EUSEDcollab: a network of data from European catchments to monitor net soil erosion by water.

As a network of researchers we release an open-access database (EUSEDcollab) of water discharge and suspended sediment yield time series records collected in small to medium sized catchments in Europe. EUSEDcollab is compiled to overcome the scarcity of open-access data at relevant spatial scales for studies on runoff, soil loss by water erosion and sediment delivery. Multi-source measurement data from numerous researchers and institutions were harmonised into a common time series and metadata structure. Data reuse is facilitated through accompanying metadata descriptors providing background technical information for each monitoring station setup. Across ten European countries, EUSEDcollab covers over 1600 catchment years of data from 245 catchments at event (11 catchments), daily (22 catchments) and monthly (212 catchments) temporal resolution, and is unique in its focus on small to medium catchment drainage areas (median = 43 km2, min = 0.04 km2, max = 817 km2) with applicability for soil erosion research. We release this database with the aim of uniting people, knowledge and data through the European Union Soil Observatory (EUSO).

Trapped microplastics within vertical redeposited sediment: Experimental study simulating lake and channeled river systems during resuspension events.

Plastic waste and its fragments (microplastics; <5 mm) have been observed in almost all types of environments. However, the mechanisms underlying the flow and transport processes of plastics are unknown. This is particularly valid for river sediments, where complex interactions occur between particles and influence their vertical and horizontal distribution patterns. In this study, we investigated the vertical redistribution of 14 pristine microplastics (MPs) with different densities, sizes, and shapes within disturbed sediment without lateral transport (i.e., low-velocity flow). MPs were spiked into sediments (height: 8 cm) in a column with a height of 1 m (diameter: 6 cm) filled to the top with water. The sediment was perturbed by turning the column upside-down to simulate remobilization and the subsequent deposition of sediment. After the complete sedimentation of the particles, the water column was filtered and the sediment was cut into vertical sections. MPs were then extracted from the sediment using sieves and a density separation method, and were counted under a stereomicroscope. Low-density polymers were mainly recovered in the water column and at the surface of the sediment, whereas high-density polymers were found within all sediment sections. The vertical distribution of high-density polymers changes primarily with the sediment grain size. The distribution of each polymer type changes depending on the size and/or shape of the particles with complex interactions. The observed distributions were compared with the expected distributions based only on the vertical velocity formulas. Overall, the formulas used did not explain the sedimentation of a portion of low-density polymers and predicted a lower distribution in the sediment than those observed in the experiment. In conclusion, this study highlights the importance of considering MPs as multi-dimensional particles and provides clues to understand their fate in low-velocity flow systems, considering that they undergo scavenging in sediments.

Extraction of microplastics from sediment matrices: Experimental comparative analysis.

Microplastics are small (<5 mm) fragments of plastic debris that are ubiquitous in oceans and terrestrial ecosystems. Studies on microplastics in sediment and soil matrices are particularly challenging because of the need to separate the plastics from the sediments. We investigated the efficiencies of 18 combinations of six extracting solutions (ESs) (oil, water, oil-in-water, NaCl, oil-in-NaCl, and NaI) and three isolation methods (IMs) (hand stirring, centrifugation, and aeration) for fine and coarse sediments, with low and high density polymers. IMs did not affect the extraction efficiency. Except in case of oil, all ESs enabled good extraction (84 ± 17%) of light polymers (PE and PE-ABS). NaI presented the best extraction efficiency (71 ± 17%) for the densest polymers (PET, PES, and PA). For these ESs, fibers were extracted at a lower efficiency than pellets and fragments, and sediment gran size did not affect the extraction. For other ESs, mean extraction rates ranged from 5% to 48%. Overall, the extraction efficiencies were lower than those found in the literature, despite repeating the separation process three times. The collection of floating materials remained a problem, as plastics tended to adhere to the glass wall. Our work will help the comparability between previous and future monitoring results and the selection of the most suitable protocols for future studies. This work clearly demonstrates also that there is no robust protocol for extracting all types and forms of microplastics from fine sediments and that research efforts to arrive at a reliable method remain by taking account the interaction of MPs with other particles as well as the electrostatic properties of MP.

To What Extent Can Micro- and Macroplastics Be Trapped in Sedimentary Particles? A Case Study Investigating Dredged Sediments.

