Development and Validation of a Submersible Oceanic Luminescent Analyzer of Reactive Intermediate Species (SOLARIS)

海洋的健康和功能是由广泛的化学品的生产和消费所控制的。虽然可以用传统的水收集方法以及船上或实验室分析方法来测量稳定的化学物种，但这种方法不适用于寿命为数小时或更短的化学品，因为这些化学品的生产和消耗速度很快，因此它们的寿命很短，通常在海洋中的含量很低;然而，它们对周围环境的影响却大得不成比例。事实上，人们逐渐认识到，这些寿命短的活性化学品甚至可能对海洋的整体效率和健康至关重要。测量短寿命物种的固有困难一直是测量这些重要化学品的严重制约因素，从而限制了预测它们在海洋及其居民健康中的作用的能力。因此，这项研究将开发、建造和验证一种远程操作的水下化学传感器，从而能够直接测量海洋中这些关键的反应性化学物质。该仪器最初将使用目标过氧化氢和超氧化物进行设计和测试，这两种活性氧（ROS）是众所周知的难以测量，但对海洋的健康和海洋地球化学至关重要。该项目还将支持与波士顿绿色学院合作开展的教育工作，向高中生介绍深海仪器世界及其对了解海洋的重要性，该项目旨在设计、开发和验证用于海洋研究的生物地球化学传感器，其形式为水下海洋活性中间物质（化学）发光分析仪（SOLARIS）。SOLARIS将把先进的自适应射流系统与高灵敏度的光电探测分析仪结合起来，该分析仪包括一个潜水式原位荧光传感器。这一仪器将扩大分析能力，使之能够确定迄今为止无法达到的环境中，特别是深海中活性化学物质的动态特征。SOLARIS将代表四个模块的开发和集成，这些模块共同构成一个分析平台，能够在皮科纳摩尔检测水平上进行校准的原位测量。这些模块将包括定制设计的软件可控泵送和阀组，允许仔细控制和实时修改流体传输和泵送配置，以进行校准、背景测量和标准化。在其中心，水下光电探测系统将涉及开发一个透明的、承压的蓝宝石流动池，该流动池将被集成到一个包含高灵敏度光电倍增管的压力外壳中。连同用于进行校准和分析物衰减测量的集成分光光度计，这些系统将构成分析模块。SOLARIS的配置和部署方式既包括安装在玫瑰花上的“远洋模式”，用于检查沿海和近海沃茨的水柱动态，也包括“海底模式”，同时与潜水器结合，用于对深海生物群落进行初步调查。这两个平台都将作为综合科学计划的一部分进行验证，以进行超氧化物和过氧化氢的首次原位测量-研究将使科学探索ROS在控制全球海洋所有深度的元素循环，碳降解和生物健康方面的作用。

The health and function of the ocean is controlled by the production and consumption of a broad spectrum of chemicals. While stable chemical species can be measured using traditional methods of water collection and either shipboard or lab-based analyses, this approach is not amenable to chemicals that have lifetimes on the orders of hours or less. Due to their rapid production and consumption, these reactive compounds are short-lived and typically exist in low levels within the ocean; yet, they have a disproportionately large influence on their surrounding environment. In fact, there is an emerging recognition that these short-lived reactive chemicals may even be essential to the overall efficiency and health of the ocean. The intrinsic difficulty in measuring short-lived species has been a crippling constraint on measuring these important chemicals, and has thereby limited the ability to predict their role in the health of the ocean and its inhabitants. Thus, this research will develop, build and validate a remotely-operated, underwater chemical sensor that will enable direct measurements of these key reactive chemicals in the ocean. The instrument will be initially designed and tested using the targets hydrogen peroxide and superoxide, two reactive oxygen species (ROS) that are notoriously difficult to measure and yet are key to the health and biogeochemistry of the ocean. This project will also support collaborative education efforts with the Boston Green Academy by introducing high school students to the world of deep-sea instrumentation and its importance in understanding our ocean.This project aims to design, develop and validate a biogeochemical sensor for marine research, in the form of a submersible oceanic (chemi)luminescent analyzer of reactive intermediate species (SOLARIS). The SOLARIS will combine an advanced and adaptive fluidics system with a highly sensitive photodetection analyzer, comprising a submersible in situ chemiluminescent sensor. This instrument will extend analytical capabilities toward an ability to characterize the dynamics of reactive chemical species in environments that have been heretofore out of reach, in particular the deep sea. The SOLARIS will represent the development and integration of four modules, which together comprise an analytical platform capable of calibrated in situ measurements at pico- to nano-molar detection levels. These modules will include custom designed software controllable pumping and valve manifolds, allowing careful control and on-the-fly modification of fluid transfer and pumping configurations for calibration, background measurements, and standardization. At its hub the underwater photodetection system will involve the development of a transparent, pressure-bearing sapphire flow cell to be integrated into a pressure housing containing a highly sensitive photomultiplier tube. Together with an integral spectrophotometer used for conducting calibrations and analyte decay measurements, these systems will comprise the analytical module. The SOLARIS will be configured and deployed in both a rosette-mounted "pelagic mode" for examining water column dynamics in coastal and more offshore waters, as well as in a "benthic mode" while integrated onto a submersible vehicle for preliminary investigation of deep sea biological communities. Both of these platforms will be validated as part of an integrated science plan to make the first in situ measurements of superoxide and hydrogen peroxide - research that will enable scientific exploration of the role of ROS in controlling the elemental cycling, carbon degradation, and organismal health throughout all depths of the global ocean.