CN106771027B - Ocean dissolved inorganic carbon in situ measurement instrument - Google Patents
Ocean dissolved inorganic carbon in situ measurement instrument Download PDFInfo
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- CN106771027B CN106771027B CN201611128421.8A CN201611128421A CN106771027B CN 106771027 B CN106771027 B CN 106771027B CN 201611128421 A CN201611128421 A CN 201611128421A CN 106771027 B CN106771027 B CN 106771027B
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Abstract
Ocean dissolved inorganic carbon in situ measurement instrument, is related to marine monitoring.Equipped with four-way valve, syringe pump, acidification reactor, CO2UF membrane and absorber, CO2Selective permeable membrane capillary, C4D detector, signal generator, acid solution constant flow pump, absorbing liquid constant flow pump, microprocessor, computer, standard specimen storage tank, acid solution storage tank, absorbs liquid storage tank, pure water circulator, standard sample dilution device, acid dilution device, diluted absorption solution device at detector capillary；Seawater injection port, standard sample dilution device, the outlet of pure water circulator are connect with four-way valve connects acidification reactor through syringe pump again, and acidification reactor is equipped with acid-adding port, the outlet of acidification reactor and CO2The connection of the sample inlet of UF membrane and absorber, CO2UF membrane and absorber are provided at least 1 CO2Selective permeable membrane capillary, the absorbing liquid outlet of capillary and C4The connection of D detector, C4The waste liquid of D detector outlet is connected with pure water circulator.
Description
Technical field
The present invention relates to marine monitorings more particularly to a kind of high-precision, high time resolution, micrometeor to be suitable for boat-carrying
Walk the ocean dissolved inorganic carbon in situ measurement instrument of boat.
Background technique
Seawater dissolved inorganic carbon (Dissolved Inorganic Carbon, DIC) is research marine biogeochemistry
The indispensable key parameter of process, it is various inorganic carbonates, bicarbonate, carbonic acid and carbon dioxide gas in ocean
The summation of concentration of carbon.DIC has become the important basic parameter of Ocean acidification research, is the important of understanding marine organisms production process
Parameter.Accurately, quickly and convenient and high time-space resolution measure the spatial and temporal distributions and variability of seawater DIC concentration, for
Ocean acidification and ocean are solved to CO2Absorption, conversion and transition process it is most important.
The seawater DIC monitoring technology for obtaining international endorsement at present mainly includes coulometric titration and using non-dispersive infrared
CO2Analytic approach.These methods have the characteristics that precision is high, stability is good, but since device is complicated, bulky and operation is not square
Just, it is only used for lab analysis, it is difficult to walk boat with boat-carrying on site and observe.Develop recently as technology, DIC detection device
Tend to minimize, more suitable for field observation.Chinese patent CN101806789B discloses analyzing concentration of inorganic carbon in a kind of water body
Analyzer, Chinese patent CN103913553A disclose a kind of seawater dissolved inorganic carbon and walk measuring device of navigating, this 2 kinds of public technologies are adopted
With first converting CO for the dissolved inorganic carbon (DIC) in water body2, then pass through CO2Detector Analysis for CO2Concentration, this method will
DIC is converted into CO2, air lift process is needed, addition carrier gas process makes device operation complicated, since gas is by temperature and humidity and pressure
Influence it is very big, when field application, the stability of device is difficult to ensure that detection accuracy is also affected.Chinese patent
CN102042981A discloses a kind of dissolved inorganic carbon in-site detecting instrument, and DIC is dense in the method measurement water sample which passes through colorimetric
Although degree, this method overcome CO2The problem of air lift and detection, but using colorimetric method need that color developing agent is added, using optical spectroscopy
It measures, is affected by temperature greatly, measurement accuracy is difficult to be guaranteed.CO2Detection and colorimetric method measurement DIC are required to enough
Sample size can just measure, it is therefore desirable to biggish sample size, thus water sample acidification needed for acid solution, measurement standard specimen and
The reagent consumption of addition is big, and very big difficulty is brought to prolonged field observation.
Summary of the invention
The purpose of the present invention is for device complexity, low measurement accuracy, CO existing for existing DIC field observation technology2
The problems such as air lift and measurement are troublesome, addition reagent consumption is big and is influenced by field observation environment, is provided based on C4D detects skill
Art, high-precision, high time resolution and micrometeor are suitable for the ocean dissolved inorganic carbon in situ measurement instrument that boat-carrying walks boat observation.
