FP7-OCEAN-2013 - SCHeMA: integrated in Situ Chemical MApping Probes

M.-L. Tercier Waeber1, E. Bakker1, C. Nardin1, S. Mongin1, E. Prado1, M. Cuartero Botia1, B. Mazaikoff2, F. Luxenburger2,

I. Klimant3, G. Mistlberger3, B. Mueller3, P. Van Der Val4, M. Fighera4, J. Fernandez Sanchez5, A. L. Medina Castillo5, A. Valero Navarro5, J. Schaefer6, M. Abdou6, A. Novellino7, P. D'Angelo7,

F. Confalonieri8, M. Castellano9, E. Magi9, F. Massa9, P. Povero9

1Université de Genève, CH; 2Universitaet Ulm, DE; 3Technische Universitaet Graz, AT; 4Ecole Polytechnique Fédérale de Lausanne, CH; 5NanoMyP S.L., Granada, ES; 6Université de Bordeaux, FR;

7Idronaut S.r.l. Milan, IT; 8ETT S.p.A., Genova, Italy; 9Università degli Studi di Genova, IT;

Abstract — Coastal areas are vulnerable ecosystems comprising

unique biological niches that require protection. Identification of relevant types of hazards at the appropriate temporal and spatial scale is crucial to detect their sources and origin, to understand the processes governing their magnitude and distribution, and to ultimately evaluate and manage their risks and consequences preventing economic losses. SCHeMA aims to provide an open and modular sensing solution for autonomous in situ high resolution mapping of a range of anthropogenic and natural chemical compounds coupled to master bio-physicochemical parameters. User-friendly data discovery, access and download as well as interoperability with other projects will be achieved via dedicated interface compatible with INSPIRE and GEO/GEOSS standards and principles.

Keywords - (Submersible probes, autonomous measurements, nutrients, trace metals, VOCs, saxitoxins, algae species, INSPIRE, OGC-SWE, EMODNet)

I. INTRODUCTION Marine environments are highly vulnerable and influenced

by a wide diversity of anthropogenic and natural substances and organisms that may have adverse effects on the ecosystem equilibrium, on living resources and, ultimately, on human health. The majority of the pollution impact on coastal environment comes from land-based sources, but also some naturally present compounds generated in the marine environment (e.g. biotoxins, viruses) are highly relevant to coastal sustainable development. Identification of relevant types of hazards at the appropriate temporal and spatial scale is crucial to detect their sources and origin, to understand the processes governing their magnitude and distribution, and to ultimately evaluate and manage their risks and consequences preventing economic losses. This can be addressed only by the development of innovative, compact, rugged, automated, sensor networks allowing long-term monitoring. Development of such tools is a challenging task as it requires many analytical and technical innovations. SCHeMA aims at providing an open and modular sensing solution for in situ high resolution mapping of a range of anthropogenic and natural chemical compounds that may have feedback (synergic) interaction. It

will acquire a wealth of information, at high spatial and temporal resolution, on a range of chemical hazardous compounds coupled to environmental master variables. SCHeMA will contribute to enhance ocean observing capabilities and support policies of several EU directives.

A. SCHEMA vision SCHeMA is a multi-disciplinary research initiative to

develop a network of submersible probes that is flexible, modular, web-accessible, and refines the state of the art by incorporating different sensors to map a range of inorganic and organic hazardous compounds in marine ecosystems. The field application of the SCHeMA system at selected coastal observation sites will produce a new type of high-resolution environmental data in these areas by covering a broad range of major contaminant types (nutrients, metals, organic contaminants, biotoxins, specific algae) and relevant, representative study sites (protected marine areas, seafood production areas). The SCHeMA system is designed so that it can operate from different facilities: platform, moored buoy, boat, unmanned surface or submersible vehicles, and landers. The network of submersible probes is connected (wired or wireless) to a network controller acting as the front-end of the measuring system that provides information and data according to international standards (e.g. EU Fisheries Data Collection Framework, the Marine Strategy Framework Directive [1], the INSPIRE directive, the GMES and GOOS/GEOSS initiatives, OGC standard). The proposed infrastructure will provide a plug-and-play tool to monitor water quality, store data and disseminate information on marine specific area status. It will contribute to develop the definition of Global Monitoring for Enviroment and Security (GMES) marine core service, in compliance with INSPIRE standards, and have a deep impact on the European natural resources management and exploitation policies.

