Optimising punctual water sampling with an on-the-fly algorithm based on multiparameter high-frequency measurements.

The way in which aquatic systems is sampled has a strong influence on our understanding of them, especially when they are highly dynamic. High frequency sampling has the advantage over spot sampling for representativeness but leads to a high amount of analysis. This study proposes a new methodology to choose when sampling accurately with an automated sampler coupled with a high frequency (HF) multiparameter probe. After each HF measurement, an optimised sampling algorithm (OSA) determines on-the-fly the relevance of taking a new sample in relation to previous waters already collected. Once the OSA was optimised, considering the number of HF parameters and their variabilities, it was demonstrated through a study case that the number of samples could be significantly reduced, while still covering periods of low and high variabilities. The comparison between the total HF dataset and the sampled subdataset shows that physicochemical parameter variability is preserved (Pearson correlations > 0.96) as well as the multiparameter variability (PCA axes remained similar with Tucker congruence > 0.99). This algorithm simplifies HF studies by making it easier to take samples during brief phenomena such as storms or accidental spills that are often poorly monitored. In addition, it optimises the number of samples to be taken to correctly describe a system and thus reduce the human and financial costs of these environmental studies.

Leaching of two northern France slag heaps: Influence on the surrounding aquatic environment.

After the exploitation of coal mines in the 19th and 20th centuries in northern France, many mining slag heaps (SH) were left without any particular management or monitoring. Currently, the influence of these SHs on the quality of surrounding wetlands is hardly known. The purpose of this work is to determine the water quality in the neighbourhood of two SHs located near the city of Douai and its influence on the distribution of aquatic invertebrates in local wetlands. Our approach involves (1) the spatial and temporal characterization of the water composition (anions, major elements, sulphide, DOC and alkalinity) and of the biological diversity (aquatic invertebrates) and (2), based on this chemical and biological screening, the establishment of relationships between water quality and biodiversity distribution through multivariate data analysis. The results clearly indicate that substantial leaching from the slag heaps occurs, given the very high concentrations of dissolved sulphates (in the range of 2 g L-1). While the pH remains weakly basic, indicating that the leaching water has been neutralized by the highly carbonated regional substratum, high levels of biodegradable organic matter and sulphate contents have been noticed. They sporadically cause significant drops in dissolved oxygen and the occurrence of dissolved sulphides that massively reduce biodiversity, qualitatively and quantitatively. In Summer, oxygen saturation is generally lower due to the higher rate of organic matter degradation, and the risk of anoxic episodes therefore increases. Finally, as wetlands are vulnerable environments, these preliminary results suggest that monitoring and management of these sites must be attempted quickly to avoid the degradation of those valuable habitats.

Trace metal speciation in North Sea coastal waters.

Most trace metals exhibit a dual role in marine waters, acting as nutrients at low concentration and being toxic at high concentration. But besides concentration range, speciation is also an important factor. They both show both seasonal and spatial variations. A thorough comparison between total dissolved and particulate concentrations estimated from manual sampling and an assessment of the bioavailability using Diffusive Gradients in Thin Films (DGT) has been performed in this work for Cd, Co, Cu, Ni and Pb, at several sampling points of the Belgian Coastal Zone (BCZ). Additional information to trace back the origin and identify the anthropogenic fingerprint of Suspended Particulate Matter (SPM) was measured using stable carbon isotope measurements in particulate organic matter. Our results show that: (i) particulate and total dissolved metal concentrations are higher at two stations, one in the harbor of Oostende and one offshore; (ii) dissolved and particulate trace metal concentrations do not correlate with the dissolved labile fractions; and (iii) SPM in the harbor zone is likely from allochthonous sources, while in the offshore station marine origin has been evidenced. Our results indicate that, even though contamination is higher in the harbor zones, the trace metal toxicity, which is linked to the metal bioavailability, is most likely not higher than in the open sea. However, with increasing acidification of the ocean, a shift from particulate to dissolved phase might lead to increasing adverse effects on the coastal environment.

In situ measurements of micronutrient dynamics in open seawater show that complex dissociation rates may limit diatom growth.