Plastic wastes and their fragments (microplastics, MPs < 5 mm) represent a global, persistent, and ubiquitous threat to ecosystems. Their sources, transfers, and fates are still poorly understood, especially in rivers. To fill this gap, sediments were collected from two dredging disposal sites along the Aa River (France). Four pits were dug, and triplicate samples were obtained at four depths (down to 140 cm). The sediments were sieved to 5 mm to collect macroplastics (MaPs). MPs were separated from the sediment based on density using a NaI solution (1.6 g/mL). Suspected plastics were analyzed with Fourier transform infrared spectroscopy. The studied sediments were found to be widely contaminated with concentrations ranging from 0.97 to 77 MaPs/kg and from 0.78 to 2800 MPs/kg, which were 1-4 orders of magnitude lower than those in most polluted European riverbeds. The MaPs were principally polyethylene, polypropylene, polystyrene, and polyvinyl chloride films, whereas the MPs were mainly polyamide and polyester fibers. The plastic concentrations and features of the two sites, which were filled at two different times, differed. Several factors occurring before and after dredging operations may explain these discrepancies. Nevertheless, no relationships with the sediment features were noted, and thus, one major driving force could not be identified. At the site scale, more than 1 ton of plastic could be stored. In conclusion, this study highlights the importance of dredged sediments for past plastic pollution studies and global plastic budget estimations.

Environmental availability and oral bioaccessibility of Cd and Pb in anthroposols from dredged river sediments.

Dredging and disposal of sediments onto land sites is a common practice in urban and industrial areas that can present environmental and health risks when the sediments contain metallic elements. The aim of this study was to characterise and study the environmental and toxicological availability of Cd and Pb in anthroposols from dredged river sediments. To do this, 67 surface samples spread over 12 sediment disposal sites in northern France were studied. The results showed substantial heterogeneity for this matrix in terms of physicochemical parameters and contamination degree; however, ascending hierarchical clustering made it possible to classify the samples into eight groups. For each group, the mobile fraction of Cd and Pb was studied using single EDTA extraction, solid-phase distribution was analysed with sequential extractions and toxicological availability was assessed with the oral bioaccessibility test. The results showed that (i) Cd had a higher environmental and toxicological availability than Pb; (ii) this availability depends on the physicochemical characteristics of the matrix; and (iii) it is necessary to take into account the environmental and toxicological availability of contaminants when requalifying these sites in order to propose appropriate management measures. In the first years after sediment disposal, it would appear that the environmental and toxicological availability of Cd and Pb increased (from 52.5 to 71.8% and from 28.9 to 48.9%, respectively, by using EDTA and from 50.2 to 68.5% for Cd with the bioaccessibility test). Further studies would therefore be required to confirm this trend and understand the mechanisms involved.

Assessing temporal variability and controlling factors of the sediment budget of a small agricultural catchment in Northern France (the Pommeroye).

A high-frequency monitoring station was implemented at the outlet of the small catchment of the Pommeroye (0.54 km2) in Northern France to study erosion by runoff and hydro-sedimentological responses to heavy rainfall events in the context of Quaternary loess deposits. The aim of this experimental work is to assess the temporal variability of sediment yield and to identify the factors controlling the hydro-sedimentary response. To achieve this goal, statistical and hydro-sedimentary dynamic analyses were performed. During two years of monitoring (April 2016-April 2018), 48 flood events were recorded. The specific sediment yield (SSY) is highly variable and was evaluated to 29.4-70 t km-2 yr-1 which is conventional for the study region. Most of the sediment yield was produced in winter (55%) and autumn (42%). Only 3% of SSY were produced during spring and summer periods. According to our results, only 6% of the erosive events are responsible for the transport of more than 40% of the sediment flux recorded at the outlet. This underlines the temporal variability of the hydro-sedimentary production in small agricultural catchments for which most of the hydro-sedimentary flux is produced during a limited number of events. The results of statistical analyses show that the total amount of rainfall and the duration of a rainfall episode are the main controlling factors on the hydro-sedimentary response. Our results also suggest that the rainfall kinetic energy better reflects the sediment detachment, and that the 48 h-antecedent rainfall is not linked to the hydro-sedimentary response.

Quantification of tributaries contributions using a confluence-based sediment fingerprinting approach in the Canche river watershed (France).

