Purpose The EU Water Framework Directive (European Union Off J Eur Comm 2000) and EU Waste Framework Directive (European Union Off J Euro Union 2008) impacted the Beneficial Use (BU) of sediments in Europe. INTERREG has supported initiatives to change the perception that sediments are a waste. In this paper we provide an overview of tools, pilot sites and measuring techniques developed and used for the BU of sediments within seven European Union INTERREG projects. We illustrate the lessons learned regarding barriers and enablers for BU of sediments.Materials and methods BU of sediments is a combination of factors. The following aspects are considered. The sediment must be suitable for use and be in engineering compliance. The sediment must also need to meet the end of waste criteria, as well as to be in environmental compliance. To check in the field if engineering and environmental compliance is feasible, on-site analyses and decision support tools are needed. When BU use is possible, there must be a benefit, either in an added socio-economic value or in ecosystem services. To define benefits the impact of Business as Usual (BAU) should also be expressed. Stakeholder perception and spatial restraints determine areas for BU of sediments with spatial consensus.Results and discussion The pilots and case studies described in this paper are examples of different applications of BU of sediments in northwest Europe. The tools, equipment, pilot tests and on-site monitoring techniques developed by the identified INTERREG projects are useful as BU enablers, for both citizens (an enabler is what is in it for me versus a barrier like residents opposing to proposed developments in their local area or the Not In My Back Yard (NIMBY) principle), and for regulators (what are the risks versus benefits as compared to BAU).Conclusions The main barriers for beneficial use of sediments are the social acceptance when sediments are used on land (often seen as waste disposal) and the extra direct cost versus the cost for disposal, while indirect benefits such as the potential for nature development, the impact on Gross Domestic Product (GDP) or more locally on the extra jobs created, are generally not considered. Also, the impact of BAU is often not explicitly considered.

As the drive towards recycling electronic waste increases, demand for rapid and reliable analytical methodology to analyse the metal content of the waste is increasing, e.g. to assess the value of the waste and to decide the correct recycling routes. Here, we comprehensively assess the suitability of different x-ray fluorescence spectroscopy (XRF)-based techniques as rapid analytical tools for the determination of critical raw materials, such as Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nb, Pd and Au, in three electronic waste matrices: printed circuit boards (PCB), light emitting diodes (LED), and lithium (Li)-ion batteries. As validated reference methods and materials to establish metrological traceability are lacking, several laboratories measured test samples of each matrix using XRF as well as other independent complementary techniques (instrumental neutron activation analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS) and ICP optical emission spectrometry (OES)) as an inter-laboratory comparison (ILC). Results highlighted key aspects of sample preparation, limits of detection, and spectral interferences that affect the reliability of XRF, while additionally highlighting that XRF can provide more reliable data for certain elements compared to digestion-based approaches followed by ICP-MS analysis (e.g. group 4 and 5 metals). A clear distinction was observed in data processing methodologies for wavelength dispersive XRF, highlighting that considering the metals present as elements (rather than oxides) induces overestimations of the mass fractions when compared to other techniques. Eventually, the effect of sample particle size was studied and indicated that smaller particle size (<200 µm) is essential for reliable determinations.

In a number of applications, the use of portable X-ray fluorescence (pXRF) instruments offers a time and cost-saving alternative to standard laboratory instruments. This is particularly true in a mining context where decisions must be taken quickly in the field. However, pXRF is a technique known to be efficient, provided that samples are well prepared, i.e., dried and finely ground. On the mine face, little-to-no sample preparation is conceivable as mining vehicles must be able to operate continuously. Therefore, solutions have to be found even for raw materials and one of the most critical problems is the sample water content, in particular in the context of open pit mines in a tropical area. A large number of analysis shows that knowledge of humidity enables the measured concentration to be effectively corrected for the three instruments used (Niton, X-met, Titan). It is possible to overcome the difficulty of measuring water content in the field by fixing it to its maximum value (saturation). The results show that the saturation method is reliable, or at least, promising.