Key targets are chemicals that may adversely affect marine ecosystems, living resources and ultimately human health and may have feedback (synergic) interaction such as a range of trace metals (Hg, Cd, Pb, As and Cu) and nutrients, species relevant to the carbon cycle, volatile organic constituents

978-1-4799-8736-8/15/$31.00 ©2015 European Union

(VOCs), relevant algae species and toxins. Such a rich database will offer the possibility to gain insights into phenomena that are currently poorly understood but are significant for understanding aquatic ecosystems functioning, for predictions of toxicological impact and, ultimately, for sustainable management based on scientific knowledge. SCHEMA will provide novel innovative and versatile tools to enhance ocean observing system capabilities in term of number of hazardous chemical compounds that can be quantified simultaneously and in term of temporal resolution and spatial dimension to rapidly localize problems, to alert targeted groups and to take remedial action at appropriate time scale. Moreover it will let to evaluate the behavior and fate of the target chemical compounds in order to: i) promote new discoveries leading to better understanding of the link between the target analytes and their impact on water quality, marine organisms, society and economy; ii) propose EQS standards based on scientific knowledge; iii) define strategies to set up efficient water quality monitoring programs of estuaries and coastal zones; iv) support implementation of European Maritime Policies and development of knowledge-based protective policies for sustainable management.

B. SCHEMA Consortium, funding and duration The consortium is composed by 9 partners from 6 countries

and it represents a multi-sectorial partnership between:

• three SMEs : Idronaut (Italy), nanoMyP (Spain), ETT (Italy)

• five Universities: UNIGE (Switzerland), UULM (Gernany), TUGRAZ (Austria), UBX1 (France), UNIGe-IT (Italy)

• one Federal Institute of Technology : EPFL-SAMLAB (Switzerland)

All partners share leading expertise in one or two of the sectors shown in Fig. 1.

Fig. 1. Skills involved in the SCHEMA project

SCHeMA is funded by the EU Commission as part of the FP7-Ocean 2013.2 program under the Grant Agreement 614002. The EU financial contribution is € 5.2 million. The project started October 1th 2013 for a duration of 4 years.

II. SPECIFIC OBJECTIVES AND ANALYTICAL METHODS The SCHeMA’s overall aim is to develop an array of

rugged, easy-to-use, innovative submersible chemical sensor probes that can be readily interfaced and deployed from multiple platforms for the in situ measurements of a range of key chemicals and biological hazards.

A. Sensors for nutrients and species relevant to the carbon cycle (UNIGE,EPFL). Development of electrochemical probes for direct detection

of species relevant to the carbon cycle and nutrients are underway. These probes are based on: i) solid state ion-selective membrane sensors and on-line desalination module, allowing reagentless, potentially calibration-free, detection of nutrients (nitrite, nitrate and phosphate); ii) solid-state sensors for simultaneous measurements of species relevant to the carbon cycle (H+ , CO3

2-, and Ca2+). Promising preliminary results have been obtained in synthetic solutions for several sensors. A new type of carbon dioxide sensor comprising a pH glass electrode measured against a carbonate-selective membrane electrode based on a tweezer type carbonate ionophore is under final optimization. This potentiometric carbon dioxide sensing probe does not require a gas permeable membrane and offers improved sensing characteristics compared to the classical Severinghaus CO2 electrode (Fig.2 ).

a)

b)

Fig. 2. Comparison of calibration curves and response time obtained with the ion-selective CO2 sensor (PCO2) and the Severinghaus CO2 electrode (SH)