Since a few years, land use management aims to reduce and control water erosion processes in watersheds but there is a lack of quantitative information on the contribution of the sources of transported sediment. This is most important in agricultural areas where soils are sensitive to erosion. The geology of these areas is often characterized by large expanses of relatively homogeneous quaternary silts. The possibility of distinguishing the sources of erosion according to their geological substratum is thus very delicate. This information is important because its lack can lead to the mis-implementation of erosion control measures. To address this request, a confluence-based sediment fingerprinting approach was developed on the Canche river watershed (1274 km2; northern France), located in the European loess belt, an area that is affected by diffuse and concentrate erosion processes. Suspended particulate matter was collected during five seasonal sampling campaigns using sediment traps at the outlet of each tributary and confluence with the main stream of the Canche river. The final composite fingerprint was defined using physico-chemical and statistical analyses. The best tracer parameters for each tributary were selected using stepwise discriminant function analyses. These parameters were introduced into a mass balance mixing model incorporating Monte-Carlo simulations to represent the uncertainty. Estimates of the overall mean contributions from each tributary were quantified at different temporal scales. The annual sediment flux tributaries contributions range from 3 to 22% at the outlet of the Canche river, and annual sediment flux range from 0.87 to 40.7 kt yr-1. The Planquette and the Créquoise tributaries appear to be those producing the largest sediment flux. In contrast, tributaries with the highest number of erosion control on their area exhibit the lowest values of sediment flux. Our results indicate a positive impact of recent land management policies in the Canche river watershed.

Analyzing the uncertainty of diffusive gel-based passive samplers as tools for evaluating the averaged contamination of surface water by organic pollutants.

Agarose gel-based passive samplers are nowadays one of the most effective sampling devices able to provide a quantitative evaluation of water contamination level for a broad range of organic contaminants. These devices show significant improvements in comparison to the previous passive samplers dedicated to hydrophilic compounds because they tend to reduce the effect of hydrodynamic flow conditions on the uptake rate of compounds and thus subsequently to improve their accuracy. However, albeit their effects minimized, hydrodynamic water flow and temperature are reported as variables likely to change the uptake rate of compounds that may lead to some inaccuracy if they are not adequately taken into account. This work aims to investigate the magnitude of effects of such uncorrected variables on the bias of the deduced water contamination level. The analysis of the error structure shows that the uncertainty on the diffusivity of contaminants in agarose gel and its dependency on temperature are the most inferring factors. At 8 °C, these factors are, respectively, responsible of 34 and 33% of the squared uncertainty on the final deduced contamination level. The overall uncertainty for a single exposed passive sampler is in the order of 39% and drops to 23% if threesamplers are co-exposed (at 8 °C). Despite this uncertainty, we present results for a set of pesticides and personal care products throughout a field monitoring conducted over a 4-month period, which show the potential of passive samplers to allow assessing the temporal trend of water contamination.

Understanding and predicting the diffusivity of organic compounds in polydimethylsiloxane material for passive sampler applications using a simple quantitative structure-property relationship model.

The diffusivity of 145 compounds in polydimethylsiloxane (PDMS) material was determined in the laboratory using a film stacking technique. The results were pooled with available literature data, providing a final data set of 198 compounds with diffusivity (DPDMS ) spanning over approximately 5 log units. The principal variables controlling the diffusivity of penetrants were investigated by comparing DPDMS within and between different homologous series. The dipole moment, molecular size, and flexibility of penetrants appear to be the most prevalent factors controlling a compound's diffusivity. A nonlinear quantitative structure-property relationship is proposed using as predicting variables the molecular volume, the number of rotatable bonds, the topological polar surface area, and the number of O and N atoms. The final relationship has a correlation coefficient of R2 = 0.81 and a mean absolute error of 0.26 m2 s-1 (log unit), approaching the average error for the experimentally determined values (0.12 m2 s-1 ). The model, based on a heuristic approach, is ready for use by analytical chemists with no specific background in theoretical chemistry (notably for passive sampler development). Environ Toxicol Chem 2018;37:1291-1300. © 2018 SETAC.

Near-surface distribution of pollutants in coastal waters as assessed by novel polyethylene passive samplers.

We report a novel and inexpensive method to provide high resolution vertical measurements of temporally integrated organic contaminants in surface and sub-surface waters in polluted coastal environments. It employs a strip of polyethylene deployed as a passive sampler. Verifications are confirmed via conventional spot sample analyses and against Performance Reference Compound (PRC) calibration methods. Analytes targeted include 16 Polycyclic Aromatic Hydrocarbons, 15 personal care products, 8 organophosphorus flame retardants, 4 antifouling 'booster' biocides and 15 n-alkanes. Whilst all contaminants typically revealed homogeneous concentrations from 10 cm to 3 m depth in the selected harbour (<30% variations), many increased sharply at the air-sea interface. The passive sampler was shown to afford better resolution than could be achieved using conventional analytical techniques at the surface microlayer (SML). Whilst hydrophobicity appeared to be a key factor for the enrichment of many determinants, less correlation was found for the emerging contaminants.

