發(fā)布時(shí)間：2019-07-04 13:35

【摘要】：水是生命之源，人類在生活和生產(chǎn)活動(dòng)中都離不開水。然而，隨著我國(guó)經(jīng)濟(jì)的高速發(fā)展和城市化進(jìn)程的加快，暴露的水環(huán)境污染問題也日趨嚴(yán)重，水質(zhì)或水體污染事件頻發(fā)，凸顯了我國(guó)水環(huán)境形勢(shì)不容樂觀。 水質(zhì)的優(yōu)劣不僅與工農(nóng)業(yè)生產(chǎn)安全和人類健康密切相關(guān)，而且還依賴于水質(zhì)檢測(cè)技術(shù)做保障，以此評(píng)判、預(yù)測(cè)和監(jiān)測(cè)水質(zhì)的優(yōu)劣。誠(chéng)然，傳統(tǒng)的儀器檢測(cè)設(shè)備可以對(duì)水質(zhì)參數(shù)進(jìn)行檢測(cè)，但一般只對(duì)單一參數(shù)進(jìn)行測(cè)量。例如，水質(zhì)COD、TOC、TURB和NO3-N等參數(shù)的檢測(cè)，其通常需要COD分析儀，TOC分析儀，濁度計(jì)，NO3-N分析儀等設(shè)備進(jìn)行單獨(dú)測(cè)量，這不僅不利于數(shù)據(jù)的整合，而且還增加了檢測(cè)成本。近年來，作為光譜分析的水質(zhì)檢測(cè)技術(shù)之一的紫外-可見光吸收光譜法，它不僅摒棄了化學(xué)分析和電化學(xué)分析及色譜分析等水質(zhì)檢測(cè)技術(shù)水樣預(yù)處理繁雜、測(cè)量周期長(zhǎng)、所需化學(xué)試劑多的缺點(diǎn)，而且還具有檢測(cè)速度快、成本低和可實(shí)現(xiàn)在線、原位測(cè)量等優(yōu)點(diǎn)，日漸為世人所矚目。然而，目前的紫外-可見光吸收光譜法，一般為單一參數(shù)在線檢測(cè)，國(guó)內(nèi)尚不能實(shí)現(xiàn)水質(zhì)COD、TOC、TURB、NO3-N的多參數(shù)同時(shí)在線檢測(cè)。 本文在四川省科技支撐計(jì)劃項(xiàng)目“多功能水質(zhì)實(shí)時(shí)自動(dòng)監(jiān)測(cè)技術(shù)開發(fā)與產(chǎn)品研制”（項(xiàng)目編號(hào)：2012SZ0111）和四川碧朗科技有限公司橫向合作科研項(xiàng)目“光譜多參數(shù)水質(zhì)在線自動(dòng)監(jiān)測(cè)儀研制”（合同編號(hào)：1042012920140453）及國(guó)家自然科學(xué)基金項(xiàng)目“SFL-Contourlet的構(gòu)造及其特性研究”（批準(zhǔn)號(hào)：61201346）的聯(lián)合資助下，開展了紫外-可見光譜水質(zhì)多參數(shù)檢測(cè)的理論、儀器、方法技術(shù)及應(yīng)用研究工作，研制了一套涵蓋水質(zhì)光譜數(shù)據(jù)采集、水質(zhì)光譜處理、水質(zhì)參數(shù)解算，到實(shí)驗(yàn)室分析驗(yàn)證，再到實(shí)際水質(zhì)多參數(shù)檢測(cè)完整流程的水質(zhì)多參數(shù)檢測(cè)儀器系統(tǒng)，且系統(tǒng)已具有完全自主知識(shí)產(chǎn)權(quán)。論文的研究?jī)?nèi)容，主要包括： ①闡述了光譜法或光譜技術(shù)水質(zhì)參數(shù)檢測(cè)的國(guó)內(nèi)外研究現(xiàn)狀及發(fā)展趨勢(shì)，通過對(duì)國(guó)內(nèi)外現(xiàn)有水質(zhì)檢測(cè)技術(shù)進(jìn)行詳盡對(duì)比分析的基礎(chǔ)上，本文提出了紫外-可見光譜法水質(zhì)多參數(shù)檢測(cè)的原理和方法技術(shù)及應(yīng)用，基此，系統(tǒng)、深入開展了紫外-可見光譜法水質(zhì)多參數(shù)檢測(cè)的水質(zhì)光譜處理、水質(zhì)參數(shù)解算等的關(guān)鍵技術(shù)問題研究。 ②研制了紫外-可見光譜法水質(zhì)多參數(shù)檢測(cè)的儀器系統(tǒng)。通過對(duì)紫外-可見光譜法水質(zhì)檢測(cè)的原理進(jìn)行詳細(xì)分析，研究了水質(zhì)多參數(shù)的檢測(cè)原理，分析了多參數(shù)光譜檢測(cè)的可行性。在此基礎(chǔ)上，構(gòu)建了水質(zhì)多參數(shù)檢測(cè)儀器系統(tǒng)的實(shí)現(xiàn)方案，設(shè)計(jì)、仿真、加工制作和測(cè)試了浸入式光程差分水質(zhì)檢測(cè)探頭。該探頭在進(jìn)行水質(zhì)光譜數(shù)據(jù)采集時(shí)，能有效地降低噪聲干擾，提高系統(tǒng)靈敏度，并能快速、準(zhǔn)確找出待測(cè)水體的敏感波長(zhǎng)范圍。通過采用以微型光纖光譜儀為核心的光譜測(cè)量單元，結(jié)合紫外-可見吸收光譜分析法，完成水樣的COD、TOC、TURB和NO3-N多參數(shù)檢測(cè)。同時(shí)，基于LabVIEW開發(fā)平臺(tái)，進(jìn)行系統(tǒng)軟件設(shè)計(jì)并進(jìn)行調(diào)試，實(shí)現(xiàn)了對(duì)流路、清洗、處理、顯示、存儲(chǔ)、打印及主控系統(tǒng)的儀器功能，此為光譜法水質(zhì)多參數(shù)檢測(cè)的實(shí)現(xiàn)提供了硬、軟件條件或平臺(tái)。 ③研究了基于小波包去噪的水質(zhì)光譜處理方法和多元散射校正的水質(zhì)光譜處理技術(shù)方法。針對(duì)地表水、城市生活污水中主要污染物在線檢測(cè)與控制的需求，以紫外-可見光譜法水質(zhì)COD、TOC、TURB和NO3-N多參數(shù)檢測(cè)為具體研究對(duì)象，在分析水質(zhì)光譜信息特征的基礎(chǔ)上，提出了基于小波包去噪的水質(zhì)光譜處理方法，借以提高水質(zhì)光譜的信噪比。研究結(jié)果表明，水樣的原始紫外-可見吸收光譜經(jīng)小波包去噪處理后，噪聲得到了明顯抑制，且特征得到了較好的保留。針對(duì)水中懸浮物對(duì)光譜的散射會(huì)對(duì)水樣的紫外-可見吸收光譜產(chǎn)生基線漂移、平移等，此將嚴(yán)重影響系統(tǒng)的穩(wěn)定性和檢測(cè)精度問題，進(jìn)而將直接影響光譜法對(duì)水質(zhì)COD的檢測(cè)。為此，研究了一種基于多元散射校正的水質(zhì)光譜處理方法。通過多元散射校正方法，可在不影響水樣紫外-可見吸收光譜特征的前提下，能夠?qū)λ袘腋∥镆鹕⑸涓蓴_或水質(zhì)濁度引起基線偏移的吸收光譜曲線進(jìn)行有效的校正。這不僅提高了光譜法檢測(cè)水質(zhì)COD的信噪比，而且還對(duì)化學(xué)計(jì)量法建立準(zhǔn)確有效的水質(zhì)檢測(cè)COD分析模型進(jìn)行了有效的數(shù)據(jù)預(yù)處理。 ④研究了主元分析進(jìn)行水質(zhì)光譜降維和最小二乘支持向量機(jī)對(duì)水質(zhì)參數(shù)軟測(cè)量建模的水質(zhì)光譜處理方法技術(shù)。由于水質(zhì)紫外-可見光譜通過小波包去噪和多元散射校正后，依然存在水質(zhì)光譜采集的冗余及多重共線問題，應(yīng)用主元分析方法對(duì)水質(zhì)光譜信號(hào)進(jìn)行降維處理，再應(yīng)用最小二乘支持向量機(jī)對(duì)水質(zhì)參數(shù)COD進(jìn)行軟測(cè)量建模。研究結(jié)果表明，經(jīng)主元分析方法降維處理后的水質(zhì)光譜數(shù)據(jù)，去除了冗余信息，保留了有效特征，在此基礎(chǔ)上，應(yīng)用最小二乘支持向量機(jī)進(jìn)行水質(zhì)參數(shù)的軟測(cè)量建模，可以提高系統(tǒng)的建模精度和水質(zhì)COD參數(shù)的解算精度。 ⑤開展了紫外-可見光譜法水質(zhì)多參數(shù)檢測(cè)儀器樣機(jī)的性能測(cè)試研究工作。