The present invention is equipped with four-way valve, syringe pump, acidification reactor, CO2UF membrane and absorber, CO2Selective permeable membrane capillary
Pipe, C4D detector, detector capillary, signal generator, acid solution constant flow pump, absorbing liquid constant flow pump, microprocessor, computer,
Standard specimen storage tank, absorbs liquid storage tank, pure water circulator, standard sample dilution device, acid dilution device, diluted absorption solution device at acid solution storage tank；
Seawater injection port, standard sample dilution device, the outlet of pure water circulator are connected with four-way valve, and are connected to by syringe pump
Acidification reactor, acidification reactor are equipped with acid-adding port and carry out acid solution addition, the outlet of acidification reactor by acid solution constant flow pump
With CO2UF membrane is connected with the sample inlet of absorber, CO2UF membrane and absorber are provided at least 1 CO2Selectivity is thoroughly
Membrane capillary, for efficiently quickly by the CO in acidified sample2It infiltrates into capillary, to be inhaled by the absorbing liquid in capillary
It receives, the absorbing liquid outlet of capillary and C4D detector is connected, and carries out sample concentration measurement, C4D detector outlet waste liquid with
Pure water circulator is connected, and the dilution through the purified pure water of pure water circulator for acid solution and absorbing liquid is used.In instrument operation
Long-term automatic running may be implemented without adding pure water.
Control circuit of the invention is equipped with microprocessor, for controlling valve position, the syringe pump, C of four-way valve4D detector, letter
The starting and operation order of number generator, acid solution constant flow pump, absorbing liquid constant flow pump, and by RS-232 interface, with computer phase
Connection carries out parameter setting by software, and the operation of control system, the operating parameter of real time monitoring apparatus and acquisition and storage are surveyed
Measure data.
Application method of the invention is given below:
When carrying out seawater sample measurement, C is first turned on4D detector, signal generator and microprocessor, are preheated,
It opens computer and carries out parameter setting.After being provided with, start absorbing liquid constant flow pump, liquid stabilization to be absorbed flows through C4D detector
Capillary after, open C4D data acquisition software, and start to acquire data, it is recorded as measurement background value, stabilization to be measured at this time
When, switch the valve position of four-way valve to injection port, while starting syringe pump and acid solution constant flow pump, carries out single injected sampling, sample and acid
Solution is sufficiently mixed reaction in acidification reactor, and controlling the additive amount of acid solution, so that it is in excess in carbonate in sample to be tested total
Amount, it is ensured that the carbonate in sample is completely converted into CO2, the sample solution after acidification enters CO2UF membrane and absorber,
CO in absorber2Entered in capillary by capillary outer wall and be absorbed by liquid absorption, the change procedure of absorbing liquid ion concentration by
C4D detector recording, to C4When D detector restores measurement background value, one-shot measurement process terminates, and waits next sample introduction measurement.
When progress sample continuously measures, keeps absorbing liquid constant flow pump and acid solution constant flow pump is normally open, each sample
Start one injection pump when measurement and carry out sample introduction, the valve position of four-way valve need to only be switched to standard specimen mouth by when mark sample can be by above-mentioned
Step is automatically performed measurement process.
Beneficial effects of the present invention are as follows:
Dissolved inorganic carbon automatic observation device in ocean of the present invention, using C4D detector, with high sensitivity,
The feature that detection time is short, precision is high and stability is good, greatly improves DIC measurement accuracy and temporal resolution, and highest is surveyed
Amount frequency can reach 30 times/hour；The sample channel of detector uses capillary channel, and it is considerably less to measure required sample size,
Lower than 0.2ml, the consumption of reagent is greatly reduced, detection solution is not in direct contact with the electrode, and avoids solution to the damage of electrode
Evil, improves the service life of detector.Using CO2UF membrane and absorption process, in the whole process no gaseous CO2It generates, solution
Determined CO2Air lift and detection there are the problem of, using more CO2Selective permeable membrane capillary, greatly improves CO2Conversion effect
Rate and time greatly reduce the time of measuring of sample.During apparatus measures, standard liquid storage tank, acid storage tank and absorbing liquid
Storage tank stores the sample of high concentration, and when measurement is diluted in real time, solves sample and supplies and spoilage problems；It is returned simultaneously using pure water
With technology, in instrument operational process without supply water, it can be achieved that instrument long-term continuous operation.The invention is particularly suited to it is high when
Between the boat-carrying of resolution ratio walk navigation water DIC in-situ observation.The configuration of the present invention is simple, detection accuracy are high, temporal resolution is high, sample
It measures small, amount of reagent consumption less, realizes that the long-time of dissolved inorganic carbon (DIC) in water body detects automatically.
