating, various concentration mark-on sample is obtained Comparison result is listed in table 23.It should be pointed out that it is bigger with addition of standard specimen volume because of institute, tap water is weighed in configuration process Sample uses simple electronic scale, and the scale precision is inadequate and uncertified.Therefore with addition of standard specimen concentration it is for reference only Value rather than standard value.

Table 23

By table 23 as it can be seen that same mark-on sample, the tritium concentration result that is obtained respectively with atmospheric distillation and RO membrane separation process It is not much different, the absolute value of rate value En is respectively less than 1, and comparison result is satisfied.It is relatively inclined between measurement result and reference value From the point of view of difference, the latter's relative deviation is smaller, closer to reference value.

To sum up, visible by the above control experiment: 1. for environmental water sample, two methods analysis result be in it is current I In state's natural environmental water within the normal range (NR) of tritium concentration, the two result relative deviation absolute value range be 2.61%~ 25.45%, all within 30%, the absolute value range of rate value En is 0.06~0.79, and less than 1, comparison measurement results can be with Receive；2. the absolute value of rate value En is respectively less than 1, and comparison result is satisfied, wherein the analysis method of RO film sample preparation for mark-on sample Acquired results are closer with reference value.

Accordingly, it demonstrates tritium automatic analysis method in the water based on RO film sample preparation of this research and analyzes tritium acquired results in water It is accurate, reliable.

Further, in summary, 1) system of tritium automatic analysis method in the water based on RO film sample preparation is constituted and is carried out It introduces.Wherein introduce the working principle of RO UF membrane sample preparation device, device is constituted and the device is for tritium in water The sample preparation workflow of analysis.In addition, having carried out brief Jie to relevant issues such as principle, the workflows of liquid flashing counting measurement It continues.

2) comprehensive performance of RO UF membrane sample preparation device is had studied.Using the RO film sample preparation device to varying environment water sample Treatment effect has carried out research, and the preliminary identification device is lower than 1.00NTU to turbidity, and conductivity is in 900 μ s/cm environment below Water sample has good treatment effect；The research for having carried out device processing water sample process consumption sample and time-consuming situation, as the result is shown should Device normally prepares sample average consumption water sample 13L or so, average about 40 minutes time-consuming, consumes compared with atmospheric distillation Sample size greatly increases, but the required time has and significantly shortens；Carry out the research of service using life situation, research shows that The number that the device normally can effectively deal with water sample should be at 70 times or more, and specifically used life situations and device handle water sample Water quality is related, and water quality is better, and the service life of device is longer；The tritium residue problem of RO film in device is studied, as a result When showing the normal processing environment water sample of the device, analysis result is impacted without considering that the tritium of RO film remains, but when processing After complete has the water sample of higher tritium concentration (10Bq/L or more), the tritium residue problem of RO film need to arouse attention.

3) optimization of liquid flashing counting measurement method and condition is studied.100ml capacity counting vial is selected, it is corresponding to visit Lower limit is surveyed to be greatly reduced to 0.4Bq/L or so, can effectively solve at present because detection limit be too high to tritium in ambient water into The problem of row is effectively analyzed.Under 100ml capacity counting vial measurement pattern, water sample uses the volume proportion of 50:50 with scintillation solution It is than convenient.Experimentation discovery, whether no matter standing, there are larger waves for first measurement data of each sample It is dynamic, statistics should not be included in and calculated, in addition, result of study is not necessarily to too long of standing for showing standard sample higher for tritium concentration It is protected from light the time.For this purpose, can sequentially be placed in liquid by standard sample, to test sample and this original pattern dodges spectrometer, standard sample measures 60 minutes/time, Remaining sample measures 100 minutes/time, and each sample duplicate measurements 11 times is protected from light without specially standing, can measure immediately.

4) the method for developing compares, to verify this research method tritium precision of analysis.Air-distillation and RO are used respectively Two kinds of method for making sample of UF membrane carry out sample preparation to the tritium mark-on sample of various environmental water samples and various concentration, are then studied with this Determining liquid dodges measurement method method and measures comparison to the above sample.The results show that for environmental water sample, two methods ratio Relative deviation absolute value range to result is 2.61%~25.45%, and the absolute value range of rate value En is 0.06~0.79, |En|<1；For tritium mark-on sample, two methods analyze the rate value of result | En | < 1, and the analysis method gained of wherein RO film sample preparation As a result closer with reference value.It demonstrates tritium automatic analysis method in the water based on RO film sample preparation of this research and analyzes tritium institute in water It obtains the result is that accurate, reliable.

