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Technical conference on passive samplers and MONITOOL project takes place in the Basque Country

Evento AZTI 3Under the framework of MONITOL project, the last 12th  March AZTI hosted a technical conference on passive samplers with the aim of presenting the MONITOOL project and the use of the most commonly used passive sampling techniques to evaluate the contamination of the environment.

Dr. Jean-Luis Gonzalez (IFREMER), Dr Iratxe Menchaca and Dr María Jesús Belzunce from AZTI explained to the attendees the main lines of the project and recent results, the advantages of passive sampling methods and how passive samplers have been used in MONITOOL campaigns as well as in other previous case studies. Dr Natalia Montero from the University of Cagliari presented a case study on the use of passive samplers to evaluate the impact of human activities in harbours.

Among other passive samplers, the Diffusive Gradient in Thin Films (DGT) were presented in depth to the participants as it is the passive sampling device used in MONITOOL. Among other issues, the advantages that they could have over other current methods to control heavy metal levels for coastal and transitional waters in the compliance of the Water Framework Directive were discussed.

The Conference took place in one of the headquarters of AZTI Foundation, located in Pasaia harbour, in the Basque Country.  It was attended, among others, by representatives of government agencies, universities, environmental consultants, research centres, students, port authorities and laboratories.

Interview with Isabelle Amouroux, leader of MONITOOL Work Package 6 (EQS Adaptation and Chemical Status Assessment)

Isabelle Amouroux works in the Biogeochemistry and Ecotoxicology Unit (Chemical Risk Analysis group) of Ifremer (Institut Français de Recherche pour l'Exploitation de la Mer: French Research Institute for Exploitation of the Sea) a French public organisation.

She has many years of experience working on monitoring of marine water quality and chemical risk assessment.

What is the aim of Work Package 6?

As DGT results cannot be directly compared to EQS marine water layed down by the regulation (WFD), the general objective of this WP is to define a methodology to adapt an EQS marine water to DGT for nickel, lead and cadmium, so that DGT results could be used in a regulatory context for waterbody quality assessment. This innovative project is based on simultaneous collection of water samples and DGT deployments. This will enable comparison of measured DGT-labile metal concentrations to access chemical status of transitional and coastal waters and, thus, implementation of DGTs for regulatory monitoring within European Directives.

Isabelle IFREMER 2

3 actions are carried out within the framework of this WP:

  • EQS adaptation for priority metals (Pb, Ni, Cd);
  • Thresholds adaptation for other specific metals (Co, Fe, Mn, Zn) ;
  • Simulation of obtained EQS values of DGTs metal data for chemical status assessment.

Which kind of data had to be acquired to achieve this objective?

The first step is to understand how EQS marine water have been determined, what are the barriers that prevent the use of DGTs in a regulatory framework, and to define the difference between a filtered water result and a DGT result. This expertise is essential in order to understand how an adaptation of the EQS to DGT can be done.

The second step is to acquire relevant, reliable and comparable field data. One of the objectives was to acquire data over a wide range of concentration and to reach and even exceed if possible the EQS value. As we knew that such level of concentration (EQS values) are not met usually in marine environment, we have selected some sites suspected to be highly contaminated for Cd, Ni or Pb, for example, harbours. In the framework of the Monitool project, we have acquire relevant, reliable and comparable results on DGT and filtered water (Seafast ICPMS), these results comes from different marine environment context, which gives even more consistency to this precious database (more than 250 DGT samples and more than 500 water samples which correspond to 2,500 data of metal concentrations in DGT resins, and about 6,500 data of metal concentrations in marine and estuarine water).

The last step is to establish a methodology and to propose EQS DGT values.

What are the links of WP6 with others WP?

For the consistency of the EQS DGT determination, WP6 need to have a robust and reliable dataset and an appropriate statistical treatment. The database was designed by AZTI (leader of WP4) and each Partner was responsible for their data to be recorded in the database following the agreed protocol (WP5 lead by CEFAS). The data processing in the framework of the WP6, complete the exploration of data done by AZTI (WP4).

Have you got first results?

The first results were presented in Nantes in February at the 5th MONITOOL progress meeting. They are still preliminary. Prior the adaptation of EQS marine water to DGT, it is necessary to highlight a correlation (statistically representative) between the DGT measurements and concentrations in dissolved water (spot sampling).

