深海原位激光拉曼光谱系统机械结构设计及海上试验关键问题研究
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摘要
海洋研究主要围绕三个中心问题：海洋权益、海洋资源、海洋环境。国际间以开发和占有深海资源为核心的海洋维权斗争愈演愈烈,而与之相伴的深海技术实力的较量也日益凸显。
深海原位激光拉曼光谱系统可搭载于水下运载器,能够应用于各种深海和极端环境下海底岩石、矿床、间隙水等多种介质的成分分析,是海底固、液、气态目标物的水下原位快速探测的重要技术手段。对相关技术的发展和现状做出总览,指出了目前国内外同类研究中存在的共性与拟解决的问题。本文基于国家863项目“深海原位激光拉曼光谱系统”的研究工作,针对深海原位激光拉曼光谱系统需求,对相关的机械结构设计及海上试验关键问题进行了研究探索,以期为深海原位拉曼光谱探测机械架装海试及样品释放提供有价值的参考。
本文首先介绍了深海原位激光拉曼光谱系统的主要结构、功能及技术指标,着重介绍了与本文工作密切相关的机械架装设计、释样系统设计及海试检验等关键技术。
第三章设计了可用于浅海原理样机的仪器舱及架装结构,确定了舱体尺寸及内部设备的一系列重要参数,为深海原位激光拉曼光谱系统样机设计奠定了良好基础。在此基础上,根据深海样机的机械技术指标,通过对搭载平台的功能、结构、尺寸、承重等方面深入分析,研究了系统与海上试验搭载平台的融合技术,并对深海样机架构进行了模块化、集成化改进与创新,设计了适用于深海环境试验样机的仪器舱。并对关系到系统正常运行的待机唤醒装置、钢丝绳长度及张力调整进行了详细阐述。
在海洋仪器原位探测性能测试评价过程中,自带样品试验是重要的一环,对于将仪器推向实际应用是不可或缺的。本文第四章研制了可与深海原位激光拉曼光谱仪联合工作的释样机构,实现了深海化学物质原位快速探测性能的评测。通过采用标准气缸作为样品盛装容器,借用海鸟采水器动作原理,利用弹簧拉力将样品排放至探测区域,并配合样品缓存装置,根据拉曼峰强度随着样品扩散的变化性质,反演其浓度随着时间的变化规律。该方案规避了深海环境携带样品必须考虑的高压密封限制,成功解决了高压环境下样品难以释放的问题,试验结果验证了释样系统设计的可靠性及合理性,满足了“耐压、释放动作简单、可重复使用、成本低”的要求。另外,设计了样品缓存装置,保证释放样品与海水混合后再扩散到探测窗口,同时限制样品扩散区域,延长光谱探测系统可获取自带样品拉曼光谱时间。
作为该系统的未来发展方向之一就是搭载ROV进行海底原位探测甚至长期观测。为了使仪器设备舱能够稳固地施放于海底,或着床后能进行姿态调整以获得最佳的工作状态,对设备舱姿态(三维倾角)的精确检测便成为至关重要的技术环节。该项测量对其他海底探测长期工作站的吊装施放也是必要的,施放设备的倾角监测数据可为甲板操作提供一个可靠的判断依据,以保证施放过程的安全和系统的准确定位。本文第五章对深海海底原位观测站倾角测量优化设计进行了预研。采用差动输入运算放大器形式,通过分区间对倾角数据进行A/D转换,使分辨率大幅提高,实现了全角度范围内精确采集倾角数据,尤其在敏感轴与1g接近平行时的分辨率优于0.5°,并在实验室测试中得到了满意的结果,为海底原位观测站获得最佳工作状态奠定了基础。
作为后期工作展望,在对论文工作进行总结的基础上,从工程样机小型化、释样与探测时刻时间差及气体释样三个方面提出了进一步努力方向：选用新材料进行结构及耐压优化设计；采用自主释样方式,对释样时刻及释样量实行精确地自动控制,实现零时差原位探测；研究深海环境脱气处理方法。
The marine studies center around three major issues:the maritime rights and interests, ocean resources and marine environments. The protection of the rights to exploit and occupy marine resources is bringing about more conflicts among countries, and the deep-ocean technology is coming to the forefront in the competition.
The Deep Ocean Compact Automatic Raman Spectrometer can be widely applied in various kinds of deep ocean environments, both normal and extreme. When carried by the underwater vehicles, the Spectrometer is capable of analyzing the components of such media as seabed rocks, mineral deposits and interstitial water, so the rapid in-situ detection of solid, liquid and gaseous undersea objects is available. Based on the national 863 project "The Deep Ocean Compact Automatic Raman Spectrometer", this thesis studies the mechanical structure design of the spectrometer and critical issues in sea tests, in order to provide valuable reference to the construction, testing and sample releasing of this spectrometer in related researches.
The thesis firstly introduces the main structure, function and specifications of the Deep Ocean Compact Automatic Raman Spectrometer, and focuses on several key technologies such as the frame structure design, sample release system design and sea trial testing.