The fast automatic analysis method of tritium, utilizes reverse osmosis membrane separation skill in the water proposed according to the utility model embodiment Art carries out quick separating-purifying to water sample to be measured to reach the condition requirement for meeting liquid and dodging measurement, effectively shortens pre-treatment Time improves analysis efficiency, and the liquid that reselection is suitable for dodges measurement method to sample progress count measurement, so as to effective It reduces detection limit and the applicability of analysis is effectively improved with the analysis of the tritium suitable for a variety of ambient waters, realize the automation of tritium Analysis, it is simple easily to realize.

The fast automatic analytical equipment of tritium in the water proposed according to the utility model embodiment is described referring next to attached drawing.

Figure 23 is the structural schematic diagram of the fast automatic analytical equipment of tritium in the water of the utility model one embodiment.

As shown in figure 23, in the water the fast automatic analytical equipment 10 of tritium include: back purge system 100 and automatic liquid matching with Convey measuring system 200.

Wherein, back purge system 100 obtains back segment by reverse osmosis membrane purification and filters out for obtaining water sample to be measured Liquid；Automatic liquid matching and conveying measuring system 200 be used for injected respectively into counting vial the first preset volume back segment filter liquor and The scintillation solution of second preset volume, and counting vial fullys shake and makes being uniformly mixed for back segment filter liquor and scintillation solution, to obtain Sample to be tested, and spectrometer is dodged by liquid, count measurement is carried out to sample to be tested, to obtain the analysis result of tritium in water sample to be measured.This The device 10 of utility model embodiment can effectively shorten the time of analysis, improve the efficiency of analysis, and can be effectively reduced Detection limit effectively improves the applicability of analysis, realizes the automated analysis of tritium, simple easily to realize.

It should be noted that back purge system 100 can be RO UF membrane sample preparation device, RO UF membrane sample preparation device is in side Method part has been discussed in detail, and to avoid redundancy, this will not be repeated here.

Further, in one embodiment of the utility model, the device 10 of the utility model embodiment further include: sample Product bottle automatic control system.Wherein, sample bottle automatic control system into counting vial for injecting the first preset volume respectively Back segment filter liquor and the second preset volume scintillation solution after, screw the bottle cap of counting vial automatically, and count fulling shake Bottle make back segment filter liquor and scintillation solution it is uniformly mixed after, wiping processing is carried out to counting vial automatically.

Further, in one embodiment of the utility model, the volume of counting vial is 100ml, the first preset volume It is 50ml with the second preset volume.

Further, in one embodiment of the utility model, back purge system 100 includes: water sample wash module, one Secondary filtering module, sample preparation module and drain module.

Wherein, water sample wash module, for being rinsed using water sample to be measured；Filtering module, for passing through reverse osmosis Permeable membrane separating and filtering water sample to be measured, to obtain spare water sample, and excludes waste water；Sample preparation module, for passing through the reverse osmosis membrane The spare water sample is filtered again, proposes to obtain back segment filter liquor with purification；Drain module, for emptying remaining water to be measured Sample.

Further, in one embodiment of the utility model, the device 10 of the utility model embodiment further include: inspection Survey module, judgment module and processing module.

Wherein, detection module, for detecting the conductivity value of back segment filter liquor；Judgment module, for judging conductivity value Whether default conductivity value is less than；Processing module, for being injected into counting vial when conductivity value is less than default conductivity value The back segment filter liquor of first preset volume, and when conductivity value is more than or equal to default conductivity value, pass through reverse osmosis membrane Purification back segment filter liquor again, until conductivity value is less than default conductivity value.

It should be noted that the aforementioned explanation to the fast automatic analysis method embodiment of tritium in water is also applied for this The fast automatic analytical equipment of tritium in the water of embodiment, details are not described herein again.