Detailed description of the invention
Fig. 1 is structural schematic diagram of the invention.
Specific embodiment
Referring to Fig. 1, the embodiment of the present invention includes: four-way valve 1, syringe pump 2, acidification reactor 3, CO2UF membrane and absorption
Device 4, CO2Selective permeable membrane capillary 5, C4D detector 6, signal generator 8, acid solution constant flow pump 9, absorbs detector capillary 7
Liquid constant flow pump 10, computer 12, standard specimen storage tank 13, acid solution storage tank 14, absorbs liquid storage tank 15, pure water circulator at microprocessor 11
16, standard sample dilution device 17, acid dilution device 18, diluted absorption solution device 19.
In use, seawater injection port A, standard specimen storage tank 13 (passing through standard sample dilution device 17) and pure water storage tank 14 (are passed through acid
Liquid diluter 18) it is connected respectively to valve position 1A, 1B and 1C of four-way valve 1, valve position 1D is connected through syringe pump 2 with acidification reactor 3
It connects, the outlet of acidification reactor 3 is connected to CO2UF membrane and 4 acidifying solution entrance of absorber；It is dilute by absorbing liquid to absorb liquid storage tank 15
It releases device 19 and absorbing liquid constant flow pump 10 is connected to CO2The absorbing liquid entrance of UF membrane and absorber 4, CO2UF membrane and absorber 4
Absorbing liquid outlet be connected to C4D detector capillary 7, the acidifying solution after absorbing liquid waste liquid and conversion after detection are connected to pure
Water circulator 16 carries out cleansing and recycling, C4D detector 6 is connected with signal generator 8, and is controlled by microprocessor 11, micro process
Device 11 is connected by RS-232 interface with computer 12, is remotely controlled, data acquisition and storage.
When carrying out seawater sample measurement, C is first turned on4D detector 6, signal generator 8 and microprocessor 11, preheating
15min opens computer 12 after the completion of preheating, carries out system parameter setting, including C4The stimulating frequency of D detection 6, acid solution constant current
Pump 9 and the flow of absorbing liquid constant flow pump 10, the flow of syringe pump 2 and starting interval time, 1 valve position transfer sequence of four-way valve etc.,
After being provided with, saves and be arranged as a result, starting to measure.
Before measuring seawater sample, measurement standard specimen, starting absorbing liquid constant flow pump 10, liquid stabilization to be absorbed flow through C first4D inspection
After surveying device capillary 7, start C4D data acquisition software, and start to acquire data, recording at this time is measurement background value, to be measured
When amount is stablized, switch the valve position of four-way valve 1 to standard specimen mouth 1B, while starting syringe pump 2 and acid solution constant flow pump 9, complete once into
Sample, standard specimen is sufficiently mixed in acidification reactor 3 with acid solution to react, and the additive amount of acid solution must be in excess in carbon in sample to be tested
Acid group total amount, it is ensured that the carbonate in sample is completely converted into CO2, the sample solution after acidification enters CO2UF membrane and absorption
Device 4, sample after acidification is from CO2The outside wall surface of selective permeable membrane capillary 5 passes through, and the sample after absorbing liquid and acidification exists respectively
CO2It is flowed in a counter-current configuration in selective permeable membrane capillary 5 is managed and outside pipe, CO2Entered in pipe by capillary outer wall permeable membrane and is inhaled
Liquid is received to absorb.CO2The absorbing liquid that UF membrane and absorber 4 export enters C4D detector 6, the change procedure of absorbing liquid ion concentration
By C4D detector 6 measures, and data are by 12 acquisition and recording of computer, to C4D detector signal restore to measurement background value when, standard specimen
Measurement process terminates.