Calibration and response of an agarose gel based passive sampler to record short pulses of aquatic organic pollutants.

A passive sampler inspired from previous devices was developed for the integrative sampling of a broad range of contaminants in the water column. Our primary objective was to improve the performance of the device to provide accurate and averaged pollutant water concentrations. For this purpose, an agarose diffusive gel was used as the boundary layer that drives the analyte uptake rate. Contrary to conventional passive samplers, the developed device does not require the sampling rates to be corrected for exposure conditions (e.g. hydrodynamic flow) because the diffusive gel boundary layer selected was sufficiently large to control the pollutant diffusion rate from the aqueous phase. The compounds diffusion coefficients in agarose gel and the gel thickness are the only required data to accurately calculate the time weighted averaged water concentration of pollutants. The performance of the developed sampler was evaluated in the laboratory under two contamination scenarios and in the field in 8 contrasting exposure sites for a selection of 16 emerging pollutants and pesticides. The results show that detection limits of this method are environmentally relevant and allow the determination of the averaged pollutant concentrations. Additionally, the ability of the device to sense very short contamination pulses (5-320min) was evaluated through a theoretical approach and laboratory tests. Results show that the device is suitable for sampling contamination pulses as short as 5min without deviation from the actual average concentrations of pollutants.

Assessing the transport of PAH in the surficial sediment layer by passive sampler approach.

A new method based on passive samplers has been developed to assess the diffusive flux of fluorene, fluoranthene and pyrene in the sediment bed and across the sediment-water interface. The dissolved compound concentration gradient in the sediment in the vertical direction was measured at the outlet of a storm water pond by using polyethylene strips as passive samplers. Simultaneously, the dissipation of a set of tracer compounds preloaded in the passive samplers was measured to estimate the effective diffusion coefficients of the pollutants in the sediment. Both measurements were used to evaluate the diffusive flux of the compounds according to Fick's first law. The diffusive fluxes of the 3 studied compounds have been estimated with a centimetre-scale resolution in the upper 44cm of the sediment. According to the higher compound diffusion coefficient and the steeper concentration gradient in the surficial sediment layer, the results show that the net flux of compounds near the sediment interface (1cm depth) is on average 500 times higher than in the deep sediment, with average fluxes at 1cm depth on the order of 5, 0.1 and 0.1ng/m2/y for fluorene, fluoranthene and pyrene, respectively.

A new application of passive samplers as indicators of in-situ biodegradation processes.

In this paper, a method for evaluating the in-situ degradation of nitro polycyclic aromatic hydrocarbons (nitro-PAH) in sediments is presented. The methodology is adapted from the passive sampler technique, which commonly uses the dissipation rate of labeled compounds loaded in passive sampler devices to sense the environmental conditions of exposure. In the present study, polymeric passive samplers (made of polyethylene strips) loaded with a set of labeled polycyclic aromatic hydrocarbons (PAH) and nitro-PAH were immersed in sediments (in field and laboratory conditions) to track the degradation processes. This approach is theoretically based on the fact that a degradation process induces a steeper concentration gradient of the labeled compounds in the surrounding sediment, thereby increasing their compound dissipation rates compared with their dissipation in abiotic conditions. Postulating that the degradation magnitude is the same for the labeled compounds loaded in polyethylene strips and for their native homologs that are potentially present in the sediment, the field degradation of 3 nitro-PAH (2-nitro-fluorene, 1-nitro-pyrene, 6-nitro-chrysene) was semi-quantitatively analyzed using the developed method.

Relationship between the water-exchangeable fraction of PAH and the organic matter composition of sediments.