The fast automatic analytical equipment of tritium, utilizes reverse osmosis membrane separation skill in the water proposed according to the utility model embodiment Art carries out quick separating-purifying to water sample to be measured to reach the condition requirement for meeting liquid and dodging measurement, and the separation that effectively shortens mentions The pure time improves the efficiency of analysis so as to effectively shorten time of analysis, and the suitable liquid of reselection dodges measurement side Formula carries out count measurement to sample, with the analysis of the tritium suitable for a variety of ambient waters, to be had so as to which detection limit is effectively reduced Effect improves the applicability of analysis, realizes the automated analysis of tritium, simple easily to realize.

In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or Implicitly include at least one this feature.The meaning of " plurality " is at least two, such as two in the description of the present invention, It is a, three etc., unless otherwise specifically defined.

In the present invention unless specifically defined or limited otherwise, fisrt feature is in the second feature " on " or " down " It can be that the first and second features directly contact or the first and second features are by intermediary mediate contact.Moreover, first is special Sign can be fisrt feature above the second feature " above ", " above " and " above " and be directly above or diagonally above the second feature, or only Indicate that first feature horizontal height is higher than second feature.Fisrt feature under the second feature " below ", " below " and " below " can be with It is that fisrt feature is directly under or diagonally below the second feature, or is merely representative of first feature horizontal height less than second feature.

In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example Point is contained at least one embodiment or example of the utility model.In the present specification, to the schematic table of above-mentioned term It states and is necessarily directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be with It can be combined in any suitable manner in any one or more of the embodiments or examples.In addition, without conflicting with each other, this field Technical staff can by the feature of different embodiments or examples described in this specification and different embodiments or examples into Row combination and combination.

Although the embodiments of the present invention have been shown and described above, it is to be understood that above-described embodiment is Illustratively, it should not be understood as limiting the present invention, those skilled in the art are in the scope of the utility model Inside it can make changes, modifications, alterations, and variations to the above described embodiments.

Claims (5)

1. the fast automatic analytical equipment of tritium in a kind of water characterized by comprising

Back purge system obtains back segment filter liquor by reverse osmosis membrane purification for obtaining water sample to be measured；

Automatic liquid matching and conveying measuring system, for injecting the back segment filter liquor and the of the first preset volume into counting vial respectively The scintillation solution of two preset volumes, and counting vial fullys shake, back segment filter liquor and scintillation solution are uniformly mixed, it is to be measured to obtain Sample, and spectrometer is dodged by liquid, count measurement is carried out to the sample to be tested, to obtain the analysis knot of tritium in the water sample to be measured Fruit.

2. the fast automatic analytical equipment of tritium in water according to claim 1, which is characterized in that further include:

Sample bottle automatic control system, in the back segment filter liquor and second for injecting the first preset volume into counting vial respectively After the scintillation solution of preset volume, the bottle cap of the counting vial is screwed automatically, and counting vial fullys shake back segment is filtered out Liquid and scintillation solution it is uniformly mixed after, wiping processing is carried out to the counting vial automatically.

3. the fast automatic analytical equipment of tritium in water according to claim 1 or 2, which is characterized in that the counting vial Volume is 100ml, and first preset volume and second preset volume are 50ml.

4. the fast automatic analytical equipment of tritium in water according to claim 1, which is characterized in that the back purge system packet It includes:

Water sample wash module, for being rinsed using water sample to be measured；

Filtering module, for filtering the water sample to be measured by the reverse osmosis membrane separation, to obtain spare water sample, side by side Except waste water；

Sample preparation module proposes to obtain back segment filter with purification for filtering the spare water sample again by the reverse osmosis membrane Liquid out；

Drain module, for emptying remaining water sample to be measured.

5. the fast automatic analytical equipment of tritium in water according to claim 4, which is characterized in that further include:

Detection module, for detecting the conductivity value of the back segment filter liquor；

Judgment module, for judging whether the conductivity value is less than default conductivity value；

Processing module, for it is default to inject first into counting vial when the conductivity value is less than the default conductivity value The back segment filter liquor of volume, and when the conductivity value is more than or equal to the default conductivity value, pass through reverse osmosis membrane Purification back segment filter liquor again, until the conductivity value is less than the default conductivity value.