Exposure to potentially toxic trace elements (PTTEs) in inhalable particulate matter (PM10) is associated with an increased risk of developing cardiorespiratory diseases. Therefore, in multi-source polluted urban contexts, a spatially-resolved evaluation of health risks associated with exposure to PTTEs in PM is essential to identify critical risk areas. In this study, a very-low volume device for high spatial resolution sampling and analysis of PM10 was employed in Terni (Central Italy) in a wide and dense network (23 sampling sites, about 1 km between each other) during a 15-month monitoring campaign. The soluble and insoluble fraction of 33 elements in PM10 was analysed through a chemical fractionation procedure that increased the selectivity of the elements as source tracers. Total carcinogenic risk (CR) and non-carcinogenic risk (NCR) for adults and children due to concentrations of PTTEs in PM10 were calculated and quantitative source-specific risk apportionment was carried out by applying Positive Matrix Factorization (PMF) to the spatially-resolved concentrations of the chemically fractionated elements. PMF analysis identified 5 factors: steel plant, biomass burning, brake dust, soil dust and road dust. Steel plant showed the greatest risk contribution. Total CR and NCR, and source-specific risk contributions at the 23 sites were interpolated using the ordinary kriging (OK) method and mapped to geo-reference the health risks of the identified sources in the whole study area. This also allowed risk estimation in areas not directly measured and the assessment of the risk contribution of individual sources at each point of the study area. This innovative experimental approach is an effective tool to localize the health risks of spatially disaggregated sources of PTTEs and it may allow for better planning of control strategies and mitigation measures to reduce airborne pollutant concentrations in urban settings polluted by multiple sources.

Beneficial use of dredged sediments, either in harbours or waterways, is based on their potential as alternative resources. Such sediments can be considered as bulk materials for industrial needs, which is predicated on their current waste status or meeting end-of-waste constraints. They also can be an integral part of beneficial use projects using sediments as a bulk component, including civil engineering and landscaping. This is particularly important for beneficial use projects focusing on climate change effects mitigation, such as flood protection works, coastline defence or littoral urban areas redevelopment. When dredged sediment is used as a bulk material, its acceptability is based on an assumed homogeneity of its properties. On-site analyses allow pre-dredging detailed mapping at a denser scale than laboratory ones; monitoring dredgings during operations and during processing; and continuous control of their properties at the implementation site. This is currently possible only for a selection of inorganic analytes. When dredgings are part of a larger beneficial use project, on-site analyses facilitate first the baseline survey and the sediment source characterisation. Continuous monitoring of the sediment load allows a fast detection of contamination hot spots and their adequate management. Site survey via on-site instruments allow end users and communities to check themselves the contamination level, hence acceptability is better. On-site dredged sediment analyses monitor both building properties and environmental compliance; soil and sediment analyses at receiving sites; surface and groundwater, either for impact assessment or for monitoring works. On-site instruments provide immediate results and allow dynamic or adaptive sampling strategies, as well as allowing operational decisions in real time. Confirmation by laboratory analyses is required for validation, but on-site sample screening for laboratory analyses improves their efficiency. The present paper was developed on the basis of an earlier presentation, which it developed and updated extensively.

