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RESEARCH ARTICLE
Contents Vol 20(5)

Validation of a calibration model able to estimate the concentration of pesticides in an alpine stream through passive sampling (POCIS) monitoring

Anna Casari A , Loris Tonidandel https://orcid.org/0000-0002-4221-4176 B * , Guido Zolezzi A C , Alberto Bellin A C , Paolo Negri D , Alice Barbero B and Roberto Larcher B
+ Author Affiliations
- Author Affiliations

A University of Trento, C3A - Center Agriculture Food Environment, Via Edmund Mach, 1 38098 San Michele all’Adige (TN), Italy.

B Fondazione Edmund Mach Istituto Agrario di San Michele all’Adige, CTT, Via Edmund Mach, 1 38098 San Michele all’Adige (TN), Italy.

C Department of Civil, Environmental and Mechanical Engineering, Via Mesiano, 77 38123 Trento (TN), Italy.

D Environmental Protection Agency of the Autonomous Province of Trento, Water Quality Unit, Via Mantova, 16 38122 Trento (TN), Italy.

* Correspondence to: loris.tonidandel@fmach.it

Handling Editor: Peter Croot

Environmental Chemistry 20(5) 197-211 https://doi.org/10.1071/EN23052
Submitted: 18 May 2023  Accepted: 25 August 2023  Published: 18 September 2023

© 2023 The Author(s) (or their employer(s)). Published by CSIRO Publishing.

Abstract

Environmental context

Pesticides and other contaminants released by agricultural activities negatively impact aquatic biota and water quality, but are not always measured. The Polar Organic Chemical Integrative Sampler (POCIS) is among the most suitable tools for identifying pesticides and other organic compounds in water bodies. However, determination of a mean concentration (over the duration of the deployment) is still a significant challenge, which is addressed in the present work using field observations and a computational model.

Rationale

The Polar Organic Chemical Integrative Sampler (POCIS) is a passive sampler composed of a receiving phase, Oasis HLB, enclosed between two polyethersulfone (PES) membranes. It is used for monitoring organic compounds in surface water and in groundwater. The measurement of pesticide concentrations by passive samplers in streams still represents an open challenge, which limits the samplers’ use in environmental monitoring of the quality status of water bodies in accordance with the EU Water Framework Directive.

Methodology

We addressed these limitations by calibrating a POCIS with concentration measurements performed on samples collected by means of an automatic sampler from the same section of a small alpine river where a passive sampler was deployed. In the majority of published studies, the analytes were extracted only from the receiving phase, but recent works show that some compounds were also adsorbed by the PES membrane, suggesting the importance of extracting the analytes from both the phase and the membrane.

Results

The POCIS was calibrated for 31 compounds, by a comparison between the total amount of pesticides adsorbed by POCIS (Ms) and the time-weighted average concentration (TWAc) obtained from several grab samples, and by estimation of the sampling rate (Rs), which allows linking the Ms with the TWAc over time. The data showed an increasing Rs trend with hydrophobicity for the most hydrophobic and hydrophilic compounds, while compounds with 1.5 ≤ log Kow ≤ 3.5 assumed a value of Rs independent of log Kow. The contribution of PES membranes allows expansion of the calibration of Rs to the most hydrophobic compounds and allows monitoring of pesticides that would hardly have been detected if they were extracted only from the Oasis HLB phase, such as fluazinam.

Discussion

The calibration was then verified on the same stream and the model extended to a different sampling site; in both cases, the calibration allowed estimation of a value of TWAc that fits with the reality within a factor of 5, and in the majority of cases within a factor of 2. If this level of accuracy is accepted, the Rs reported here can be used to estimate TWAc from sampling with POCIS.

Keywords: alpine stream, in situ calibration, Oasis HLB phase, passive sampling, pesticide, Polar Organic Chemical Integrative Sampler (POCIS), polyethersulfone (PES), sampling rate.

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