In chapter three, the equipment cabin and the frame structure of a prototype that can work in the shallow sea are designed, and some key parameters about the cabin size and internal devices are fixed, which serves as good preparations for the prototype design targeted at deep-sea activities. On this basis, according to the technical specifications of the deep-sea prototype, more analyses are made on the functionality, structure, size and load-bearing of the carrying platform, and the integration of the Spectrometer and the platform is further studied. An equipment cabin of the prototype designed for deep-sea environment is constructed through modularization, integration and innovation on the original prototype. In addition, the thesis also discusses the standby wake-up device as well as length and tension adjustment of the wire rope, which are crucial to the normal functioning of the system.
In the performance evaluation process, the sample release device is an important link, and it is indispensible to the practical application of the Spectrometer. In order to evaluate the system's performance in rapid in-situ deep-sea detection, a sample release mechanism is developed in the forth chapter to cooperate with the Spectrometer. It uses a standard air cylinder to hold samples, and releases the sample into the testing area with the force of mechanical spring. This mechanism satisfies the requirements of resistance to pressure, simple release action, reusability and low cost. Additionally, accommodating the SBE's release action, this scheme avoids the concerns on pressure-bearing and sealing in deep-sea environment, and successfully deals with sample release problem in high-pressure surroundings. According to the property that the amplitude of Raman Peaks varies with the spread of samples and with the help of the sample cache device, the variation of density with time can be deduced, and thus the correctness and reliability of the sample release system are proved. Moreover, a sample cache device is invented to ensure that the sample spreads to the detection window again after blending with sea water. The device also restricts the spread area, so extends the time that the Spectrometer is exposed to the Raman spectroscopy of the self-prepared sample.
Carrying an ROV to conduct undersea in-situ detection and even long-term observation is one of the future development of the System. In this situation, the equipment cabin needs to be placed stably under the sea, or to adjust its own posture after reaching the bottom of the sea, so the precise measurement of the cabin's posture (three dimensional dip angle) becomes one of the most essential technological task. The measurement of the angle is also of great importance to the lifting and placing of other undersea long-term workstations, as such data provides reference to on-deck operations to ensure the safety and accurate location of the placement of devices. The fifth chapter discusses the pre-researches on how to optimize the dip angle measurement of the deep-sea in-situ observation station. With the differential-input operational amplifier and A/D conversion in separate domains, the resolution is greatly improved, making possible the precise acquisition of dip-angle data in all ranges. The lab observation is very satisfactory especially when the sensitive axis is approximately parallel with 1g (gravity), where the resolution can be improved to better than 0.5°. With sufficient energy supply, the observation station adjusts its posture based on the dip-angle data acquired, so as to maintain the best working status of the in-situ detection.
The last part of the thesis summarizes the discussions above and proposes some topics worth further researches from three perspectives:miniaturization of engineering prototypes, time difference between sample release and detection, and gaseous sample release. New materials shall be used to optimize the structure and pressure resistance design. In order to precisely and automatically control the time and dose of sample release, and to reduce the time difference of in-situ detection to zero, an automatic mechanism should be adopted. Moreover, the degassing technique in the deep-sea environment should be further studied. Keywords:laser Raman spectroscopy; in-situ detection in deep-sea; pressure test; seal; sample release; sea trial
深海原位激光拉曼光谱系统可搭载于水下运载器,能够应用于各种深海和极端环境下海底岩石、矿床、间隙水等多种介质的成分分析,是海底固、液、气态目标物的水下原位快速探测的重要技术手段。对相关技术的发展和现状做出总览,指出了目前国内外同类研究中存在的共性与拟解决的问题。本文基于国家863项目“深海原位激光拉曼光谱系统”的研究工作,针对深海原位激光拉曼光谱系统需求,对相关的机械结构设计及海上试验关键问题进行了研究探索,以期为深海原位拉曼光谱探测机械架装海试及样品释放提供有价值的参考。
本文首先介绍了深海原位激光拉曼光谱系统的主要结构、功能及技术指标,着重介绍了与本文工作密切相关的机械架装设计、释样系统设计及海试检验等关键技术。
第三章设计了可用于浅海原理样机的仪器舱及架装结构,确定了舱体尺寸及内部设备的一系列重要参数,为深海原位激光拉曼光谱系统样机设计奠定了良好基础。在此基础上,根据深海样机的机械技术指标,通过对搭载平台的功能、结构、尺寸、承重等方面深入分析,研究了系统与海上试验搭载平台的融合技术,并对深海样机架构进行了模块化、集成化改进与创新,设计了适用于深海环境试验样机的仪器舱。并对关系到系统正常运行的待机唤醒装置、钢丝绳长度及张力调整进行了详细阐述。
在海洋仪器原位探测性能测试评价过程中,自带样品试验是重要的一环,对于将仪器推向实际应用是不可或缺的。本文第四章研制了可与深海原位激光拉曼光谱仪联合工作的释样机构,实现了深海化学物质原位快速探测性能的评测。通过采用标准气缸作为样品盛装容器,借用海鸟采水器动作原理,利用弹簧拉力将样品排放至探测区域,并配合样品缓存装置,根据拉曼峰强度随着样品扩散的变化性质,反演其浓度随着时间的变化规律。该方案规避了深海环境携带样品必须考虑的高压密封限制,成功解决了高压环境下样品难以释放的问题,试验结果验证了释样系统设计的可靠性及合理性,满足了“耐压、释放动作简单、可重复使用、成本低”的要求。另外,设计了样品缓存装置,保证释放样品与海水混合后再扩散到探测窗口,同时限制样品扩散区域,延长光谱探测系统可获取自带样品拉曼光谱时间。