為了確保紫外-可見光譜法水質(zhì)多參數(shù)檢測(cè)儀器系統(tǒng)的有效、穩(wěn)定運(yùn)行，需要依據(jù)相關(guān)標(biāo)準(zhǔn)，對(duì)研制的儀器樣機(jī)的性能進(jìn)行測(cè)試。測(cè)試結(jié)果表明，儀器樣機(jī)對(duì)COD即化學(xué)需氧量標(biāo)液的測(cè)試精度小于4.70%，重復(fù)性小于1.43%；對(duì)TOC即總有機(jī)碳的測(cè)試精度小于2.69%，重復(fù)性小于1.98%；對(duì)TURB即濁度的測(cè)試精度小于4.78%，重復(fù)性小于1.55%；對(duì)NO3-N即硝酸鹽氮的測(cè)試精度小于4.67%，重復(fù)性小于2.92%�？梢姡兄频膬x器樣機(jī)性能指標(biāo)，不僅達(dá)到了立項(xiàng)研究項(xiàng)目《任務(wù)書》的設(shè)計(jì)要求，而且由中國(guó)測(cè)試技術(shù)研究院化學(xué)研究所出具的測(cè)試報(bào)告證明，性能指標(biāo)滿足我國(guó)及行業(yè)的有關(guān)標(biāo)準(zhǔn)規(guī)范。 本文將光譜學(xué)、光電技術(shù)、環(huán)境科學(xué)、化學(xué)計(jì)量方法、信號(hào)分析與處理等學(xué)科專業(yè)知識(shí)進(jìn)行了有機(jī)結(jié)合，率先在國(guó)內(nèi)研究并構(gòu)建了基于紫外-可見光譜法水質(zhì)多參數(shù)檢測(cè)儀器系統(tǒng)。論文研究成果——研制的儀器樣機(jī)，，已通過了四川省科技廳組織專家的成果鑒定，這對(duì)進(jìn)一步開展紫外-可見光譜水質(zhì)多參數(shù)檢測(cè)的理論、儀器、方法技術(shù)及應(yīng)用研究工作，具有重要的理論和現(xiàn)實(shí)意義。
文內(nèi)圖片：
圖片說明：013年十大流域水質(zhì)狀況
[Abstract]:Water is the source of life, and human is inseparable from water in life and production activities. However, with the rapid development of China's economy and the acceleration of the process of urbanization, the environmental pollution of the exposed water is becoming more and more serious. The quality of water is not only closely related to the safety of industrial and agricultural production and human health, but also on the quality detection technology to judge, predict and monitor the quality of water. It is true that conventional instrument detection equipment can detect water quality parameters, but generally only a single parameter is measured Quantity. For example, the detection of parameters such as COD, TOC, TURB and NO3-N of water quality, which usually requires separate measurement of equipment such as COD analyzer, TOC analyzer, turbidity meter, and NO3-N analyzer, is not only detrimental to the integration of the data, but also increases the detection. In recent years, the ultraviolet-visible-light absorption spectrum method, which is one of the water quality detection techniques for spectral analysis, has not only discarded the water samples such as chemical analysis and electrochemical analysis and chromatographic analysis, but also has the advantages of complex pretreatment, long measurement period and many chemical reagents needed. the invention also has the advantages of high detection speed, low cost and can realize on-line and in-situ measurement and the like, However, the present ultraviolet-visible-light absorption spectrum method is generally used for on-line detection of single parameter, and the multi-parameter simultaneous on-line inspection of water quality COD, TOC, TURB and NO3-N cannot be achieved in China Test. In the "Development and product development of multi-functional water quality real-time automatic monitoring technology" of Sichuan Science and Technology Support Project (Project No.:2012 SZ0111) and the "Development of on-line automatic monitor for spectral multi-parameter water quality" (Contract No.:1042012920140453) of the horizontal cooperation scientific research project of Sichuan Biang Technology Co., Ltd. and the "Study on the Structure and Characteristics of SFL-Contourlet" of the National Natural Science Foundation of China (Approval No.:61201346) The theory, apparatus, method and application of the multi-parameter detection of UV-visible spectral water quality are carried out with the aid of the aid of the financial support, and a set of data collection, water quality spectrum treatment and water quality parameter calculation covering water quality spectrum data acquisition, water quality spectrum treatment and water quality parameter calculation are developed. The system of multi-parameter detection of the water quality of