B. Sensors and probes for trace metals (UNIGE, nanoMyP, Idronaut) A miniaturized multichannel voltammetric probe is being

developed by Idronaut and UNIGE taking advantages of expertise acquired from previously [2]. This probe will incorporate various types of gel integrated microsensors arrays, namely: a GIME sensor developed as part of the EU project “VAMP” (MAS3-CT95-0033) [2] and allowing reliable long-term in situ monitoring of the bioavailable fraction of Cd, Pb, Cu and Zn; SCHeMA gold nanoparticles-plated GIMEs, chemically functionalized or not, for selective and sensitive measurements of inorganic arsenic species (As(III) and As(V)), inorganic mercury and potentially methyl mercury. The GIME sensors consist on integrated micro-analytical system allowing: minimization of chemical and physical interferences; on-line separation, chemical pre-treatment and/or preconcentration steps; sensitive (ppt) voltammetric detection without sample pre-treatment [2].

A renewable and reproducible AuNP-GIME was successfully developed for continuous direct sub-nanomolar As(III) detection, at natural pH and without interference of copper, up to a period of one week (Fig. 3). The same sensor allows direct measurements of inorganic mercury species present at 0.2 nM level.

a) b)

0.60.40.20.0-0.2-0.4

As(III) = 50 nM

Cu(II) = 40 nM

E/V vs Ag/AgCl /3M KCl

Fig. 3. Example of reliability and sensitivity obtained for direct voltammetric As(III) measurements using the novel AuNP-GIME.

(Bio-)polymer functionalization of the AuNP are investigate to improve sensitivity for mercury detection and extend the capability of this sensor to the direct detection of As(V).

C. Optical detection of organic pollutants: detection of harmful VOCs (UULM, nanoMyP) An optochemical sensor probe is developed (Fig. 4) for the

detection of harmful dissolved volatile organic constituents (VOCs) (e.g.: benzene, toluene, xylenes, tetrachloroethylene). It is based on waveguide-assisted evanescent field absorption spectroscopy in the mid-infrared (MIR; 3-15 m) spectral regime.

Fig. 4. (A) CAD rendering of the IR sensor system fitted into a tubular underwater housing with dimensions of 24x60 cm. (B) Layout of the IR sensor system comprising control electronics, an IR spectrometer module, and IR sensing optics with the active transducer (i.e., IR fiberoptic chemical sensing element) located in a μ-flowcell.

Several studies [3,4,5] revealed that a portable MIR is unaffected by salinity, turbidity and natural organic matter/organic pollutants. Hence, while the fundamental feasibility of this analysis concept has been demonstrated by the UULM [6] team and others, a miniaturized submersible sensing module remained to be developed.

D. Optical detection of biotoxin and early warning system for toxic algae species (TUGRAZ, EPFL, UNIGE) Development of optical devices, involving selective

reversible immobilization of target molecules to sense relevant algae species and toxins (saxitoxin, ovatoxin/palytoxin), are underways.

Promising results have been obtained using first prototypes of flexible, fully integrated multi-channel optical sensor modules based on low-cost optical equipment such as LEDs, optical filters and photodiodes and:

• multi wavelength unit for direct detection of relevant algae species (Fig. 5) based on characteristic ratios of their photosystem compounds

Fig. 5. Schematic representation of the multi-channel algae detection module.

• selective reversible immobilization of target chemical (bio)molecules to sense specific algae toxins (Fig. 6)

Calibration

Fig. 6. Preliminary data of a novel, direct method for saxitoxin determination developed in the SCHeMA project.

III. SCHEMA INTEGRATED CHEMICAL MAPPING PROBES

A. Multichannel probes (Idronaut, UNIGE) The SCHeMA trace metal and nutrient measuring units

imply the integration of challenging sensors and micro-fluidics elements in a single, very compact submersible package provided with advanced OGC-SWE wired and wireless software interfaces (Fig. 8).

Micro-fluidic developments are performed taking into account the specific needs of the individual sensing probes and minimum complexity of the system. The miniature, low power consumption, multichannel probes being developed are based on Eco-Design-ISO/IEC standards and EnOcean technology as well as energy harvesting devices.