What is also important to consider is that the adaptation of an EQS for DGT is not the only possibility for the use of DGT in the framework of the WFD. Depending on the metal considered, if the model allows it, it is possible to determine a concentration in the dissolved fraction from a concentration in the DGT and thus compare this value to EQS marine water. This is what we will be working on in the coming months.

MONITOOL Partners during the last meeting in Nantes, FranceMONITOOL partners share and assess the results in Nantes and proceed with the last steps of the project

Ifremer has hosted the 5th progress meeting of MONITOOL Project, where all the partners shared the remarkable work done during the last months and showed their commitment for the next steps to be taken.

The meeting of 11th and 12th  of February was held in IFREMER facilities (Institut Français de Recherche pour l'Exploitation de la Mer)  in Nantes (France), and all the partners  were given the opportunity to share the work they had done during the last period (last meeting took place in May 2019  in Gran Canaria).

Much time of this 5th meeting was spent on the presentation and discussion of the results of two work packages: WP 4- Database Management and correlation studies (led by Fundación AZTI-Spain) and WP 6- EQS Adaptation and Chemical Status Assessment (led by IFREMER-France).

Regarding WP4, after the processing of the data obtained in the two sampling campaigns performed in the different regions of the MONITOOL-consortium, interesting outcomes were observed:

  • A first and remarkable result of the MONITOOL project is that 100% of the water samples collected during the two sampling campaigns (winter and summer) and analysed for dissolved metal concentrations (with ICP-MS), are below the AA-EQS (annual average) values established for cadmium (200 ng/L) and nickel (8600 ng/L). In the case of lead, only the 15% of the samples have exceeded the EQS value (1300 ng/L).
  • Once the necessary statistical analyses to study the relationships between the concentrations of metals measured in water and those measured with DGTs have been carried out, it can be affirmed that there is a strong correlation for all the metals under study (cadmium, nickel, lead, copper, manganese and zinc) with the exception of cobalt.
  • Finally, for most sampling locations, none of the environmental variables considered (salinity, temperature, dissolved oxygen, turbidity, pH, dissolved organic carbon, total organic carbon and concentration of suspended solids) were found to affect the relationship between metals measured by spot sampling and those measured with DGT. However, in a small/reduced group of stations, where high salinity and/or temperature was present, different relationships have been found for some metals (cadmium, manganese and lead) that require further investigation.

Concerning WP6, as DGT metal concentration results cannot be directly compared to marine water Environmental Quality Standards (EQS marine water), the adaptation of these EQS is essential. During the 5th meeting, two different approaches applied were presented to all partners: the first approach is to determine EQSDGT, as expected in the MONITOOL project, which can be done either using conversion factor or using simple linear regression.

The second approach does not involve the determination of EQSDGT, it consists to convert the DGTs results into ICP data using linear regression for direct comparison with AA-EQS marine water.

The suitability of each approach was discussed. This task will be further refined and completed in the following months

The main findings of MONITOOL Project are expected to be published by the consortium in several science and technology journals. In this respect, it is intended that at least four publications are ready to be published at project completion. For this purpose, during the following months, the partners will continue working on the processing of the data and looking for the more suitable journals. 

The consortium is considering the continuity of the current successful partnership by submitting a joint proposal when applying to new European calls for projects. Several innovative project ideas of transnational relevance have been proposed, which will be developed as strong proposals.

Interview with Maria J. Belzunce Ph.D., leader of MONITOOL Work Package 4 (Database Management and correlation studies)

Maria J. Belzunce Ph.D. leads the Work Package 4 (Database Management and correlation studies) of the MONITOOL project. She works in the Marine Research Division of AZTI Foundation, located in the Basque Country - Spain. She has over 20 years experience working on trace metals and their effects in the marine environment.ebelzunce 3

What is the aim of Work Package 4?

The purpose of Work Package 4 (WP4) is to develop a common database to allow the compilation and interchange of all information related with physico-chemical parameters and metal concentrations for quality water assessment. The participation of all Partners is required in this work package because they must provide data from their regions to the database.

AZTI, as leading partner of WP4, guarantees an efficient cooperation between partners which is relevant to achieve the goals of this activity within the timeframe and accordingly to the methodology established by all Partners.

Which type of data is provided in the database?