作为该系统的未来发展方向之一就是搭载ROV进行海底原位探测甚至长期观测。为了使仪器设备舱能够稳固地施放于海底,或着床后能进行姿态调整以获得最佳的工作状态,对设备舱姿态(三维倾角)的精确检测便成为至关重要的技术环节。该项测量对其他海底探测长期工作站的吊装施放也是必要的,施放设备的倾角监测数据可为甲板操作提供一个可靠的判断依据,以保证施放过程的安全和系统的准确定位。本文第五章对深海海底原位观测站倾角测量优化设计进行了预研。采用差动输入运算放大器形式,通过分区间对倾角数据进行A/D转换,使分辨率大幅提高,实现了全角度范围内精确采集倾角数据,尤其在敏感轴与1g接近平行时的分辨率优于0.5°,并在实验室测试中得到了满意的结果,为海底原位观测站获得最佳工作状态奠定了基础。
作为后期工作展望,在对论文工作进行总结的基础上,从工程样机小型化、释样与探测时刻时间差及气体释样三个方面提出了进一步努力方向：选用新材料进行结构及耐压优化设计；采用自主释样方式,对释样时刻及释样量实行精确地自动控制,实现零时差原位探测；研究深海环境脱气处理方法。
The marine studies center around three major issues:the maritime rights and interests, ocean resources and marine environments. The protection of the rights to exploit and occupy marine resources is bringing about more conflicts among countries, and the deep-ocean technology is coming to the forefront in the competition.
The Deep Ocean Compact Automatic Raman Spectrometer can be widely applied in various kinds of deep ocean environments, both normal and extreme. When carried by the underwater vehicles, the Spectrometer is capable of analyzing the components of such media as seabed rocks, mineral deposits and interstitial water, so the rapid in-situ detection of solid, liquid and gaseous undersea objects is available. Based on the national 863 project "The Deep Ocean Compact Automatic Raman Spectrometer", this thesis studies the mechanical structure design of the spectrometer and critical issues in sea tests, in order to provide valuable reference to the construction, testing and sample releasing of this spectrometer in related researches.
The thesis firstly introduces the main structure, function and specifications of the Deep Ocean Compact Automatic Raman Spectrometer, and focuses on several key technologies such as the frame structure design, sample release system design and sea trial testing.
In chapter three, the equipment cabin and the frame structure of a prototype that can work in the shallow sea are designed, and some key parameters about the cabin size and internal devices are fixed, which serves as good preparations for the prototype design targeted at deep-sea activities. On this basis, according to the technical specifications of the deep-sea prototype, more analyses are made on the functionality, structure, size and load-bearing of the carrying platform, and the integration of the Spectrometer and the platform is further studied. An equipment cabin of the prototype designed for deep-sea environment is constructed through modularization, integration and innovation on the original prototype. In addition, the thesis also discusses the standby wake-up device as well as length and tension adjustment of the wire rope, which are crucial to the normal functioning of the system.
In the performance evaluation process, the sample release device is an important link, and it is indispensible to the practical application of the Spectrometer. In order to evaluate the system's performance in rapid in-situ deep-sea detection, a sample release mechanism is developed in the forth chapter to cooperate with the Spectrometer. It uses a standard air cylinder to hold samples, and releases the sample into the testing area with the force of mechanical spring. This mechanism satisfies the requirements of resistance to pressure, simple release action, reusability and low cost. Additionally, accommodating the SBE's release action, this scheme avoids the concerns on pressure-bearing and sealing in deep-sea environment, and successfully deals with sample release problem in high-pressure surroundings. According to the property that the amplitude of Raman Peaks varies with the spread of samples and with the help of the sample cache device, the variation of density with time can be deduced, and thus the correctness and reliability of the sample release system are proved. Moreover, a sample cache device is invented to ensure that the sample spreads to the detection window again after blending with sea water. The device also restricts the spread area, so extends the time that the Spectrometer is exposed to the Raman spectroscopy of the self-prepared sample.
Carrying an ROV to conduct undersea in-situ detection and even long-term observation is one of the future development of the System. In this situation, the equipment cabin needs to be placed stably under the sea, or to adjust its own posture after reaching the bottom of the sea, so the precise measurement of the cabin's posture (three dimensional dip angle) becomes one of the most essential technological task. The measurement of the angle is also of great importance to the lifting and placing of other undersea long-term workstations, as such data provides reference to on-deck operations to ensure the safety and accurate location of the placement of devices. The fifth chapter discusses the pre-researches on how to optimize the dip angle measurement of the deep-sea in-situ observation station. With the differential-input operational amplifier and A/D conversion in separate domains, the resolution is greatly improved, making possible the precise acquisition of dip-angle data in all ranges. The lab observation is very satisfactory especially when the sensitive axis is approximately parallel with 1g (gravity), where the resolution can be improved to better than 0.5°. With sufficient energy supply, the observation station adjusts its posture based on the dip-angle data acquired, so as to maintain the best working status of the in-situ detection.