the complete flow is detected by the multi-parameter detection of the actual water quality, and the system has the full self-knowledge. Know the property right. The research content of the paper, the main In order to include: the present situation and the development trend of the domestic and foreign research on the detection of water quality parameters of the spectrum or the spectral technique are set forth, and the score of the existing water quality detection technology at home and abroad is analyzed in detail. On the basis of the analysis, this paper puts forward the principle and method of the multi-parameter detection of water quality of ultraviolet-visible spectrum, and the key techniques such as water quality spectrum treatment, water quality parameter calculation and so on are carried out in this paper. The study of the problem of operation has developed the multi-parameter of the water quality of the ultraviolet-visible spectrum. The principle of multi-parameter detection of water quality is studied by analyzing the principle of water quality detection of ultraviolet-visible spectrum, and the multi-parameter light is analyzed. On the basis of this, the realization plan, design, simulation and processing of the water quality multi-parameter detection instrument system are constructed, and the immersion type optical path difference is designed, simulated, processed and tested. the water quality detection probe can effectively reduce the noise interference, improve the system sensitivity, and can quickly and accurately find the water body to be detected when the water quality spectrum data acquisition is carried out, And the COD, TOC, TURB and NO3 of the water sample are finished by adopting a spectral measurement unit which is a core of the micro-optical fiber spectrometer and combining the ultraviolet-visible absorption spectrum analysis method. and based on the LabVIEW development platform, the system software is designed and debugged, and the instrument functions of the convection circuit, the cleaning, the processing, the display, the storage, the printing and the main control system are realized, The water quality spectrum processing method based on wavelet packet de-noising and the water of multi-element scattering correction are studied in this paper. According to the requirement of on-line detection and control of main pollutants in surface water and urban domestic sewage, the water quality COD, TOC, TURB and NO3-N multi-parameter of the ultraviolet-visible spectrum are detected as specific research objects, and the water quality light is analyzed On the basis of the characteristic of spectral information, a method of water quality spectrum processing based on wavelet packet de-noising is proposed, The signal-to-noise ratio of the high water-quality spectrum is obtained. The results show that the original UV-visible absorption spectrum of the water sample is obviously inhibited by the wavelet packet de-noising process, and the signal-to-noise ratio of the high-water-quality spectrum is very low. A good retention is obtained. In view of the scattering of the suspended matter on the spectrum, the base line drift, translation, etc. can be caused to the ultraviolet-visible absorption spectrum of the water sample, which will seriously affect the stability and the detection accuracy of the system, and then the direct influence spectroscopy will be obtained. In this paper, a kind of multi-element scattering correction is studied in this paper. By means of a multi-element scattering correction method, the absorption spectrum of the baseline offset caused by scattering interference or water quality