Next Generation Raman: Developing A Monolithic Spatial Heterodyne Spectrometer For Multi-Scale Chemical Mapping In Marine Environments

下一代拉曼：开发用于海洋环境中多尺度化学测绘的整体空间外差光谱仪

• 批准号: 1829333
• 负责人: Stanley Angel
• 金额: $ 59.09万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1829333&HistoricalAwards=false
• 关键词: Next; Generation; Raman; Developing; Monolithic

The goal of this project is to develop a radically new type of instrument, a monolithic Raman spectrometer, designed to generate chemical images of solids liquids and/or gases in ocean environments at all depths. The instrument uses a technique called Raman Spectroscopy, where light scattered off of a sample at composition specific wavelengths (colors) is collected in a 2-dimensional (2D) image (picture) to produce a chemical map of the sampling area. In this project the key technological advancement is the new type of Raman instrument, called a Monolithic Spatial Heterodyne Raman Spectrometer (MSHRS). Although great progress has been made in the development of instrument platforms and sampling systems necessary to support Raman spectroscopy for oceanographic applications, advances in Raman spectrometer technology have not kept pace for use in these environments. The value of Raman measurements, balanced by the effort and cost of deploying current instruments, justifies the development of a new type of Raman spectrometer that is suitable for extreme environments like the deep ocean. The MSHRS being developed in this project overcomes some major limitations with existing systems for operation in the oceans such as instrument size and weight, power requirement, ruggedness (no moving parts), and sensitivity. The MSHRS technology being developed will allow deployment of instrument platforms and sampling systems necessary to support Raman spectroscopy for a broad range of oceanographic applications. This will support Raman measurements on minerals, opaque solids, and in water for important chemical species such as methane, carbon dioxide (CO2), sulfate, and sulfides in environments to depths up to 3.6 km, where the pressure is 360 times higher than at the surface. The MSHRS will generate chemical maps to show the 1D and 2D spatial distribution of these and other chemicals, even in complex mixtures typical of natural environments. The value of Raman measurements, balanced by the effort and cost of deploying current instruments, justifies the development of this new type of Raman spectrometer. The proposed MSHRS alone will be a major advance over "off the shelf" spectrometers currently used in marine Raman applications, reducing the size while increasing robustness and sensitivity over conventional designs. And, when combined with small diode lasers and the latest imaging detectors, the instrument can be truly miniaturized with no loss of performance. The MSHRS is potentially small enough to be deployed on autonomous swimming and drifting platforms (called gliders, Argo floats) or manipulator arms on remotely operated vehicles (ROVs). This work will support the development of a new Raman capability that will facilitate a wide range of new applications as well as basic chemical measurements in marine systems and will fuel transformative oceanographic research. While the focus of the proposed work is the study of process dynamics for oceanographic applications; the technology has much wider applicability. In addition to support of basic and applied research, industrial applications using the new capability for on-line analysis and process evaluation are likely. The investigators have a long history of mentoring students from underrepresented groups and the two students supported by this project are current female graduate students. These students will also benefit by collaborating with scientists at Lawrence Livermore National Laboratory and will gain a National Lab perspective on homeland security and defense applications. The Spatial Heterodyne Raman Spectrometer (SHRS), recently described by Angels group (the project principal investigator, PI), is a radically different design, offering tremendous advantages over conventional dispersive Raman systems, including 10 to 100 times larger acceptance angle and subsequently a much larger field of view, 100 to 10,000 higher light throughput for extended sources, very high spectral resolution and a wide spectral range. The SHRS design also allows for the spectrometer to be extremely small because the spectral resolution is not a strong function of device size. In the proposed work we will take the SHRS to the next level by developing a Monolithic SHRS (MSHRS) where the spectrometer optical components are a single piece of fused silica. This will provide a robust Raman spectrometer, immune to shock and vibrations, with increased sensitivity at a size and weight orders of magnitude smaller than current oceanographic Raman instruments. The MSHRS will be evaluated in terms of resolution, spectral range, throughput and robustness to vibration. Raman system figures of merit (e.g., resolution, sensitivity, light throughput, etc.) will be determined using solid, liquid, solutions and gases. In model applications we will evaluate the MSHRS for monitoring reaction dynamics in model oxic/anoxic mixing systems characteristic of a range of oceanographic environments. As a measure of the stability and precision of the MSHRS we will also evaluate its use for measuring selected isotope ratios for species relevant to the fundamental ocean.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