Two types of data:

  • Data obtained from the literature related with dissolved metal concentrations from “classical” spot water sampling, with chemically labile metals and with labile metal concentrations derived from Diffusive Gradient Thin films (DGTs), and
  • Data obtained in this project from the eight consortium regions that cover the whole Atlantic region, including also the Mediterranean areas. These data include the dissolved metal concentration from spot water sampling, the chemically labile metals and the labile metal concentrations derived from DGTs. Furthermore, the physico-chemical parameters measured "in situ" every sampling time in 8 different regions are also collected in the database.

The physico-chemical parameters are the following: salinity, temperature, sampling depth, dissolved organic carbon, suspended matter, turbidity and "in situ" observations.

How many data have you provided to the database?

Data from literature are very scarce. We have not found many studies related with parallel measurement of metal concentrations in dissolved water (taken by spot sampling) and labile metal concentration in DGT resins with raw data available. In this sense, this study represents a novelty as it is the first database that compiles a large number of this type of data from different European regions.

In the framework of Monitool project we have produced more than 250 DGT samples and more than 500 water samples. In each DGT sample, the concentration of priority (Cd, Ni and Pb) and specific metals (Al, Cr, Co, Cu, Fe, Mn and Zn) have been analyzed and the data reported in the database. In each water sample the priority and specific metals have been analyzed by seaFAST ICP-MS. Besides, in each water sample, the priority metals have been analyzed by voltammetry technique. All the obtained data have been recorded in the database.

This means that, apart from the physico-chemical parameters data, the database compiles about 2,500 data of metal concentrations in DGT resins, and about 6,500 data of metal concentrations in marine and estuarine water samples.

With such large amount of data how did you deal with the database in order to minimize errors in data transcription, to reduce variability and to guaranty the homogeneity and comparability of data, same units, etc.?

The database was designed by AZTI as leader of WP4 and put in consensus with the other partners. In the same way, the protocol for the database management was proposed by AZTI and discussed among partners until reach a common agreement.

Each Partner was responsible for their data to be recorded in the database following the agreed protocol. After all data collection, several revisions were done by AZTI to guaranty the homogeneity of data.

Apart from the data collection, what other function fulfils the database?

The database is not only for data collection, but it is need for the information interchange between partners and for the statistical analysis to relate metal concentrations in Diffusive Gradient Thin films (DGTs) with spot water samplings. It is also necessary to evaluate the effect of water physical-chemical parameters in trace metal concentrations, and finally, based on the data recorded and on the correlations between data, it is possible to propose a methodology to obtain Environmental Quality Standards (EQS) adapted to the labile metal concentration obtained by DGTs. This step is the final purpose of the database and it is performed in close collaboration with Work Package 6 leaded by IFREMER.

As a matter of fact, last September, AZTI and IFREMER had a workshop to analyze correlations between data and to propose a methodology for adapted “labile metal concentration” EQS.

IPMA complete metal analysis in seawater samples

The MONITOOL project aims to establish technical/scientific conditions to monitor existing metal contaminants in the coastal and estuarine waters using passive sampler devices. This objective is particularly important for monitoring the chemical state of these waters to further application to the Water Framework Directive (WFD) and the Marine Strategy Framework Directive. 

Nuno at IPMAThe Portuguese Institute of the Sea and Atmosphere (IPMA) was the partner responsible for the task involving the determination of the total concentration of trace metals in water using a seaFAST sampling system coupled with an ICP-MS (Perkin-Elmer NexION 2000C).

Up to 400 estuarine/seawater samples were collected and analysed. Total dissolved concentrations of Cd, Pb, Ni, Co, Cu, Mn and Zn were determined in coastal and estuarine waters from several areas of France, Ireland, Italy (Sardinia), Portugal, Spain (Basque country and Canary Islands), Scotland and United Kingdom.

Based on the obtained results, metal levels varied within wide ranges evidencing conditions from pristine to anthropogenic metal contamination. For metals regulated by the WFD (Cd, Pb and Ni) by the EQS (Environmental Quality Standards), the higher concentrations were found in estuarine waters even surpassing the regulatory values. This pattern was also found for the other analysed elements although some high values are related with natural processes. Are example Mn and Co which are related with freshwater input and early diagenetic processes.

An exercise was performed among all partners to evaluate contamination during the sampling procedure. Adequate sampling conditions were found for Cd, Ni, Co, Cu and Mn, while for Pb and Cd and additional cleaning step is needed.