The sorption of PAH on 12 different sediments was investigated and was correlated to their corresponding organic matter (OM) content and quality. For this purpose, the OM was precisely characterized using thermal analysis consisting in the successive combustion and quantification of the increasingly thermostable fractions of the OM. Simultaneously, the water-exchangeable fraction of the sorbed PAH defined as the amount of PAH freely exchanged between the water and the sediment (by opposition to the PAH harshly sorbed to the sediments particles) was determined using a passive sampler methodology recently developed. The water concentrations, when the sediment-water system is equilibrated, were also assessed which allows the determination of the sediment-water distribution coefficients without artifacts introduced by the non water-exchangeable fraction of PAH. Hence, the present study provides the distribution coefficients of PAH between the water and 4 different OM fractions combusted at a specific temperature range. The calculated distribution coefficients demonstrate that the sedimentary OM combusted at the intermediate temperature range (between 300 °C and 450 °C) drives the reversible sorption of PAH while the inferred sorption to the OM combusted at a lower and higher temperature range does not dominate the partitioning process.

Simulation of aromatic polycyclic hydrocarbons remobilization from a river sediment using laboratory experiments supported by passive sampling techniques.

Resuspension of bedded sediments was simulated under laboratory-controlled conditions in order to assess the amount of polycyclic aromatic hydrocarbons (PAH) remobilized in the dissolved fraction during one short and vigorous mixing. The desorbed amount of PAH was compared to the exchangeable fraction, the total amount of PAH sorbed on the sediment particles, and the dissolved PAH amount contained in the interstitial pore waters in order to evaluate the contribution of each fraction to the total amount of PAH released. To monitor the desorption of PAH and measure low trace level concentrations, passive samplers were used in an experimental open flow through exposure simulator. Results show that for the selected sediment, a substantial fraction of sorbed PAH (69 % of the total amount) is not available for remobilization in a depleted medium. Obtained data pinpoint that over 9 days, only 0.007 % of PAH are desorbed by passive diffusion through a water-sediment interface area of 415 cm(2) and that an intense resuspension event of 15 min induces desorption of 0.015 % of PAH during the following 9 days. Results also highlight that during resuspension simulation, modifications of the sediment and the water body occurred since partitioning constants of some pollutants between sediment and water have significantly decreased.

Thickness and material selection of polymeric passive samplers for polycyclic aromatic hydrocarbons in water: Which more strongly affects sampler properties?

Three configurations of single-phase polymer passive samplers made of polyoxymethylene (POM), silicone rubber, and polyethylene (PE) were simultaneously calibrated in laboratory experiments by determining their partitioning coefficients and the POM diffusion coefficients and by validating a kinetic accumulation model. In addition, the performance of each device was evaluated under field conditions. With the support of the developed model, the device properties are discussed with regard to material selection and polymer thickness. The results show that a sampler's properties, such as its concentration-averaging period and ability to sample a large amount of polycyclic aromatic hydrocarbons, are widely affected by material selection. Sampler thickness also allows modulation of the properties of the device but with a much lower magnitude. Selection of the appropriate polymer and/or thickness allows samplers to be adapted either for quick equilibration or for the kinetic accumulation regime and promotes either membrane or water boundary layer control of the kinetic accumulation. In addition, membrane-controlled or equilibrated compounds are quantified with greater accuracy because they are not corrected by the performance reference compounds approach. However, the averaged concentrations cannot be assessed when compounds reach equilibrium in the sampler, whereas membrane-controlled devices remaining in the kinetic accumulation regime provide averaged concentrations without requiring performance reference compound correction; detection limits are then increased because of the higher mass transfer resistance of the membrane. Environ Toxicol Chem 2016;35:1708-1717. © 2015 SETAC.

Factorial Kriging Analysis as a tool for explaining the complex spatial distribution of metals in sediments.

Rivers flowing through urbanized and industrial areas are usually greatly damaged by anthropogenic activities discharging contaminants. Characterizing the spatial distribution of pollutants in sediments is of high importance for selecting a suitable remediation operation, but is a complex task because this spatial variability is the result of various physical and chemical mechanisms occurring at different scales. Factorial Kriging Analysis (FKA) was applied on data collected in a canalized river (Scarpe, France) for that purpose, because this geostatistical technique allows to decompose a given variable into components of different spatial correlations and map them separately. This decomposition is meaningful provided that it can be related to physical phenomena occurring at the identified spatial scales. FKA applied to Cd and Zn concentrations in sediments of the Scarpe river proved to be effective, allowing their mapping to be decomposed in a first map related to a short-range spatial correlation corresponding to hot spots interpreted as the impact of industrial and urban inputs located along the canal, and a second map related to a long-range spatial variability associated with long pollutant plumes interpreted as the effect of one major upstream pollutant input.