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In Situ Detection of Species Relevant to the Carbon Cycle in Seawater with Submersible Potentiometric Probes
Environmental Science & Technology Letters ( IF 8.9 ) Pub Date : 2017-10-02 00:00:00 , DOI: 10.1021/acs.estlett.7b00388
Maria Cuartero 1 , Nadezda Pankratova 1 , Thomas Cherubini 1 , Gaston A. Crespo 1 , Francesco Massa 2 , Fabio Confalonieri 3 , Eric Bakker 1
Affiliation  

We report on the development of a submersible probe for the simultaneous potentiometric detection of carbonate, calcium, and pH in seawater. All-solid-state electrodes incorporating nanomaterials provide an adequate response time (<10 s), stability (drifts of <0.9 mV h–1), reproducibility (calibration parameter deviation of <0.7%), and accuracy (deviation of <8% compared to reference techniques) for real-time monitoring of seawater using a flow system. The functioning of the deployable prototype was checked in an outdoor mesocosm and via long-term monitoring in Genoa Harbor. The electrodes worked properly for 3 weeks, and the system demonstrated the capability to autonomously operate with routines for repetitive measurements, data storage, and management. In situ profiles observed in Genoa Harbor and Arcachon Bay were validated using on site and ex situ techniques. The validation of in situ-detected carbonate is a challenge because both re-equilibration of the sample with atmospheric CO2 and the use of apparent thermodynamic constants for speciation calculations lead to some differences (<20% deviation). The submersible probe is a promising tool for obtaining rapid and trustworthy information about chemical levels in marine systems. Moreover, the fluidic approach allows for the integration of other ion sensors that may require sample pretreatment.

中文翻译:

用潜水电位计原位检测与海水中碳循环有关的物种

我们报告了一种潜水探针的发展,该探针可同时电位检测海水中的碳酸盐,钙和pH。包含纳米材料的全固态电极可提供足够的响应时间(<10 s),稳定性(漂移<0.9 mV h –1),使用流量系统实时监测海水的重现性(校准参数偏差<0.7%)和准确性(与参考技术相比偏差<8%)。可部署原型的功能在室外环境中进行了检查,并通过热那亚港口的长期监控进行了检查。电极可以正常工作3周,并且该系统展示了可以自动进行重复测量,数据存储和管理的例程的功能。在热那亚港口和阿尔卡雄湾观察到的原位剖面已使用现场和非原位技术进行了验证。原位检测碳酸盐的验证是一个挑战,因为样品与大气CO 2的重新平衡并且将表观热力学常数用于物种形成计算会导致一些差异(<20%偏差)。潜水探针是一种有前途的工具,可用于获取有关海洋系统中化学物质含量的快速且可信赖的信息。此外,流体方法允许集成可能需要样品预处理的其他离子传感器。
更新日期:2017-10-03
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