In order to develop methods to determine the chemical composition of Waste Printed Circuit Boards (WPCB), this study focused on the analysis of 10 metals (Cu, Fe, Sn, Zn, Pb, Ni, Sb, Cr, Mo and Pd) using portable X-ray fluorescence (pXRF) compared to ICP-MS measurements after aqua regia digestion. Different experimental conditions were tested: 3 particle sizes (200 mu m, 750 mu m and 2 mm) and 3 sample preparations (tube, cup and loose powder). For each condition tested, 8-16 independent replicates were done. ICP measurements with the 200 mu m sample, considered as the reference condition in this study, confirmed the homogeneity of the sample at this particle size and the robustness of the sampling protocol (RSD < 5% for all elements). For this particle size, pXRF has low data dispersion too (Cu, Fe, Sn, Zn, Pb, Sb and Cr showed RSD < 10%) and the use of loose powder seems to be a sufficient preparatory step. Moreover, the deviation of pXRF measurements with the 200 mu m sample from the reference condition was acceptable (<20%) for Cu, Sn, Zn, Pb, Ni, Sb and Mo. For coarser samples, i.e. 750 mu m and 2 mm, the homogeneity was much more doubtful, which needs to be offset by a larger number of repetitions. For these particles sizes, pXRF set to factory-installed mining mode did not produce accurate measurements but could provide a rapid non-intrusive approach for first-level screening to assess the relative difference of metal contents between WPCB samples.

Portable X-ray fluorescence spectroscopy is now widely used in almost any field of geoscience. Handheld XRF analysers are easy to use, and results are available in almost real time anywhere. However, the results do not always match laboratory analyses, and this may deter users. Rather than analytical issues, the bias often results from sample preparation differences. Instrument setup and analysis conditions need to be fully understood to avoid reporting erroneous results. The technique’s limitations must be kept in mind. We describe a number of issues and potential pitfalls observed from our experience and described in the literature. This includes the analytical mode and parameters; protective films; sample geometry and density, especially for light elements; analytical interferences between elements; physical effects of the matrix and sample condition, and more. Nevertheless, portable X-ray fluorescence spectroscopy (pXRF) results gathered with sufficient care by experienced users are both precise and reliable, if not fully accurate, and they can constitute robust data sets. Rather than being a substitute for laboratory analyses, pXRF measurements are a valuable complement to those. pXRF improves the quality and relevance of laboratory data sets.

Anthropogenic activities release many types of contaminants, such as trace metals, in the environment. For recent decades, numerous studies investigated their behavior, particularly in the dissolved phase. The transfer of contaminants adsorbed on the particulate phase received less attention although particulate matter also plays a key role in their propagation. One first difficulty is the variability of adsorption and releasing processes driven by both water physico-chemical conditions and contaminants properties. Secondly, there are different compartments in particulate phases, e.g. bed-load sediments and suspended particles, and the proportion of these two worlds is highly variable according to climate conditions (temperature, rainfall) and stream (hydro)geomorphological characteristics. In this context, our study investigates trace metal dynamics (Pb, Zn, Cu) in bed-load sediments and suspended particles from a small tributary of the Loire River, the Egoutier stream (Loiret, France). High spatial and temporal sampling frequency of the two fractions allowed to understand the patterns of trace metals transfer. Trends of trace metals contents observed in the particulate phase correspond to those in the dissolved one, except for Pb, the most insoluble compound. Contaminants concentrations and behaviors are driven both by trace metals order of solubility in bed-load sediments and suspended particles, and by external factors such as meteorological conditions, stream geochemistry and geomorphology. Besides, they are mostly adsorbed on iron and manganese oxides from suspended particles and on organic compounds from the bed-load sediments. Their temporal dynamics are controlled by seasons variabilities, notably rain amounts and humid periods, whereas their spatial distribution essentially reflects stream geomorphology, notably by the presence of a small pond creating a disconnection between the upstream and the downstream part of the watercourse and therefore two different patterns of transfert. Upstream, bed-load sediments contamination presents large fluctuations regulated by anthropogenic releases during dry periods and organic supplies during the humid ones, whereas homogeneous levels were observed downstream. In the suspended particles fraction, upstream higher contents are only correlated to humid periods, where more oxides are transported, while downstream transport is amplified by higher rain amounts.