Start to measure seawater sample, keeping acid solution constant flow pump 9 and absorbing liquid constant flow pump 10 is normally open, by four-way valve 1
Valve position switch to seawater injection port 1A, starting 2 sample introduction of syringe pump is continuously being surveyed by above-mentioned process automatic measurement seawater sample
When measuring sample, only needs starting one injection when the measurement of each sample to pump sample introduction, carry out continuous sample introduction and measurement, the most high frequency of measurement
Rate are as follows: 30 times/hour.The measurement of standard specimen can according to need, and be preset, and carry out standard specimen survey automatically in sample measurement
Amount.
After observation, four-way valve is switched into pure water injection port 1C, closes acid solution constant flow pump 9 and absorbing liquid constant flow pump
10, starting syringe pump cleans system, finally closes system power supply.
Claims (2)
1. ocean dissolved inorganic carbon in situ measurement instrument, it is characterised in that be equipped with four-way valve, syringe pump, acidification reactor, CO2Film point
From with absorber, CO2Selective permeable membrane capillary, C4D detector, signal generator, acid solution constant flow pump, is inhaled detector capillary
It receives liquid constant flow pump, microprocessor, computer, standard specimen storage tank, acid solution storage tank, absorb liquid storage tank, pure water circulator, standard sample dilution
Device, acid dilution device, diluted absorption solution device；
Seawater injection port, standard sample dilution device, the outlet of pure water circulator are connected with four-way valve, and are connected to acidification by syringe pump
Reactor, acidification reactor are equipped with acid-adding port and carry out acid solution addition, the outlet of acidification reactor and CO by acid solution constant flow pump2
UF membrane is connected with the sample inlet of absorber, CO2UF membrane and absorber are provided at least 1 CO2Selective permeable membrane capillary
Pipe, for efficiently quickly by the CO in acidified sample2It infiltrates into capillary, the absorbing liquid outlet of capillary and C4D detector phase
Connection, C4The waste liquid of D detector outlet is connected with pure water circulator.
2. dissolved inorganic carbon in situ measurement instrument in ocean as described in claim 1, it is characterised in that the microprocessor is for controlling
The valve position of four-way valve, syringe pump, C4The starting and operation of D detector, signal generator, acid solution constant flow pump, absorbing liquid constant flow pump
Sequentially, and by RS-232 interface it is connected to a computer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128421.8A CN106771027B (en) | 2016-12-09 | 2016-12-09 | Ocean dissolved inorganic carbon in situ measurement instrument |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128421.8A CN106771027B (en) | 2016-12-09 | 2016-12-09 | Ocean dissolved inorganic carbon in situ measurement instrument |
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| CN106771027A CN106771027A (en) | 2017-05-31 |
| CN106771027B true CN106771027B (en) | 2019-04-26 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108195995A (en) * | 2017-12-26 | 2018-06-22 | 中国科学院海洋研究所 | The measuring device of carbonate content in a kind of marine sediment |
| CN111735921A (en) * | 2020-06-12 | 2020-10-02 | 自然资源部第三海洋研究所 | Multi-parameter observation instrument for marine acidification during ship-borne navigation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102042981B (en) * | 2010-11-09 | 2012-01-11 | 厦门大学 | In-situ tester of dissolved inorganic carbon |
| CN102879590A (en) * | 2012-10-15 | 2013-01-16 | 国家海洋局第二海洋研究所 | Automatic acidification reaction device for seawater sample |
| CN103913553A (en) * | 2014-03-31 | 2014-07-09 | 中国科学院海洋研究所 | Sailing measurement device for seawater dissolved inorganic carbon (DIC) |
| EP3146315B1 (en) * | 2014-05-23 | 2019-11-27 | Hach Company | Measurement of total organic carbon |
| CN104198538B (en) * | 2014-09-24 | 2016-06-29 | 国家海洋局第三海洋研究所 | Boat-carrying walks navigation water dissolution DIC observation device and method |
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Address after: 361005 No. 178 University Road, Siming District, Xiamen City, Fujian Province Applicant after: Third Institute of Oceanography, Ministry of Natural Resources Address before: 361005 No. 178 University Road, Siming District, Xiamen City, Fujian Province Applicant before: Oceanography Inst. No.3, State Bureau of Oceanography |
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