The last part of the thesis summarizes the discussions above and proposes some topics worth further researches from three perspectives:miniaturization of engineering prototypes, time difference between sample release and detection, and gaseous sample release. New materials shall be used to optimize the structure and pressure resistance design. In order to precisely and automatically control the time and dose of sample release, and to reduce the time difference of in-situ detection to zero, an automatic mechanism should be adopted. Moreover, the degassing technique in the deep-sea environment should be further studied. Keywords:laser Raman spectroscopy; in-situ detection in deep-sea; pressure test; seal; sample release; sea trial
引文
[1]R. M. Haymon and K. C. Macdonald, The Geology of Dee-Sea Hot Springs, American Scientist,1985, 73(441-449);
[2]吴世迎,世界海底热液硫化物资源,海洋出版社,2000；
[3]Seth G. John, Olivier J. Rouxel, Paul R. Craddock, et al., Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys, Earth and Planetary Science Letters,2008,269(1-2):17-28;
[4]冯士榨,李凤岐and李少菁,海洋科学导论,高等教育出版社,1999；
[5]徐肖梅,海洋技术概论,科学出版社,2000；
[6]Rene Born, Hermann Ehrlich, Vasiliy Bazhenov, et al., Investigation of nanoorganized biomaterials of marine origin, Arabian Journal of Chemistry,2010,3(1):27-32;
[7]Walter S. Borowski, Charles K. Paull and William Ussler, Global and local variations of interstitial sulfate gradients in deep-water, continental margin sediments:Sensitivity to underlying methane and gas hydrates, Marine Geology,1999,159(1-4):131-154;
[8]M. Kinoshita, R. P. Von Herzen, O. Matsubayashi, et al., Tidally-driven effluent detected by long-term temperature monitoring at the TAG hydrothermal mound, Mid-Atlantic Ridge, Physics of the earth and planetary interiors,1998,108(2):143-154;
[9]N. Le Bris, P. M. Sarradin, D. Birot, et al., A new chemical analyzer for in situ measurement of nitrate and total sulfide over hydrothermal vent biological communities. Marine Chemistry,2000,72(1):1-15;
[10]Andrew J. Reed, Ruth Dorn, Cindy L. Van Dover, et al., Phylogenetic diversity of methanogenic, sulfate-reducing and methanotrophic prokaryotes from deep-sea hydrothermal vents and cold seeps, Deep Sea Research Part Ⅱ:Topical Studies in Oceanography,2009,56(19-20):1665-1674;
[11]Christopher R. German, Dana R. Yoerger, Michael Jakuba, et al., Hydrothermal exploration with the Autonomous Benthic Explorer, Deep Sea Research Part I:Oceanographic Research Papers,2008, 55(2):203-219;
[12]C. Bachraty, P. Legendre and D. Desbruyeres, Biogeographic relationships among deep-sea hydrothermal vent faunas at global scale, Deep Sea Research Part Ⅰ:Oceanographic Research Papers, 2009,56(8):1371-1378;
[13]Jory Bell, Joe Betts and Edward Boyle, MITESS:a moored in situ trace element serial sampler for deep-sea moorings, Deep Sea Research Part I:Oceanographic Research Papers,2002, 49(11):2103-2118;
[14]D. O. B. Jones, B. J. Bett, R. B. Wynn, et al., The use of towed camera platforms in deep-water science, Underwater Technology,2009,28(2):41-50;
[15]T. Marsset, B. Marsset, S. Ker, et al., High and very high resolution deep-towed seismic system: Performance and examples from deep water Geohazard studies, Deep Sea Research Part Ⅰ: Oceanographic Research Papers,2010,57(4):628-637;
[16]J. M. Schicks, M. A. Ziemann, H. Lu, et al., Raman spectroscopic investigations on natural samples from the Integrated Ocean Drilling Program (IODP) Expedition 311:Indications for heterogeneous compositions in hydrate crystals, Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2010,77(5):973-977;
[17]K. C. Hester, R. M. Dunk, P. M. Walz, et al.. Direct measurements of multi-component hydrates on the seafloor:Pathways to growth, Fluid Phase Equilibria,2007,261(1-2):396-406;
[18]J. D. Irish and F. E. Snodgrass, Quartz crystals as multipurpose oceanographic sensors--Ⅰ. pressure, Deep Sea Research and Oceanographic Abstracts,1972,19(2):165-169;
[19]K. Ding, W. E. Seyfried Jr, M. K. Tivey, et al., In situ measurement of dissolved H2 and H2S in high-temperature hydrothermal vent fluids at the Main Endeavour Field, Juan de Fuca Ridge, Earth and Planetary Science Letters,2001,186(3-4):417-425;
[20]叶瑛,陈鹰,杨灿军，et al.,适用于深海热液环境的全固态电化学传感器的研究进展,自然科学进 展,2004,02)：；
[21]陈鹰,杨灿军,顾临怡,et al.,基于载人潜水器的深海资源勘探作业技术研究,机械工程学报,2003，11：38-42；