turbidity can be caused to the suspended matter in water under the premise of not affecting the characteristics of the ultraviolet-visible absorption spectrum of the water sample. The method not only improves the signal-to-noise ratio of the COD of the water quality detected by the spectrum, but also establishes an accurate and effective water quality detection COD analysis model for the chemical measurement method. In this paper, effective data pre-processing is presented in this paper. The model of water quality parameter soft measurement by the least square support vector machine for water quality spectrum reduction by the principal component analysis is studied. Because the ultraviolet-visible spectrum of the water quality is corrected by the wavelet packet de-noising and the multi-element scattering, the redundant and multiple co-linear problems of the water quality spectrum acquisition still exist, and the main element analysis method is applied to water, carrying out dimension reduction processing on the quality spectrum signal, and then applying the least square support vector machine to the water quality parameter; In this paper, the soft measurement and modeling of the number of COD are carried out. The results show that the data of the water quality is reduced by the principal component analysis method, the redundant information is removed, and the effective characteristics are reserved. On the basis of this, the least-squares support vector machine is applied. Soft measurement and modeling of water quality parameters can improve the modeling precision and water quality of the system The solution precision of the parameters of the quality of the COD is determined. The multi-parameter detection of the water quality of the ultraviolet-visible spectrum is carried out. In order to ensure the effective and stable operation of the instrument system of the multi-parameter detection of the water quality of the ultraviolet-visible spectrum, it is necessary to study the performance of the instrument prototype according to the relevant standards. The test results show that the test precision of the instrument prototype is less than 4.70% and the repeatability is less than 1.43%. The test precision of TOC, which is the total organic carbon, is less than 2.69%, the repeatability is less than 1.98%, and the test precision for TURB is less than 4.7. 8%, the repeatability is less than 1.55%; the test precision for NO3-N, i.e. nitrate nitrogen, is less than 4.6 7%, the repeatability is less than 2.92%. It can be seen that the performance index of the developed instrument prototype not only meets the design requirements of the project for project initiation and research, but also the test report issued by the Institute of Chemical Research of the China Institute of Testing and Technology has proved that the performance index is full In this paper, we combine the professional knowledge of spectroscopy, electro-optical technology, environmental science, chemical measurement method, signal analysis and treatment, and take the lead in the research and construction of ultraviolet-can in China. The instrument system of multi-parameter detection of water quality is presented in this paper. The research results of the instrument and the prototype of the instrument have passed the fruit identification of the experts of the scientific and technological department of Sichuan province, and the theory, the instrument, the method and the application of the multi-parameter detection of the ultraviolet-visible spectrum water quality have been further carried out.
【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：O433

