Elsevier

Science of The Total Environment

Volume 636, 15 September 2018, Pages 1597-1607
Science of The Total Environment

Mobile dynamic passive sampling of trace organic compounds: Evaluation of sampler performance in the Danube River

https://doi.org/10.1016/j.scitotenv.2018.03.242Get rights and content

Highlights

  • A dynamic passive sampling device was designed to speed up the chemical uptake

  • The device was applied in the Danube river for sampling from a cruising ship

  • Spatially and temporally integrated samples of dissolved compounds were obtained

  • The device samples up to 5 times faster in comparison with a caged passive sampler

  • Mutual comparability of three passive samplers deployed in parallel was shown

Abstract

A “dynamic” passive sampling (DPS) device, consisting of an electrically driven large volume water pumping device coupled to a passive sampler exposure cell, was designed to enhance the sampling rate of trace organic compounds. The purpose of enhancing the sampling rate was to achieve sufficient method sensitivity, when the period available for sampling is limited to a few days. Because the uptake principle in the DPS remains the same as for conventionally-deployed passive samplers, free dissolved concentrations can be derived from the compound uptake using available passive sampler calibration parameters. This was confirmed by good agreement between aqueous concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) derived from DPS and conventional caged passive sampler. The DPS device enhanced sampling rates of compounds that are accumulated in samplers under water boundary layer control (WBL) more than five times compared with the conventionally deployed samplers. The DPS device was deployed from a ship cruising downstream the Danube River to provide temporally and spatially integrated concentrations. A DPS-deployed sampler with surface area of 400 cm2 can reach sampling rates up to 83 L d−1. The comparison of three passive samplers made of different sorbents and co-deployed in the DPS device, namely silicone rubber (SR), low density polyethylene (LDPE) and SDB-RPS Empore™ disks showed a good correlation of surface specific uptake for compounds that were sampled integratively during the entire exposure period. This provided a good basis for a cross-calibration between the samplers. The good correlation of free dissolved PAHs, PCBs and HCB concentration estimates obtained using SR and LDPE confirmed that both samplers are suitable for the identification of concentration gradients and trends in the water column. We showed that the differences in calculated aqueous concentrations between sampler types are mainly associated with different applied uptake models.

Introduction

Organic compounds are often present in the water column of rivers and lakes at trace concentrations that are difficult to detect when conventional low volume spot sampling of water is applied. Despite the low concentrations, chemicals can present a significant risk to aquatic organisms and humans, and many of them are regulated in surface waters (EU, 2013, EU, 2000). Reliable and representative monitoring is required for assessing compliance of water bodies with environmental quality standards, or for characterizing spatial and temporal contamination trends.

Among available methods, passive sampling presents a promising approach to future regulatory monitoring of trace organic compounds (Booij et al., 2016; Lohmann et al., 2012). Besides practical advantages that include passive in situ concentration and preservation of sampled compounds in sorbent materials, passive sampling provides freely dissolved compound concentrations, Cw (Vrana et al., 2005). The Cw is considered to play a key role in understanding chemical's exposure of aquatic organisms (Reichenberg and Mayer, 2006).

When conventional passive water samplers are applied, they must be deployed for several weeks or months, because their ambient sampling rates (Rs), representing the volume of water extracted per unit of time, are low. However, when the time period available for passive sampling is restricted, compensation by high sampling rate is needed to sample a sufficient volume of water for instrumental quantification or measuring chemical effects using bioanalytical tools.

Since Rs proportionally increase with the surface area of a sampler (Booij et al., 2007) they can be increased by using samplers in the form of large thin sheets. Furthermore, Rs increase when the water flow rate or turbulence on the sampler surface is higher (Estoppey et al., 2014; Li et al., 2010; Vermeirssen et al., 2009; Vrana and Schüürmann, 2002). Faster flow conditions cause a thinner water boundary layer (WBL) and lead to lower resistance to mass transfer (Levich, 1962). This is because the mass transfer of hydrophobic compounds is typically controlled by their diffusion through the WBL (Rusina et al., 2007). Flow turbulence can be increased by positioning samplers in a natural or artificially created current, by shaking, rotating or vibrating them during exposure in water (Qin et al., 2009). Allan et al. (2011) have shown increased Rs by towing samplers fastened to the end of a benthic trawl net. In general, input of some external mechanical energy is needed for increasing the water turbulence in vicinity of the samplers.

In this study, we investigated the applicability of a novel “dynamic” passive sampling device (DPS) that was developed with the aim to maximize the sampling rates of pollutants by forcing water at high flow rate along the passive sampler surface. The high flow was achieved by jetting water through a narrow flow-through sampler exposure chamber using a pump. Hereto we 1) compared the performance of DPS with conventional deployment of passive samplers in cages; 2) tested the performance of the DPS device by deployment from a moving ship in the Danube river to obtain integrated freely dissolved concentrations of pollutants in the water column over time and space; 3) compared the uptake of compounds by silicone rubber, low density polyethylene and SDB-RPS Empore™ disks samplers co-deployed inside the DPS device. The first two materials are commonly used for sampling hydrophobic compounds, whereas the latter is used also for sampling hydrophilic compounds. Finally, 4) we evaluated aqueous concentrations of atrazine derived from DPS in relation to those from spot water sampling.

Section snippets

Passive samplers

Three types of passive samplers were applied: two partitioning samplers, SR and LDPE sheets and one adsorption sampler based on styrene-divinylbenzene solid phase extraction disks, SDB-RPS Empore™ disks (ED). AlteSil™ translucent SR sheets 0.5 mm thick (Altec, UK) were cut into samplers with a size of 14 × 28 cm (392 cm2, 23 g), Soxhlet extracted in ethylacetate for 72 h and spiked according to the procedure described in Smedes and Booij (2012) with 14 performance reference compounds (PRC: D10

Comparison of caged sampler and DPS

The Cw,SR of PAHs, PCBs and HCB were calculated using analyte amounts accumulated in SR and the Rs,SR obtained as described in Section 2.4. The Cw,SR for stationary caged samplers and stationary DPS devices downstream Bratislava agreed very well (Fig. 3, left graph), with a median ratio of 0.93 and 0.83 for individual PAHs and PCBs, respectively. Similarly, a reasonably good median Cw,SR ratio was obtained for individual PAHs and PCBs from caged samplers and mobile passive samplers in the

Conclusions and perspectives

The main DPS usage domain is a representative measurement of compound levels, averaged in time (TWA) and/or space. The DPS device presents a useful alternative approach to the conventional sampler deployment technique in cages in situations where integrative uptake of compounds accumulated under WBL control must be maximized.

We demonstrated the robustness of the DPS technique in stationary and mobile deployments in a large river. When DPS is used for sampling from a cruising ship, the device

List of terms and abbreviations

    Ax

    sampler × surface area in contact with water

    Caged passive sampler

    a passive sampler deployed in a cage made of perforated stainless steel sheet; It was deployed stationary in the Danube downstream Bratislava (see Table 1).

    DPS

    Dynamic Passive Sampling device; a novel water sampling device which forces water along the surface of sorbent sheets in a stainless steel flow-through chamber. Water passes through the chamber at a high flow rate assisted by a pump. This leads to a high turbulence close to

Acknowledgement

We acknowledge the NORMAN association www.norman-network.net, the SOLUTIONS Project supported by the European Union Seventh Framework Programme (FP7-ENV-2013-two-stage Collaborative project) under grant agreement 603437. The research activities were carried out in the RECETOX Research Infrastructure supported by the Czech Ministry of Education, Youth and Sports (LM2015051) and the European Structural and Investment Funds, Operational Programme Research, Development, Education

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