Collaborative Research: A Nanostructure Sensor for Measuring Dissolved Iron and Copper Concentrations in Coastal and Offshore Seawater

铁和铜在广泛的生物系统中是许多酶的关键共同成分，它们在水系统中的升高或缺乏水平会对生物、生态系统和人类健康产生巨大影响。在过去十年中，人们越来越认识到这些影响对海洋系统的重要性。确定这些金属对环境造成负面影响的地点和时间受到相对稀疏的数据集的极大阻碍。这一问题是在盐水中以极低（痕量）浓度获得准确的铁和铜测定的分析挑战的直接后果，以及依赖于船舶的采样制度的局限性。PI申请资金用于在Tripp、Wells和King实验室的研究和技术进步的基础上开发活性纳米结构，这种纳米结构可以作为检测海水中各种对环境重要的溶解金属的平台。初步工作已经在北太平洋亚北极地区验证了一个受生物启发的传感器平台，首次展示了固体传感器在极低（50 pM）浓度下测量海水中溶解铁的效果。这项工作将1)通过调整主动纳米结构来优化原型传感器，以测量溶解的铁和铜；2)开发一种检测装置，将当前的船载方法迁移到玫瑰花形分析平台、系泊和自动驾驶车辆上。更广泛的影响：该项目有可能进一步开发一种传感器，该传感器将提供有关生物上重要金属铁和铜的化学形态的独特信息。本文提出的工作满足了海洋化学和海洋生物地球化学研究人员对这些金属的高时空分辨率数据的重要需求。这种跨学科的方法有可能填补数据的分析空白，这些数据继续阻碍人们了解海洋中铜和铁的可用性如何调节海洋环境中碳和氮的循环。该提案很好地平衡了将纳米技术与红外光谱结合起来的目标，以解决分析空白，同时为本科生和研究生的培训提供具体支持。pi计划让少数族裔学生参与到他们的研究中来。这将产生最重要的影响，因为吸引聪明的学生进入我们的领域，激励年轻学生考虑从事科学事业，对我们国家科学能力的持续增长至关重要。

Iron and Copper serve as key co-constituents for numerous enzymes in a wide range of biological systems, and their elevated or impoverished levels in aqueous systems have dramatic consequences at organismal, ecosystem, and human health scales. Over the last decade these effects have increasingly been recognized to be important in ocean systems. Identifying sites and times where these metals cause negative environmental outcomes is greatly hampered by their comparatively sparse datasets. This problem is a direct consequence of the analytical challenge of obtaining accurate Fe and Cu determinations in saline waters at very low (trace) concentrations, and the limitations of ship-dependent sampling regimes. The PI's request funding to build on research and technology advances in the Tripp, Wells and King laboratories to develop active nanostructures that can serve as platforms amenable for detection of a wide range of environmentally important dissolved metals in seawater. Preliminary work has validated a biologically-inspired sensor platform in the subarctic N. Pacific, providing the first demonstration of dissolved Fe measurements at very low (50 pM) concentrations in oceanic waters by a solid state sensor. The proposed work will 1) optimize this prototype sensor by tuning the active nanostructures to measure dissolved Fe and Cu, and 2) develop a detection device that migrates the current ship-board method to operate on rosette profiling platforms as well as on moorings and autonomous vehicles. Broader Impacts:This project has the potential to further develop a sensor that will provide unique information about the chemical speciation of the biologically important metals Fe and Cu. The work proposed here fills an important need for high spatial and temporal resolution data of these metals identified as priority by researchers in marine chemistry and marine biogeochemistry. This interdisciplinary approach has the potential to fill an analytical void for data that continues to stymie efforts to understand how and Cu and more specifically Fe availability in the oceans modulates the cycling of carbon and nitrogen in the marine environment. The proposal is well balanced in its goal of marrying nanotechnology with IR spectroscopy to address a analytical void while providing specific support for the training of students at the undergraduate and graduate levels. The PIs plan to develop minority student involvement in their research. This will have the most important impact, since bringing smart students into our field and stimulating young students to consider careers in science is essential for the continued growth of our national science capabilities.