In this first in situ study of the dynamic availability of phytoplankton micronutrients, a SeaExplorer glider was combined with Diffusive Gradients in Thin Films and deployed in the Mediterranean Sea. On the basis of their labile metal complex pools, we discovered that Fe and Co can be potentially limiting and Cu co-limiting to diatom growth, contrary to the generally accepted view that phosphorus (phosphate) is the growth limiting element in the Mediterranean Sea. For flagellates and picoplankton, phosphorus remains the main element limiting growth. Our in situ measurements showed that organic complexes of Fe and Cu (>98% of total dissolved concentration), dissociate slower than inorganic complexes of Co, Cd and Ni (>99% of total dissolved concentration being free ions and inorganic complexes). This strengthens the potential growth limiting effect of Fe and Cu versus phosphate, which is present as a free ion and, thus, directly available for plankton.

Diel cycles of reduced manganese and their seasonal variability in the Marque River (northern France).

Electrolabile reduced manganese (II) has been monitored by voltammetry during two periods of one month in summer 2014 and at the end of winter 2015 in a small river (the Marque River) located in northern France and going through a suburban area with agricultural activities. Diel variations, evolution within the one-month periods and seasonal differences have been observed. Taking into consideration the multiple physical, biological and chemical reactions regulating manganese speciation in aquatic systems, it has been demonstrated that manganese speciation is probably controlled by the competition of two antagonist reactions: the photoreduction of manganese oxides (in broad sense and represented thereafter by MnOx) and the biotic oxidation of Mn(II). Depending on the season, the biological activity in the river and the amount of luminosity reaching the MnOx, either the production of reduced labile Mn(II) or the precipitation of MnOx can become the dominant process. Other punctual events such as the drop of oxygen concentration due to large inputs of biodegradable organic matter and eutrophication phenomena, rainy events and high luminosity periods can also affect the behaviour of dissolved Mn(II) in the Marque River and so, of other contaminants.

Radial metal concentration profiles in trees growing on highly contaminated soils.

The soil around Metaleurop, a big smelter, is heavily contaminated by Zn, Pb, Cd and Cu. In order to compare the impact of different soil amendments on the metal availability to trees, the polluted soil section was divided in a reference parcel and two others with either sulfo-calcic or silico-aluminous ash amendments. Five different tree species were planted on the parcels and the uptake of heavy metals in these trees was studied. Total and labile metal fractions were assessed in each of the 3 parcels. The mobility and assimilation of the metals was highest in the non-amended, reference soil parcel which had the lowest pH, organic matter and carbonate content. In all soils, pH decreased while organic matter content and mobility of the metals increased over time. Highest bulk concentrations of trace metals were found in white willow trees (Salix alba L.). Laser ablation-ICPMS was used to study changes in metal accumulation over a period of 10 years after planting the trees. The radial metal profiles in the trunk core samples varied between elements and tree species, however, in all willow trees the radial Cd and Zn profiles were significantly correlated. Radial pollutant concentration patterns are discussed in terms of seasonal effects, health status, tree species and metal mobility in the soil. For Cd and Zn, the profiles were influenced by their mobility in the soils. In general, periodical patterns were observed for Pb. Cu concentration profiles were decreasing over time, with the strongest decrease in the initial growth period.

Dynamic behaviour of trace metals in the Deûle River impacted by recurrent polluted sediment resuspensions: from diel to seasonal evolutions.

