CN101221125A - Method for measuring eutrophication water body characteristic parameter by spectrum technology - Google Patents
Method for measuring eutrophication water body characteristic parameter by spectrum technology Download PDFInfo
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- CN101221125A CN101221125A CNA2008100594856A CN200810059485A CN101221125A CN 101221125 A CN101221125 A CN 101221125A CN A2008100594856 A CNA2008100594856 A CN A2008100594856A CN 200810059485 A CN200810059485 A CN 200810059485A CN 101221125 A CN101221125 A CN 101221125A
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Abstract
The invention discloses a method for determining the character parameters of a eutrophia water body by adopting a spectrum technology. The steps of the method are as follows: building a spectrum database of corrected sample collection; pretreating the spectrum; building a correcting module; distilling spectrum characteristics; determining the water quality character parameters of an unknown sample. The method has the following advantages of (1) utilizing the spectrum technology for analyzing the character parameters of the eutrophia water body and greatly accelerating the analyzing speed; (2) using no chemical reagents, thus reducing detecting cost and not polluting environment; (3) compared with a chemical method, system errors and artificial errors are reduced greatly, thus improving measuring precision; (4) being capable of simultaneously analyzing and detecting a plurality of water quality parameters, thus saving time and a real-time detecting technology can be better applied to environment monitoring; (5) having excellent social and economic benefits. By being further popularized, the method has good effects on solving the escalating eutrophia problems of lakes and marsh water-area environment at present.
Description
Technical field
The present invention relates to visible light and near-infrared spectral measurement method, especially relate to a kind of method with spectrum technology determining eutrophication water characteristic parameter.
Technical background
Body eutrophication be meant lake or wetland waters natural cause and (or) under the influence of mankind's activity, a large amount of nutritive salt input lake or wetland waters, a kind of phenomenon that lake or wetland waters are progressively changed to the higher eutrophic state of the level of the productive forces by the lower poor nutritional status of the level of the productive forces.In order accurately to evaluate the residing eutrophic state of eutrophication water, and then, need carry out regular monitoring to total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), the transparency characteristic parameters such as (SD) of eutrophic lake for the control of body eutrophication provides scientific basis.The classic method of Cai Yonging had in the past: the mensuration of water body total nitrogen adopts alkaline alkaline potassium per-sulfate digestion ultraviolet spectrophotometry; The mensuration of water body total phosphorus adopts the ammonium molybdate spectrophotometric method; The mensuration of chemical oxygen demand of water body adopts dichromate titration; The concentration of the chlorophyll a of water body adopts spectrophotometer method to measure; Water transparency adopts tradition match gram dish method (Secchi Disk).Because water surface area is big, measuring point is many, on the other hand owing to be the measurement of many reference amounts, therefore sample size is big, there is a lot of defectives in above-mentioned each parameter assay method: needs consume a large amount of chemical reagent and instrument and equipment, and sample preparation steps is loaded down with trivial details, and a plurality of parameters of same sample are detected respectively, cost height, the cycle of analyzing a sample are long, are not suitable for multisample, many reference amounts eutrophication water are carried out analyzing and testing.The visible light that we adopted and the principal feature of near-infrared spectrum technique are: analysis speed is fast, can finish the measurement of a sample in one minute; Simultaneous determination of multiponents, the content of total nitrogen in the sample (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) can disposablely be measured simultaneously; Sample does not need pre-service; Without any need for chemical reagent; Non-destructive analysis; Long distance is measured and real-time analysis; Harmonic analysis cost and simple to operate.Therefore spectral technique relatively is fit to multisample, many reference amounts eutrophication water are carried out analyzing and testing.
Summary of the invention
In order to overcome the problem that exists in the background technology, the object of the present invention is to provide a kind of method of effectively measuring characteristic parameter in the eutrophication water fast.Can not only carry out fast eutrophication water, detect in real time, and can detect a plurality of characteristic parameters in the water body simultaneously.
The step that the present invention solves the scheme that its technical matters adopts is as follows:
1) foundation of correcting sample light harvesting spectrum database; At first will be at the water body sample of equally distributed each measuring point in waters to be measured as the calibration samples collection, then the sample in the calibration samples set is carried out spectral scan and obtain the calibration samples standard spectrum, same sample needs repeatedly duplicate measurements, with averaged spectrum as this sample standard spectrum;
2) pre-service of spectrum; The first step behind the acquisition calibration samples collection standard spectrum is that calibration samples collection standard spectrum is carried out pre-service, and the pretreated effect of spectrum is standardization, the counteracting background interference of spectrogram and the quality that improves spectrum;
3) foundation of calibration model; Use the multiple regression algorithm and set up calibration model for the normative reference measured value of pretreated spectroscopic data and sample;
4) extraction of spectral signature; The data of spectrum generally all have hundreds of to thousands of data points, all data all are used for setting up model and often cause the model learning time long, model structure complexity, method commonly used are that the method that progressively returns is sought characteristic wave bands, and the method for perhaps using the related coefficient tracing analysis realizes;
5) the water quality characteristic parameter of unknown sample is measured; At first scan the spectrum that sample to be measured obtains them, the measuring method that is adopted when obtaining their spectrum, the measuring method that is adopted in the time of must obtaining the sample spectrum of setting up calibration model together is consistent; Each parameter that the method for sampling of being taked, resolution, sweep spacing or sweep time are adopted in the time of also should obtaining the sample spectrum of setting up calibration model together is consistent;
6) calibration model that unknown water sample has been set up through the input of pretreated spectral information can dope total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), the chlorophyll a (Chla) of unknown sample, the content of transparency (SD).