[22]Maciej Sosna, Guy Denuault, Robin W. Pascal, et al., Development of a reliable microelectrode dissolved oxygen sensor, Sensors and Actuators B:Chemical,2007,123(1):344-351;
[23]K. Grasshoff, M. Ehrhardt, K. Kremling, et al., Methods of seawater analysis, Wiley Online Library, 1976;
[24]Kang Ding, William E. Seyfried Jr, Zhong Zhang, et al., The in situ pH of hydrothermal fluids at mid-ocean ridges, Earth and Planetary Science Letters,2005,237(1-2):167-174;
[25]M. Benounis, N. Jaffrezic-Renault, J. P. Dutasta, et al., Study of a new evanescent wave optical fibre sensor for methane detection based on cryptophane molecules, Sensors and Actuators B:Chemical, 2005,107(1):32-39;
[26]G. P. Klinkhammer, Fiber optic spectrometers for in-situ measurements in the oceans:the ZAPS Probe, Marine Chemistry,1994,47(1):13-20;
[27]Zhong Chen, Chi-Yue Huang, Meixun Zhao, et al., Characteristics and possible origin of native aluminum in cold seep sediments from the northeastern South China Sea, Journal of Asian Earth Sciences,2011,40(1):363-370;
[28]V. Barale, P. Cipollini, A. Davidov, et al., Water Constituents in the North-western Black Sea from Optical Remote Sensing and In situ Data, Estuarine, Coastal and Shelf Science,2002,54(3):309-320;
[29]Sheri N. White, Laser Raman spectroscopy as a technique for identification of seafloor hydrothermal and cold seep minerals, Chemical Geology,2009,259(3-4):240-252;
[30]M. Hannington, P. Herzig, P. Stoffers, et al., First observations of high-temperature submarine hydrothermal vents and massive anhydrite deposits off the north coast of Iceland, Marine Geology, 2001,177(3-4):199-220;
[31]J. Sarrazin, P. Rodier, M. K. Tivey, et al., A dual sensor device to estimate fluid flow velocity at diffuse hydrothermal vents, Deep Sea Research Part I:Oceanographic Research Papers,2009, 56(11):2065-2074;
[32]C. R. German, J. Hergt, M. R. Palmer, et al., Geochemistry of a hydrothermal sediment core from the OBS vent-field,21°N East Pacific Rise, Chemical Geology,1999,155(1-2):65-75;
[33]James P. Cowen, Xiyuan Wen and Brian N. Popp, Methane in aging hydrothermal plumes, Geochimica et Cosmochimica Acta,2002,66(20):3563-3571;
[34]H. W. Bange, R. Ramesh, S. Rapsomanikis, et al., Methane in surface waters of the Arabian Sea, Geophys. Res. Lett.,1998,25(19):3547-3550;
[35]Ralf D. Prien, The future of chemical in situ sensors, Marine Chemistry,2007.107(3):422-432;
[36]U. Tsunogai, N. Yoshida and T. Gamo, Carbon isotopic evidence of methane oxidation through sulfate reduction in sediment beneath cold seep vents on the seafloor at Nankai Trough, Marine Geology,2002, 187(1-2):145-160;
[37]J. A. Breier, C. R. German and S. N. White, Mineral phase analysis of deep-sea hydrothermal particulates by a Raman spectroscopy expert algorithm:Toward autonomous in situ experimentation and exploration, Geochem. Geophys. Geosyst.,2009,10(5):Q05T05;
[38]Xin Zhang, Peter M. Walz, William J. Kirkwood, et al., Development and deployment of a deep-sea Raman probe for measurement of pore water geochemistry. Deep Sea Research Part I:Oceanographic Research Papers,2010,57(2):297-306;
[39]Christophe Bourry, Bertrand Chazallon, Jean Luc Charlou, et al., Free gas and gas hydrates from the Sea of Marmara, Turkey:Chemical and structural characterization, Chemical Geology,2009, 264(1-4):197-206;
[40]J. L. Charlou, J. P. Donval, Y. Fouquet, et al., Physical and chemical characterization of gas hydrates and associated methane plumes in the Congo-Angola Basin, Chemical Geology,2004, 205(3-4):405-425;
[41]Jill Pasteris, Brigitte Wopenka, John J. Freeman, et al., Raman Spectroscopy in the Deep Ocean: Successes and Challenges, Appl. Spectrosc.,2004,58(7):195A-208A;
[42]J. D. Pasteris, B. Wopenka, J. J. Freeman, et al., Spectroscopic success and challenges:Raman spectroscopy at 3.6 km depth in the ocean, Appl. Spectrosc,2004,58(7):;
[43]S. N. White, P. G. Brewer and E. T. Peltzer, Determination of gas bubble fractionation rates in the deep ocean by laser Raman spectroscopy, Marine Chemistry,2006,99(1-4):12-23;
[44]Josh N. Plant, Kenneth S. Johnson, Steve E. Fitzwater, et al., Tidally oscillating bisulfide fluxes and fluid flow rates observed with in situ chemical sensors at a warm spring in Monterey Bay, California, Deep Sea Research Part Ⅰ:Oceanographic Research Papers,2010,57(12):1585-1595;