The transfer and storage of chemical elements in particulate matter are controlled by physical, chemical and biological processes. Their dynamics are well understood, especially in environments that show strong tectonic and/or geomorphic pressures, and are frequently reconstructed over centuries or decades to evaluate climate change effects for example. However, observations carried out at high spatial and temporal resolutions are less common, particularly in lowland areas. The present study aimed to better understand the links between earth surface processes, such as soil weathering and erosion, by combining pedology, geochemistry and hydrology at a small catchment scale. It focuses on the transfer of selected chemical elements (Ca, K, Ti, Fe, Mn, Rb and Sr) associated with particulate erosion and transport. The first (topsoil) and last (subsoil) soil horizons from different soil profiles and stream bed-load sediments of the Egoutier catchment (8 km(2), Loiret, France) were studied. The objective was to investigate the relationship between the weathering and erosion processes. The soils are developed on ancient alluvium as evidenced by their physical and chemical properties, which clearly displayed a weathering profile from bedrock to topsoil layers. Ca, Fe and Rb showed migration dynamics from the topsoils to the subsoils, whereas Mn appeared immobilized within topsoils. Enrichments of all investigated elements increased in bed-load sediments. Topsoil erosion is the main source of sediment. However, Fe and Rb enrichments also highlight the remobilization of subsoils during periods of enhanced precipitation. Furthermore, Fe and Rb enrichments show a selective erosion of clay minerals. K and Sr contents evidence mineral break-up processes favoring mechanical erosion of all mineral phases. Moreover, their enrichments can be interpreted as the result of higher erosion rates and deposition during high rainfall events. The same conclusion can be drawn for Mn and Ca although their spatial variabilities depend on contributions from runoff in urban areas, as rainwaters from anthropized areas supply Ca mineral phases and diluted Mn depleted bearing phases from topsoil layers.

In 2006 the use of mercury (Hg) was banned for gold mining in French Guiana. However, mining of old placers could mobilize Hg accumulated in soils and sediment. This study aimed to measure the current impact of a mining concession (Boulanger site) on the Hg load in the watershed. Turbidity, Total Mercury (THg), and Monomethylmercury (MMHg) were measured in water, suspended particulate matter (SPM), river sediment and sediments from old tailing ponds along a river section of 30 km up and downstream from a mining concession in French Guiana during a dry and a rainy season. Total dissolved Hg (THgD) concentrations varied little from up- to down-stream but were all higher (fourfold on average) during the rainy season (3.2 to 4.4 ng L−1), than during the dry season and consistent with previous data known for the Amazonian area. Dissolved MMHg (MMHgD) represented up to 30% of THgD during the dry season, which is higher than previous results (typically around 2%). Mercury concentrations in sediments were highest in the vicinity of areas affected by old (before 2006) rather than new gold mining practices. Even though Hg was banned in 2006, present gold mining practices still release natural Hg and Hg inherited from older mining practices into the watershed.

The Interreg FWVL VALSE project aims to promote sustainable dredged sediment reuse. Reuse options and supporting research were investigated during an earlier project. In order to provide waterways operators and related industries, with case studies, full scale pilot tests are planned at Belgian and French sites. A former sediment disposal site of the French Waterways (VNF) at Saint Omer, Northern France, is considered as a potential source of mature sediment (14 to 40 years old) for reuse applications (landscaping, cycle paths, dikes). Sediments are now comparable to soil in terms of water content and mechanical behaviour. Sediment environmental characteristics are assessed with laboratory methods, and its variability with on-site methods...