An automatic trace metal monitoring station (ATMS) have been implemented in the river bank of the Deûle canal in the city of Auby (northern France), in the vicinity of metallurgical industries that have heavily polluted sediments, in Cd, Pb and Zn. Additionally, the fluvial traffic in this river is intense and surface sediments are resuspended several times per day. This paper is the following part of that published recently (Superville et al., 2014) in this journal. The main purpose of this paper is to present new information on diel and seasonal variations of trace metals in the Deûle River and highlight the potential role of sediments in the contamination of the water column. To this end, Cd, Zn and Pb were monitored at a high frequency (~1h(-1)) by voltammetry, distinguishing an electrolabile and an acid-leachable fraction. Our measurements revealed that (i) acid-leachable Cd is mainly bound to light particles such as clays and carbonates and its daily behaviour does not really depend on the intensity of sediment remobilisation process; (ii) acid-leachable Pb and Zn exhibit some seasonal variations which are explained here, suggesting they should at least partly depend on the ageing of hydrous ferric oxides in the sediments; (iii) in spring, the electrolability of Zn increases in agreement with the biological activity that may break some strong association between Zn and ligands and/or particles (e.g., organic matter, hydrous ferric oxides, etc.). This trend is observed for electrolabile Pb later in summer, but on a smaller scale since this metal is generally more strongly scavenged and less labile than Zn; and (iv) electrolabile Mn concentrations increase during the day due to desorption process of resuspended sediment particles in the water.

Daily variations of Zn and Pb concentrations in the Deûle River in relation to the resuspension of heavily polluted sediments.

Sediments in the Deûle River (northern France) are severely polluted by metals in the vicinity of several metallurgical plants. The aim of this paper is to identify the role played by the recurrent resuspension of these polluted sediments by boat traffic on the dissolved Pb and Zn concentrations in the river. For that purpose, several high-frequency on-line monitoring campaigns were performed. Our results clearly suggest that the resuspension of sedimentary particles into the overlying water significantly increased the dissolved electrolabile Pb and Zn contents. This increase does not persist for a long time because at night and during weekends and holidays, when the boat traffic strongly slows down, Pb and Zn concentrations drop again quickly. Our data also indicate that the biological processes (such as photosynthetic and respiration activities), diffusive and benthic fluxes, as well as dilution of pore water into the overlying water during sediment remobilization do not contribute significantly to the sharp increase of dissolved Pb and Zn concentrations in the river during the day. The good correlation between turbidity and electrolabile metal concentration allows us to discard slow AVS (Acid Volatile Sulfides) oxidation as well. Desorption of metals from sediment particles was clearly the most relevant process, responsible for the increase of dissolved Pb and Zn concentrations in the water column.

Identification and on-line monitoring of reduced sulphur species (RSS) by voltammetry in oxic waters.

Based on automatic on-line measurements on the Deûle River that showed daily variation of a peak around -0.56V (vs Ag|AgCl 3M), identification of Reduced Sulphur Species (RSS) in oxic waters was performed applying cathodic stripping voltammetry (CSV) with the hanging mercury drop electrode (HMDE). Pseudopolarographic studies accompanied with increasing concentrations of copper revealed the presence of elemental sulphur S(0), thioacetamide (TA) and reduced glutathione (GSH) as the main sulphur compounds in the Deûle River. In order to resolve these three species, a simple procedure was developed and integrated in an automatic on-line monitoring system. During one week monitoring with hourly measurements, GSH and S(0) exhibited daily cycles whereas no consequential pattern was observed for TA.

An adaptable automatic trace metal monitoring system for on line measuring in natural waters.

An adaptable automatic trace metal monitoring system (ATMS) was assembled and embedded in a mobile monitoring station belonging to the French Water Agency Artois-Picardie (AEAP) and deployed in the field to measure the concentration of trace metals (electroactive and acid leachable fractions) in natural waters by anodic stripping voltammetry with a hanging mercury drop electrode. Cathodic stripping voltammetry procedures were included to estimate the concentration of dissolved oxygen and reduced sulphur species. The concept of the measuring system enables easy adaptation of methods and procedures to analytes of concern and gives the opportunity to undertake in real-time a routine analysis of the dynamic behaviour of trace metals in river, pond and seawater. The system was tested in two aquatic bodies: in a pond where eutrophication processes occur recurrently and in the Deûle River, where sediments are highly contaminated by several metals such as Pb and Zn and frequently resuspended because of the river traffic. Preliminary field studies demonstrated that trace metal concentrations can evolve quickly as a function of time, depending on the turbidity and luminescence, i.e. day-night cycles. The obtained results were compared with an Environmental Quality Standard (EQS), the Criteria Maximum Concentration (CMC) and the Criterion Continuous Concentration (CCC). The whole system is also prepared for the task of "early warning".