[45]S. N. White, R. M. Dunk, E. T. Peltzer, et al., In situ Raman analyses of deep-sea hydrothermal and cold seep systems (Gorda Ridge and Hydrate Ridge),2006,;
[46]Sheri N. White, Qualitative and Quantitative Analysis of CO2 and CH4 Dissolved in Water and Seawater Using Laser Raman Spectroscopy, Appl. Spectrosc.,2010,64(7):819-827;
[47]Peter G. Brewer, George Malby, Jill D. Pasteris, et al., Development of a laser Raman spectrometer for deep-ocean science, Deep Sea Research Part Ⅰ:Oceanographic Research Papers,2004,51(5):739-753;
[48]A. D. Sherman, P. M. Walz and P. G. Brewer, Two Generations of Deep-Ocean Raman In-Situ Spectrometers, Sea Technology,2007,48(2):10-13;
[49]J. Santos Gomez, Nonlinear Raman Spectroscopy, Theory, Academic Press,1999;
[50]R. M. Dunk, E. T. Peltzer, P. M. Walz, et al., Seeing a deep ocean CO2 enrichment experiment in a new light:laser Raman detection of dissolved CO2 in seawater, Environmental science & technology,2005, 39(24):9630-9636;
[51]吕万军,I-Ming Chou, Robert C.Burruss, et al.,(?)立曼光谱原位观测水合物形成后的饱和甲烷浓度,地球化学,2005,02)：187-192；
[52]Sheri N. White, William Kirkwood, Alana Sherman, et al., Development and deployment of a precision underwater positioning system for in situ laser Raman spectroscopy in the deep ocean, Deep Sea Research Part Ⅰ:Oceanographic Research Papers,2005,52(12):2376-2389;
[53]J. A. Breier, S. N. White and C. R. German, Mineral-microbe interactions in deep-sea hydrothermal systems:a challenge for Raman spectroscopy, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences,2010,368(1922):3067-3086;
[54]Heinar Schmidt, Nguyen Bich Ha, Jens Pfannkuche, et al., Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS), Marine Pollution Bulletin,2004,49(3):229-234;
[55]Tina M. Battaglia, Eileen E. Dunn, Marvin D. Lilley, et al., Development of an in situ fiber optic Raman system to monitor hydrothermal vents, The Analyst,2004,129(7):602;
[56]柏受军,张荣标,胡海燕,et al.,差动变压器式大量程精密角位移传感器的设计,传感器与微系统,2006,11)：63-65；
[57]R. T. Short and Et Al., Development of an underwater mass-spectrometry system for in situ chemical analysis, Measurement Science and Technology,1999,10(12):1195;
[58]S. White, W. Kirkwood, A. Sherman, et al., Development and deployment of a precision underwater positioning system for in situ laser Raman spectroscopy in the deep ocean, Deep Sea Research Part Ⅰ: Oceanographic Research Papers,2005,52(12):2376-2389;
[59]吴延荣,王克河,王桂娟,et al.,基于MMA7260Q的数字倾角传感器设计，微计算机信息,2010,19)：113-114；
[60]田小芳,陆起涌,熊超,基于加速度传感器的倾角仪设计,传感技术学报,2006,02)：361-363；
[61]张礼莉,孙传友,数字式倾斜仪设计,科技信息(学术研究),2007,32)：86-88；
[2]吴世迎,世界海底热液硫化物资源,海洋出版社,2000；
[3]Seth G. John, Olivier J. Rouxel, Paul R. Craddock, et al., Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys, Earth and Planetary Science Letters,2008,269(1-2):17-28;
[4]冯士榨,李凤岐and李少菁,海洋科学导论,高等教育出版社,1999；
[5]徐肖梅,海洋技术概论,科学出版社,2000；
[6]Rene Born, Hermann Ehrlich, Vasiliy Bazhenov, et al., Investigation of nanoorganized biomaterials of marine origin, Arabian Journal of Chemistry,2010,3(1):27-32;
[7]Walter S. Borowski, Charles K. Paull and William Ussler, Global and local variations of interstitial sulfate gradients in deep-water, continental margin sediments:Sensitivity to underlying methane and gas hydrates, Marine Geology,1999,159(1-4):131-154;
[8]M. Kinoshita, R. P. Von Herzen, O. Matsubayashi, et al., Tidally-driven effluent detected by long-term temperature monitoring at the TAG hydrothermal mound, Mid-Atlantic Ridge, Physics of the earth and planetary interiors,1998,108(2):143-154;
[9]N. Le Bris, P. M. Sarradin, D. Birot, et al., A new chemical analyzer for in situ measurement of nitrate and total sulfide over hydrothermal vent biological communities. Marine Chemistry,2000,72(1):1-15;
[10]Andrew J. Reed, Ruth Dorn, Cindy L. Van Dover, et al., Phylogenetic diversity of methanogenic, sulfate-reducing and methanotrophic prokaryotes from deep-sea hydrothermal vents and cold seeps, Deep Sea Research Part Ⅱ:Topical Studies in Oceanography,2009,56(19-20):1665-1674;
[11]Christopher R. German, Dana R. Yoerger, Michael Jakuba, et al., Hydrothermal exploration with the Autonomous Benthic Explorer, Deep Sea Research Part I:Oceanographic Research Papers,2008, 55(2):203-219;