In French Guiana, native populations present high level of mercury contamination, which has been linked to the consumption of contaminated fishes. The goal of this study is to undertake a cartography of mercury contamination levels in fishes from the six main Guiana rivers. The selected species for this study is the ubiquitous piscivorous fish Hoplias aimara . A total number of 575 fishes from 134 discrete fishing sites are regrouped into 51 river sectors. Results from this study permits to rank the six main Guiana rivers by their mean level of contamination: Oyapock (0.548 mg kg −1 ), Comté (0.624 mg kg −1 ), Maroni (0.671 mg kg −1 ), Approuague (0.684 mg kg −1 ), Mana (0.675 mg kg −1 ), and Sinnamary (1.025 mg kg −1 ). The contamination is however not spatially homogenous along each river, and a map of the different levels of mercury contamination in fishes is provided. Sectors of low mean Hg contamination are observed both upstream (0.471 mg kg −1 ) and downstream (0.424 mg kg −1 ), corresponding to areas without any influence of gold mining activities and areas under the influence of estuarine dilution, respectively. Anoxia and gold mining activities are found to be the two main factors responsible for the high mercury concentration in fish muscles. While mean levels of mercury contaminations are higher in anoxia areas (1.029 mg kg −1 ), contaminations induced by gold mining activities (0.717 mg kg −1 ) present the most harmful consequences to human populations. No significant differences in Hg concentrations are observed between 2005 and 2014 for neither a pristine nor a gold mining area, while Hg concentration differences are observed between former (0.550 mg kg −1 ) and current gold mining sites (0.717 mg kg −1 ).

On-line, real-time chemical and mineralogical analyses on drill cores are highly demanded by mining companies. However, they are a challenge because of drill core surface state and sample heterogeneities. We selected four rock samples: highly porous, siliceous breccia and serpentinized harzburgite coming from the base of a nickel laterite profile in New Caledonia which were sonic drilled, and fine grained, homogeneous sandstone and coarse grained granite which were diamond drilled and provided by Eijkelkamp Sonic Drill with unknown origin. The samples were analysed at five surface states (diamond or sonic drilled, cut as squares, polished at 6 and 0.25 mu m, powdered < 80 mu m) by portable XRF spectroscopy (pXRF) in mining and soil modes and portable infrared spectroscopy (pIR, Visible and Near Infrared-Short Wave Infrared range (VNIR-SWIR)). A total of 52 pXRF and 200 pIR analyses were performed per sample at each surface state. This study shows that the surface state has minor influence on the results of the portable instruments. By comparing pIR and pXRF results with laboratory devices (Raman spectroscopy, XRD with Rietveld refinement, XRF spectroscopy and ICP-AES), we evidence the lower and less accurate information obtained from handheld instruments in terms of chemistry and mineralogy. The porosity and grain size effect on the measurement need to be taken into consideration for on-line drill core analyses. We show that the combination of complementary analytical techniques helps to overcome the drawbacks of the core texture and of the precision of portable instruments in order to define the regions of interest (ROI) for mining companies. We also demonstrate that a precise pXRF calibration is mandatory and that the concentration of light elements (Si, Mg), even if not accurate, shows sufficient contrast along the lateritic profile for ROI definition.

In situ biofilm sampling is a key step for the study of natural biofilms and using methodologies that reflect natural diversity is necessary to guarantee representative sampling. Here, we focalise on the impact of the type of substrata on which biofilms grow on bacterial and fungal communities' structure. The indirect molecular approach, Denaturing Gel Gradient Electrophoresis (DGGE) of a gene fragment coding for either 16S rRNA or 28S rRNA, for bacteria or fungi respectively, was used to evaluate the variability of microbial community structures among different biofilm substrata: natural (pebbles, live plants, wood and sediment), or artificial (glass, Plexiglas(®) and sterile wood), in a small river (the Loiret, France). Multivariate statistics, band richness and diversity indexes (Shannon and Simpson) were used to highlight variations in community structure between substrata. Results showed variations of bacterial and fungal diversity between different substrata according to substratum properties/origin (natural or artificial, organic or inorganic) but there was no optimal substratum for sampling, and artificial substrata were not significantly less applicable than natural substrata. Pooling 4 different substrata types allowed a higher bacterial and fungal biodiversity recovery. Point contact sampling may thus gain in robustness by increasing the number of substrata considered. Fungal species richness was similar to the bacterial one on most substrata which suggested they should be more frequently considered in riverine biofilm studies.