B. Network controller (Idronaut) Interfacing of the SCHeMA network of submersible probes

is achieved via a Network Controller built on an open HW/SW platform based on LINUX operating system and a custom hardware, specifically developed in the frame of the project. The Network Controller custom electronics is developed using up-to-date technologies which guarantee the maximum performance allowing the interfacing of the SCHeMA submersible chemical probes as well as other commercially available probes (e.g. CTD and multiparameter probes). The Network control unit is completed with a wireless WAN data transceiver (GPRS, UMTS) and a GPS module (Fig. 7) and a web-based front-end system compatible with EU standard requirements (OGC-SWE, INSPIRE, EMODnet, sensorML, SEIS).

Fig. 7. Block schematic of the SCHeMA Network Controller (NC) web-based communication interface

IV. WEB-BASED NETWORKING OGC SOLUTIONS

A. Data communication and web-based front-end system (ETT, UNIGe-IT) A web interface (Fig. 8) will guarantee that management

and access of data are compatible with standard requirements such as EU Fisheries Data Collection Framework, the Marine Strategy Framework Directive, the INSPIRE directive, the GMES and GOOS/GEOSS initiatives. An ad-hoc ICT wireless networking solution will allow remote control of data transfer and system reconfiguration according to the OGC standard.

The land station will provide a web-based system interface for accessing sensor information and measured sensor observation. The system will be implemented as a SOS (Sensor Observation Service) system thus providing standard

interoperability and access to measured sensor observations – through Observation and Measurements (O&M) standard - as well as sensor descriptions – encoded in Sensor Model Language (SensorML).

Fig. 8. Schematic reppresentation of the SCHEMA interfaced chemical multi-sensor mapping probes and the Web-based networking OGC solutions and data information system.

A web-based system interface for accessing, interacting and configuring the SCHeMA network, controller and probes, is developed according to the international OGC-SWE standards (Fig. 9).

Fig. 9. Demo system currently under development

The Schema Web Interface interoperability will be based on the exchange of standard messages between the service and the consumer by using the HTTP protocol. The requests are sent to the service through an HTTP POST (XML file) or an HTTP GET method (key-value-pairs) specifying the request type and the relative permitted parameters. The service responses are always XML file compliant with the OGC specifications. User-friendly data discovery, access and download as well as interoperability with other projects are achieved via dedicated interface compatible with INSPIRE and GEO/GEOSS standards and principles.

V. PROBES OPTIMISATION AND EVALUATION (ALL) The SCHeMA individual probes and integrated system will

be characterized, optimized and evaluated under laboratory controlled conditions and field time series investigations to: verify the ruggedness and capabilities for long-term operation; check plug-and-play compatibility with existing infrastructure/facilities; assess and validate the accuracy and reliability of the data obtained from in situ monitoring by inter-comparison with data obtained using well established alternative laboratory and/or field-based techniques; optimize the SCHeMA components based on field data; select the SCHeMA chemical probes ready for long-term field application.

VI. SHORT/LONG TERM FIELD APPLICATIONS (ALL) Short and long-term field applications will be performed in

Atlantic and Mediterranean coastal areas. Some pre-selected sites suitable for field tests are already included in different environmental operational monitoring programs at medium and long term scales (for example: LTER, MAGEST, RNO/ROCCH, LIFE+ Arion project, FP7 project IDREEM and other French/Italian/Spanish/Portuguese monitoring programs) and in national/international scientific collaborations (Fig. 9). These model sites provide a huge panel of contrasting environmental conditions (e.g. salinity, turbidity, nutrient situation, primary production, contaminant pressure, industrial discharges (including heat), dredging, nautical traffic, biodiversity and exploited species) and are representative of the southwest European Atlantic and Mediterranean Coast hosting major coastal protected areas and economic activities in France, Spain and Italy [7,8,9,10].

Fig. 10. Localization of some of the pre-selected sites for field-tests

This variety of potential study sites to which we already have access and/or collaboration agreements with local institutions provides the possibility to choose adequate test sites for each sensor in an early development stage and then test the sensors and the final integrated system under more challenging and/or even extreme conditions (e.g. strong currents, turbidity).

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