[12]C. Bachraty, P. Legendre and D. Desbruyeres, Biogeographic relationships among deep-sea hydrothermal vent faunas at global scale, Deep Sea Research Part Ⅰ:Oceanographic Research Papers, 2009,56(8):1371-1378;
[13]Jory Bell, Joe Betts and Edward Boyle, MITESS:a moored in situ trace element serial sampler for deep-sea moorings, Deep Sea Research Part I:Oceanographic Research Papers,2002, 49(11):2103-2118;
[14]D. O. B. Jones, B. J. Bett, R. B. Wynn, et al., The use of towed camera platforms in deep-water science, Underwater Technology,2009,28(2):41-50;
[15]T. Marsset, B. Marsset, S. Ker, et al., High and very high resolution deep-towed seismic system: Performance and examples from deep water Geohazard studies, Deep Sea Research Part Ⅰ: Oceanographic Research Papers,2010,57(4):628-637;
[16]J. M. Schicks, M. A. Ziemann, H. Lu, et al., Raman spectroscopic investigations on natural samples from the Integrated Ocean Drilling Program (IODP) Expedition 311:Indications for heterogeneous compositions in hydrate crystals, Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2010,77(5):973-977;
[17]K. C. Hester, R. M. Dunk, P. M. Walz, et al.. Direct measurements of multi-component hydrates on the seafloor:Pathways to growth, Fluid Phase Equilibria,2007,261(1-2):396-406;
[18]J. D. Irish and F. E. Snodgrass, Quartz crystals as multipurpose oceanographic sensors--Ⅰ. pressure, Deep Sea Research and Oceanographic Abstracts,1972,19(2):165-169;
[19]K. Ding, W. E. Seyfried Jr, M. K. Tivey, et al., In situ measurement of dissolved H2 and H2S in high-temperature hydrothermal vent fluids at the Main Endeavour Field, Juan de Fuca Ridge, Earth and Planetary Science Letters,2001,186(3-4):417-425;
[20]叶瑛,陈鹰,杨灿军，et al.,适用于深海热液环境的全固态电化学传感器的研究进展,自然科学进 展,2004,02)：；
[21]陈鹰,杨灿军,顾临怡,et al.,基于载人潜水器的深海资源勘探作业技术研究,机械工程学报,2003，11：38-42；
[22]Maciej Sosna, Guy Denuault, Robin W. Pascal, et al., Development of a reliable microelectrode dissolved oxygen sensor, Sensors and Actuators B:Chemical,2007,123(1):344-351;
[23]K. Grasshoff, M. Ehrhardt, K. Kremling, et al., Methods of seawater analysis, Wiley Online Library, 1976;
[24]Kang Ding, William E. Seyfried Jr, Zhong Zhang, et al., The in situ pH of hydrothermal fluids at mid-ocean ridges, Earth and Planetary Science Letters,2005,237(1-2):167-174;
[25]M. Benounis, N. Jaffrezic-Renault, J. P. Dutasta, et al., Study of a new evanescent wave optical fibre sensor for methane detection based on cryptophane molecules, Sensors and Actuators B:Chemical, 2005,107(1):32-39;
[26]G. P. Klinkhammer, Fiber optic spectrometers for in-situ measurements in the oceans:the ZAPS Probe, Marine Chemistry,1994,47(1):13-20;
[27]Zhong Chen, Chi-Yue Huang, Meixun Zhao, et al., Characteristics and possible origin of native aluminum in cold seep sediments from the northeastern South China Sea, Journal of Asian Earth Sciences,2011,40(1):363-370;
[28]V. Barale, P. Cipollini, A. Davidov, et al., Water Constituents in the North-western Black Sea from Optical Remote Sensing and In situ Data, Estuarine, Coastal and Shelf Science,2002,54(3):309-320;
[29]Sheri N. White, Laser Raman spectroscopy as a technique for identification of seafloor hydrothermal and cold seep minerals, Chemical Geology,2009,259(3-4):240-252;
[30]M. Hannington, P. Herzig, P. Stoffers, et al., First observations of high-temperature submarine hydrothermal vents and massive anhydrite deposits off the north coast of Iceland, Marine Geology, 2001,177(3-4):199-220;
[31]J. Sarrazin, P. Rodier, M. K. Tivey, et al., A dual sensor device to estimate fluid flow velocity at diffuse hydrothermal vents, Deep Sea Research Part I:Oceanographic Research Papers,2009, 56(11):2065-2074;
[32]C. R. German, J. Hergt, M. R. Palmer, et al., Geochemistry of a hydrothermal sediment core from the OBS vent-field,21°N East Pacific Rise, Chemical Geology,1999,155(1-2):65-75;
[33]James P. Cowen, Xiyuan Wen and Brian N. Popp, Methane in aging hydrothermal plumes, Geochimica et Cosmochimica Acta,2002,66(20):3563-3571;
[34]H. W. Bange, R. Ramesh, S. Rapsomanikis, et al., Methane in surface waters of the Arabian Sea, Geophys. Res. Lett.,1998,25(19):3547-3550;
[35]Ralf D. Prien, The future of chemical in situ sensors, Marine Chemistry,2007.107(3):422-432;
[36]U. Tsunogai, N. Yoshida and T. Gamo, Carbon isotopic evidence of methane oxidation through sulfate reduction in sediment beneath cold seep vents on the seafloor at Nankai Trough, Marine Geology,2002, 187(1-2):145-160;