Describedly sample spectrum is carried out pre-service be level and smooth, centralization, derivative, normalization preprocessing procedures.
Described multiple regression algorithm is multiple linear regression algorithm and nonlinear multivariable regression algorithm.
Described total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) content of setting up the calibration samples of calibration model is to adopt the method for GB regulation and the standard value that existent method measures;
Described with calibration samples spectroscopic data and their standard total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) content set up calibration model
Described spectrometer is for obtaining the water sample spectral signal at 325-2500nm wavelength place simultaneously.
The present invention compares with background technology, has the following advantages:
(1) utilize spectral technique to analyze the characteristic parameter of eutrophication water, its analysis speed is accelerated greatly.
(2) do not use any chemical reagent, reduced the detection cost, also free from environmental pollution.
(3) compare with chemical method, systematic error and personal error reduce greatly, have improved measuring accuracy.
(4) a plurality of water quality parameters of analyzing and testing are simultaneously saved time, and detection technique can be good at being applied to environmental monitoring in real time.
(5) have good social benefit and economic benefit.As further popularization, good effect is arranged to solving the lake that is on the rise at present and the water body environment eutrophication problem of wetland.
Description of drawings
Accompanying drawing is a theory diagram of the present invention.
Embodiment
This accompanying drawing has shown that whole implementation process of the present invention comprises following two parts:
First is the foundation of calibration model, mainly may further comprise the steps:
1. with data line spectrometer is linked to each other with the PC computer, sample places special glass sample container.Spectrometer probe, light source all keep vertical with the sample container baseplane.At first, with the sample in the 14.5V Halogen lamp LED irradiation sample cell, (wavelength coverage is 325～2500nm) at one end sample cell to be gathered spectral information, carries out the spectral information initialization, then water sample is injected sample cell with visible light/near infrared spectrometer, sample cell is placed on the specimen holder, the spectral information of collected specimens, light source is fixed as 45cm apart from the water surface elevation of water sample, and spectrometer probe is fixed as 30cm at opposite side apart from the water surface distance of water sample, each scan sample 30 times, resolution 3.5cm
-1, the probe field angle is 20 degree.The water sample spectroscopic data of gathering is delivered to computing machine by data line interface.
To the spectroscopic data that obtains with spectrometer with the spectral information of scan sample being carried out the spectrum average treatment with spectrum dedicated analysis software ASD ViewSpec ProV2.14, then spectral-transmission favtor is converted into absorbance, the multivariate data information processing platform of building with Unscramble V9.7 and matlab program to the spectral absorbance value carry out smoothly, derivative, the pre-service of normalization spectrum, eliminate system noise and interference.
3. the total nitrogen (TN) of the method for employing GB regulation or existent method measurement modeling sample, total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) content are as standard content.The mensuration of water quality total nitrogen adopts alkaline alkaline potassium per-sulfate digestion ultraviolet spectrophotometry (GB 11894-1989), the mensuration of water quality total phosphorus adopts ammonium molybdate spectrophotometric method (GB 11893-1989), the mensuration of hydrochemistry oxygen demand adopts dichromate titration (GB 11914-1989), the concentration of the chlorophyll a of water sample is after sampling, return experimental determination immediately, at first use the 0.45m membrane filtration, use acetone extract then, after covering light 24h, adopt spectrophotometer method to measure; Water transparency adopts tradition match gram dish method (Secchi Disk).
4. adopt polynary correcting algorithm (partial least squares regression, multiple linear regression, neural network, support vector machine etc.) to set up quantitative relationship between the near infrared spectrum of modeling sample and their total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) the content standard content, promptly set up calibration model.
5. adopt the method for progressively recurrence and the spectral signature wave band that related coefficient curve distribution feature is sought total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD).
Second portion is the mensuration of unknown water sample, mainly may further comprise the steps:
1. at first scan unknown water sample to obtain their spectrum, the measuring method that is adopted when obtaining their spectrum, the measuring method that is adopted in the time of must obtaining the sample spectrum of setting up calibration model together is consistent, be the method for sampling, resolution, sweep spacing and sweep time, should be consistent.
To the spectroscopic data that obtains with spectrometer with the spectral information of scan sample being carried out the spectrum average treatment with spectrum dedicated analysis software ASD ViewSpec ProV2.14, then spectral-transmission favtor is converted into absorbance, the multivariate data information processing platform of building with Unscramble V9.7 and Matlab program to the spectral absorbance value carry out smoothly, derivative, the pre-service of normalization spectrum, eliminate system noise and interference.