Within the framework of responsible mining, a SOLSA project (www.solsa-mining.eu) to develop an in-situ tool allowing a quick mineralogical identification of site drill cores has been recently launched. Its objective is to develop new or improved highly-efficient and cost-effective, sustainable exploration technologies. It combines and integrates non-destructive sensors: X-ray fluorescence, X-ray diffraction, infra-red and Raman spectroscopy and 3D imaging. The challenge is to address mixtures of hard and soft rocks, as encountered in a lateritic environment. This paper focuses on the determination of spectral characteristics of laterite drill-cores in the visible to short wave infrared spectral range. One of the most important prerequisites is to study the influence of the surface roughness effect on infra-red spectroscopy analyses. For this purpose, four different rock samples: breccia, sandstones, granite and peridotite, each at five surface states have been considered: as-drilled, as-sawn, polished at 6 μm, polished at 0.25 μm and crushed to powder. The reflectance spectra have been acquired with an ASD Fieldspec 3® spectroradiometer with a contact probe at a sampling surface of 1.76 cm 2 , allowing a spectral analysis at wavelengths from 350 up to 2500 nm. The powder spectrum of breccia presents a higher reflectance than the four other spectra from the same material but weak absorption features. The as-sawn sample presents the higher absorption depth, followed by as-drilled sample and the two polished samples (figure 1). At wavelength 2219 nanometers, a peak of absorption is present. The presence of clay minerals is assumed like illite/sericite with more or less smectite, due to the relatively deep water absorption around wavelength 1900 nanometers.

In order to evaluate the instrumental parameters for the combined on-line-on-mine-real-time expert system SOLSA (http://www.solsa-mining.eu), portable and laboratory analyses were carried out on coarse granite, sandstone, serpentinized harzburgite and siliceous breccia. Each sample was studied at 5 different surface roughnesses (sonic or diamond drilled, cut, polished at 6 mu m and 0.25 mu m, sample powders). X-ray diffraction (XRD), portable Infra-Red (pIR) and X-ray-fluorescence (pXRF), and laboratory micro-Raman spectroscopy gave complementary and corroborating results. No major effect on the analyses was noted for the selected surface states. pXRF gave variable results except for the homogeneously serpentinized harzburgite, related to coarse or contrasting grain sizes or pores, small spot size (3 mm) and needs close-to-surface analyses. Portable IR (spot size 1.76 cm(2)) is carried out close to surfaces while Raman spectroscopy (1-2 mu m) is performed at distance. Sampling strategies have to be defined for each lithology. Major challenges for a combined on-line analysis are to adapt the specificities of the techniques to (1) analyse similar surface areas (from 2 cm(2) (pIR) to < mu m (Raman)), (2) smartly combine all the techniques into a single instrument, and (3) develop appropriate databases to reach a reliable "real-time" outcome results, which can be used for more precise geomodeling, and to rapidly define exploration and beneficiation parameters.

Complexation with methyl groups produces the most toxic form of mercury, especially because of its capacity to bioconcentrate in living tissues. Understanding and integrating methylation and demethylation processes is of the utmost interest in providing geochemical models relevant for environmental assessment. In a first step, we investigated methylation at equilibrium, by selecting the thermodynamic properties of different complexes that form in the chemical system Hg-SO3-S-Cl-C-H2O. The selection included temperature dependencies of the equilibrium constants when available. We also considered adsorption and desorption reactions of both methylated and non-methylated mercury onto mineral surfaces. Then we assessed the kinetics of methylation by comparing a dedicated column experiment with the results of a geochemical model, including testing different methylation and demethylation kinetic rate laws. The column system was a simple medium: silicic sand and iron hydroxides spiked with a mercury nitrate solution. The modelling of methylmercury production with two different rate laws from the literature is bracketing the experimental results. Dissolved mercury, iron and sulfate concentrations were also correctly reproduced. The internal evolution of the column was also correctly modeled, including the precipitation of mackinawite (FeS) and the evolution of dissolved iron. The results validate the conceptual model and underline the capacity of geochemical models to reproduce some processes driven by bacterial activity.