该项目的目标是开发一种全新类型的仪器，即单片拉曼光谱仪，用于生成海洋环境中所有深度的固体、液体和/或气体的化学图像。该仪器使用一种称为拉曼光谱的技术，其中以组合物特定波长（颜色）从样品散射的光被收集在二维（2D）图像（图片）中以产生采样区域的化学图。 在这个项目中，关键的技术进步是新型的拉曼仪器，称为单片空间外差拉曼光谱仪（MSHRS）。 虽然在支持海洋学应用的拉曼光谱学所需的仪器平台和采样系统的开发方面取得了很大进展，但拉曼光谱仪技术的进步没有跟上在这些环境中使用的步伐。拉曼测量的价值，与部署现有仪器的努力和成本相平衡，证明了开发适用于深海等极端环境的新型拉曼光谱仪的合理性。该项目正在开发的MSHRS克服了现有系统在海洋中运行的一些主要限制，如仪器尺寸和重量，功率要求，耐用性（无移动部件）和灵敏度。正在开发的MSHRS技术将允许部署必要的仪器平台和采样系统，以支持拉曼光谱学在广泛的海洋学应用。这将支持对矿物、不透明固体和水中重要化学物质的拉曼测量，如甲烷、二氧化碳（CO2）、硫酸盐和硫化物，深度可达3.6公里，其中压力比表面高360倍。MSHRS将生成化学地图，以显示这些和其他化学品的一维和二维空间分布，即使是在自然环境中典型的复杂混合物中。拉曼测量的价值，通过部署当前仪器的努力和成本来平衡，证明了这种新型拉曼光谱仪的开发是合理的。与目前用于海洋拉曼应用的“现成”光谱仪相比，拟议中的MSHRS将是一个重大进步，与传统设计相比，它减小了尺寸，同时增加了鲁棒性和灵敏度。而且，当与小型二极管激光器和最新的成像探测器相结合时，该仪器可以真正小型化，而不会损失性能。MSHRS可能足够小，可以部署在自主游泳和漂移平台（称为滑翔机，Argo浮子）或遥控车辆（ROV）上的机械臂上。这项工作将支持发展新的拉曼能力，促进各种新的应用以及海洋系统中的基本化学测量，并将推动变革性的海洋学研究。虽然拟议工作的重点是研究海洋学应用的过程动力学，但该技术的适用性要广泛得多。除了支持基础研究和应用研究外，还可能使用在线分析和过程评估的新能力进行工业应用。 调查人员有着指导来自代表性不足群体的学生的悠久历史，该项目支持的两名学生是目前的女研究生。这些学生还将受益于与劳伦斯利弗莫尔国家实验室的科学家合作，并将获得国家实验室对国土安全和国防应用的看法。空间外差拉曼光谱仪（SHRS），最近描述的天使组（项目首席研究员，PI），是一个完全不同的设计，提供了巨大的优势，超过传统的色散拉曼系统，包括10至100倍的接受角，随后更大的视场，100至10,000高的光通量扩展源，非常高的光谱分辨率和宽的光谱范围。SHRS设计还允许光谱仪非常小，因为光谱分辨率不是设备尺寸的强函数。在拟议的工作中，我们将采取SHRS到一个新的水平，通过开发单片SHRS（MSHRS）的光谱仪光学元件是一块熔融石英。这将提供一个坚固的拉曼光谱仪，不受冲击和振动的影响，在比目前的海洋学拉曼仪器小的尺寸和重量数量级上具有更高的灵敏度。MSHRS将在分辨率、光谱范围、通量和振动鲁棒性方面进行评价。拉曼系统品质因数（例如，分辨率、灵敏度、光通量等）将使用固体、液体、溶液和气体来确定。在模型应用中，我们将评估MSHRS监测反应动力学模型的好氧/缺氧混合系统的特点，一系列的海洋环境。作为MSHRS稳定性和精确性的衡量标准，我们还将评估其用于测量与基本海洋相关的物种的选定同位素比率。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

项目成果

Model study of organic carbon attenuation and oxygen mass transfer in persistent aggregate layers in the deep sea

深海持久聚集层有机碳衰减与氧传质模型研究

• DOI: 10.1016/j.dsr2.2020.104760
• 发表时间: 2020
• 期刊: Deep Sea Research Part II: Topical Studies in Oceanography
• 作者: Shaw, Timothy J.;Boucher, Corrianna;Huffard, Christine L.;Smith, Kenneth L.
• 通讯作者: Smith, Kenneth L.

A Monolithic Spatial Heterodyne Raman Spectrometer: Initial Tests

• DOI: 10.1177/0003702820936643
• 发表时间: 2020-08-27
• 期刊: APPLIED SPECTROSCOPY
• 影响因子: 3.5
• 作者: Waldron, Abigail;Allen, Ashley;Angel, S. Michael
• 通讯作者: Angel, S. Michael

A demonstration of spatial heterodyne spectrometers for remote LIBS, Raman spectroscopy, and 1D imaging

• DOI: 10.1016/j.sab.2021.106108
• 发表时间: 2021-05
• 期刊: Spectrochimica Acta Part B: Atomic Spectroscopy
• 作者: K. Fessler;A. Waldron;A. Colón;J. Carter;S. Angel

Hyperspectral Raman Imaging Using a Spatial Heterodyne Raman Spectrometer with a Microlens Array

使用具有微透镜阵列的空间外差拉曼光谱仪进行高光谱拉曼成像

• DOI: 10.1177/0003702820906222
• 发表时间: 2020
• 期刊: Applied Spectroscopy
• 影响因子: 3.5
• 作者: Allen, Ashley;Waldron, Abigail;Ottaway, Joshua M.;Chance Carter, J.;Michael Angel, S.
• 通讯作者: Michael Angel, S.

Spatial Heterodyne Raman Spectrometer (SHRS) for In Situ Chemical Sensing Using Sapphire and Silica Optical Fiber Raman Probes

• DOI: 10.1177/0003702819868237
• 发表时间: 2019-10-01
• 期刊: APPLIED SPECTROSCOPY
• 影响因子: 3.5
• 作者: Ottaway, Joshua M.;Allen, Ashley;Carter, J. Chance
• 通讯作者: Carter, J. Chance