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 黎洪松;劉俊;;水質(zhì)檢測(cè)傳感器研究的新進(jìn)展[J];傳感器與微系統(tǒng);2012年03期

2 崔建升,郭玉鳳,王振川,王曉輝;市政污水TOC與COD相關(guān)性[J];城市環(huán)境與城市生態(tài);2003年06期

3 傅連進(jìn);紫外分光光度法同時(shí)測(cè)定生活飲用水中的硝酸鹽氮和亞硝酸鹽氮[J];城市環(huán)境與城市生態(tài);2004年04期

4 丁興號(hào),鄧善熙,楊永躍;基于小波包的圖像去噪方法[J];電子測(cè)量與儀器學(xué)報(bào);2003年02期

5 廖海洋;杜宇;溫志渝;;嵌入式多參數(shù)微小型水質(zhì)監(jiān)測(cè)系統(tǒng)的設(shè)計(jì)[J];電子技術(shù)應(yīng)用;2011年01期

6 林星杰;楊慧芬;宋存義;;UV_(254)在水質(zhì)監(jiān)測(cè)中應(yīng)用的研究[J];能源與環(huán)境;2006年01期

7 方力,張燕,丁佳,姚照兵;紫外分光光度法同時(shí)測(cè)定硝酸鹽氮和亞硝酸鹽氮[J];分析測(cè)試技術(shù)與儀器;1999年03期

8 劉立行;李萍;許文貴;盧紅艷;;多波長(zhǎng)線性回歸——階導(dǎo)數(shù)分光光度法同時(shí)測(cè)定水中 NO_3~-和 NO_2~-[J];分析化學(xué);1991年10期

9 高若梅,劉鴻皋;檢出限概念問題討論——IUPAC及其它檢出限定義的綜合探討和實(shí)驗(yàn)論證[J];分析化學(xué);1993年10期

10 袁濤;劉中原;胡連哲;徐國(guó)寶;;電化學(xué)和電化學(xué)發(fā)光核酸適體傳感器[J];分析化學(xué);2011年07期

相關(guān)博士學(xué)位論文 前1條

1 李修亮;軟測(cè)量建模方法研究與應(yīng)用[D];浙江大學(xué);2009年

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