[37]J. A. Breier, C. R. German and S. N. White, Mineral phase analysis of deep-sea hydrothermal particulates by a Raman spectroscopy expert algorithm:Toward autonomous in situ experimentation and exploration, Geochem. Geophys. Geosyst.,2009,10(5):Q05T05;
[38]Xin Zhang, Peter M. Walz, William J. Kirkwood, et al., Development and deployment of a deep-sea Raman probe for measurement of pore water geochemistry. Deep Sea Research Part I:Oceanographic Research Papers,2010,57(2):297-306;
[39]Christophe Bourry, Bertrand Chazallon, Jean Luc Charlou, et al., Free gas and gas hydrates from the Sea of Marmara, Turkey:Chemical and structural characterization, Chemical Geology,2009, 264(1-4):197-206;
[40]J. L. Charlou, J. P. Donval, Y. Fouquet, et al., Physical and chemical characterization of gas hydrates and associated methane plumes in the Congo-Angola Basin, Chemical Geology,2004, 205(3-4):405-425;
[41]Jill Pasteris, Brigitte Wopenka, John J. Freeman, et al., Raman Spectroscopy in the Deep Ocean: Successes and Challenges, Appl. Spectrosc.,2004,58(7):195A-208A;
[42]J. D. Pasteris, B. Wopenka, J. J. Freeman, et al., Spectroscopic success and challenges:Raman spectroscopy at 3.6 km depth in the ocean, Appl. Spectrosc,2004,58(7):;
[43]S. N. White, P. G. Brewer and E. T. Peltzer, Determination of gas bubble fractionation rates in the deep ocean by laser Raman spectroscopy, Marine Chemistry,2006,99(1-4):12-23;
[44]Josh N. Plant, Kenneth S. Johnson, Steve E. Fitzwater, et al., Tidally oscillating bisulfide fluxes and fluid flow rates observed with in situ chemical sensors at a warm spring in Monterey Bay, California, Deep Sea Research Part Ⅰ:Oceanographic Research Papers,2010,57(12):1585-1595;
[45]S. N. White, R. M. Dunk, E. T. Peltzer, et al., In situ Raman analyses of deep-sea hydrothermal and cold seep systems (Gorda Ridge and Hydrate Ridge),2006,;
[46]Sheri N. White, Qualitative and Quantitative Analysis of CO2 and CH4 Dissolved in Water and Seawater Using Laser Raman Spectroscopy, Appl. Spectrosc.,2010,64(7):819-827;
[47]Peter G. Brewer, George Malby, Jill D. Pasteris, et al., Development of a laser Raman spectrometer for deep-ocean science, Deep Sea Research Part Ⅰ:Oceanographic Research Papers,2004,51(5):739-753;
[48]A. D. Sherman, P. M. Walz and P. G. Brewer, Two Generations of Deep-Ocean Raman In-Situ Spectrometers, Sea Technology,2007,48(2):10-13;
[49]J. Santos Gomez, Nonlinear Raman Spectroscopy, Theory, Academic Press,1999;
[50]R. M. Dunk, E. T. Peltzer, P. M. Walz, et al., Seeing a deep ocean CO2 enrichment experiment in a new light:laser Raman detection of dissolved CO2 in seawater, Environmental science & technology,2005, 39(24):9630-9636;
[51]吕万军,I-Ming Chou, Robert C.Burruss, et al.,(?)立曼光谱原位观测水合物形成后的饱和甲烷浓度,地球化学,2005,02)：187-192；
[52]Sheri N. White, William Kirkwood, Alana Sherman, et al., Development and deployment of a precision underwater positioning system for in situ laser Raman spectroscopy in the deep ocean, Deep Sea Research Part Ⅰ:Oceanographic Research Papers,2005,52(12):2376-2389;
[53]J. A. Breier, S. N. White and C. R. German, Mineral-microbe interactions in deep-sea hydrothermal systems:a challenge for Raman spectroscopy, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences,2010,368(1922):3067-3086;
[54]Heinar Schmidt, Nguyen Bich Ha, Jens Pfannkuche, et al., Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS), Marine Pollution Bulletin,2004,49(3):229-234;
[55]Tina M. Battaglia, Eileen E. Dunn, Marvin D. Lilley, et al., Development of an in situ fiber optic Raman system to monitor hydrothermal vents, The Analyst,2004,129(7):602;
[56]柏受军,张荣标,胡海燕,et al.,差动变压器式大量程精密角位移传感器的设计,传感器与微系统,2006,11)：63-65；
[57]R. T. Short and Et Al., Development of an underwater mass-spectrometry system for in situ chemical analysis, Measurement Science and Technology,1999,10(12):1195;
[58]S. White, W. Kirkwood, A. Sherman, et al., Development and deployment of a precision underwater positioning system for in situ laser Raman spectroscopy in the deep ocean, Deep Sea Research Part Ⅰ: Oceanographic Research Papers,2005,52(12):2376-2389;
[59]吴延荣,王克河,王桂娟,et al.,基于MMA7260Q的数字倾角传感器设计，微计算机信息,2010,19)：113-114；
[60]田小芳,陆起涌,熊超,基于加速度传感器的倾角仪设计,传感技术学报,2006,02)：361-363；
[61]张礼莉,孙传友,数字式倾斜仪设计,科技信息(学术研究),2007,32)：86-88；