3. unknown water sample is imported the content of total nitrogen (TN) that calibration model that above-mentioned first sets up can dope unknown sample, total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) through pretreated spectral information.
Claims (6)
1. method with spectrum technology determining eutrophication water quality characteristic parameter is characterized in that the step of this method is as follows:
1) foundation of correcting sample light harvesting spectrum database; At first will be at the water body sample of equally distributed each measuring point in waters to be measured as the calibration samples collection, then the sample in the calibration samples set is carried out spectral scan and obtain the calibration samples standard spectrum, same sample needs repeatedly duplicate measurements, with averaged spectrum as this sample standard spectrum;
2) pre-service of spectrum; The first step behind the acquisition calibration samples collection standard spectrum is that calibration samples collection standard spectrum is carried out pre-service, and the pretreated effect of spectrum is standardization, the counteracting background interference of spectrogram and the quality that improves spectrum;
3) foundation of calibration model; Use the multiple regression algorithm and set up calibration model for the normative reference measured value of pretreated spectroscopic data and sample;
4) extraction of spectral signature; The data of spectrum generally all have hundreds of to thousands of data points, all data all are used for setting up model and often cause the model learning time long, model structure complexity, method commonly used are that the method that progressively returns is sought characteristic wave bands, and the method for perhaps using the related coefficient tracing analysis realizes;
5) the water quality characteristic parameter of unknown sample is measured; At first scan the spectrum that sample to be measured obtains them, the measuring method that is adopted when obtaining their spectrum, the measuring method that is adopted in the time of must obtaining the sample spectrum of setting up calibration model together is consistent; Each parameter that the method for sampling of being taked, resolution, sweep spacing or sweep time are adopted in the time of also should obtaining the sample spectrum of setting up calibration model together is consistent;
6) calibration model that unknown water sample has been set up through the input of pretreated spectral information can dope total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), the chlorophyll a (Chla) of unknown sample, the content of transparency (SD).
2. the method for a kind of using visible light according to claim 1 and near-infrared spectrum technique fast measuring lake eutrophication characteristic parameter is characterized in that: describedly sample spectrum is carried out pre-service be level and smooth, centralization, derivative, normalization preprocessing procedures.
3. a kind of method with spectrum technology determining eutrophication water quality characteristic parameter according to claim 1, it is characterized in that: described multiple regression algorithm is multiple linear regression algorithm and nonlinear multivariable regression algorithm.
4. a kind of method with spectrum technology determining eutrophication water quality characteristic parameter according to claim 1 is characterized in that: described total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) content of setting up the calibration samples of calibration model is to adopt the method for GB regulation and the standard value that existent method measures;
5. a kind of method with spectrum technology determining eutrophication water quality characteristic parameter according to claim 1 is characterized in that: describedly set up calibration model with the spectroscopic data of calibration samples and their standard total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD) (COD), chlorophyll a (Chla), transparency (SD) content
6. a kind of method with spectrum technology determining eutrophication water quality characteristic parameter according to claim 1, it is characterized in that: described spectrometer is for obtaining the water sample spectral signal at 325-2500nm wavelength place simultaneously.
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| CN101907565A (en) * | 2010-06-25 | 2010-12-08 | 杨季冬 | Spectral analysis method capable of measuring chemical oxygen demand and biochemical oxygen demand in waste water simultaneously |
| CN102053140A (en) * | 2009-10-27 | 2011-05-11 | 华中科技大学 | Diagnosis and evaluation method for water quality of eutrophic shallow lake subjected to ecological restoration |
| CN102507458A (en) * | 2011-11-23 | 2012-06-20 | 浙江大学 | Correction method of sunlight source in outdoor hyperspectral image acquisition system |
| CN102564965A (en) * | 2011-12-31 | 2012-07-11 | 聚光科技(杭州)股份有限公司 | Detecting method based on spectroscopy detection technology |
| CN102707025A (en) * | 2012-01-11 | 2012-10-03 | 戴会超 | Intelligent distinguishing method and intelligent distinguishing device for nutritional status of lakes and reservoirs |
| CN103473707A (en) * | 2013-09-17 | 2013-12-25 | 山东大学 | Method for establishing urban river network water body spectrum library and application |
| CN103913421A (en) * | 2012-12-28 | 2014-07-09 | 中国科学院沈阳应用生态研究所 | Method for determining water-soluble Fe content of eutrophic lake |
| CN101988894B (en) * | 2009-07-31 | 2015-01-28 | 恩德莱斯和豪瑟尔测量及调节技术分析仪表两合公司 | Method for determining a parameter of liquid sample |
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| CN105092523A (en) * | 2015-08-25 | 2015-11-25 | 江南大学 | Scheme based on near infrared technology and used for detecting phosphorous in water |
| CN105891143A (en) * | 2016-03-30 | 2016-08-24 | 安徽建筑大学 | Method for measuring total phosphorus concentration in denitrifying phosphorus removal system by means of near infrared spectrum |
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