pXRF on printed circuit boards: Methodology, applications, and challenges.

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 µm, 750 µm 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 µm 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 µm sample from the reference condition was acceptable (<20%) for Cu, Sn, Zn, Pb, Ni, Sb and Mo. For coarser samples, i.e. 750 µm 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.

Mercury contamination levels in the bioindicator piscivorous fish Hoplias aïmara in French Guiana rivers: mapping for risk assessment.

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).

Representative sampling of natural biofilms: influence of substratum type on the bacterial and fungal communities structure.

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.

Effective radium concentration in topsoils contaminated by lead and zinc smelters.

Trace elements (TE) are indicative of industrial pollution in soils, but geochemical methods are difficult to implement in contaminated sites with large numbers of samples. Therefore, measurement of soil magnetic susceptibility (MS) has been used to map TE pollutions, albeit with contrasted results in some cases. Effective radium concentration (ECRa), product of radium concentration by the emanation factor, can be measured in a cost-effective manner in the laboratory, and could then provide a useful addition. We evaluate this possibility using 186 topsoils sampled over about 783km(2) around two former lead and zinc smelters in Northern France. The ECRa values, obtained from 319 measurements, range from 0.70±0.06 to 12.53±0.49Bq·kg(-1), and are remarkably organized spatially, away from the smelters, in domains corresponding to geographical units. Lead-contaminated soils, with lead concentrations above 100mg·kg(-1) <3km from the smelters, are characterized on average by larger peak ECRa values and larger dispersion. At large scales, away from the smelters, spatial variations of ECRa correlate well with spatial variations of MS, thus suggesting that, at distance larger than 5km, variability of MS contains a significant natural component. Larger ECRa values are correlated with larger fine fraction and, possibly, mercury concentration. While MS is enhanced in the vicinity of the smelters and is associated with the presence of soft ferrimagnetic minerals such as magnetite, it does not correlate systematically with metal concentrations. When multiple industrial and urban sources are present, ECRa mapping, thus, can help in identifying at least part of the natural spatial variability of MS. More generally, this study shows that ECRa mapping provides an independent and reliable assessment of the background spatial structure which underlies the structure of a given contamination. Furthermore, ECRa may provide a novel index to identify soils potentially able to fix leached components.

Characterization and mobility of arsenic and heavy metals in soils polluted by the destruction of arsenic-containing shells from the Great War.

Destruction of chemical munitions from World War I has caused extensive local top soil contamination by arsenic and heavy metals. The biogeochemical behavior of toxic elements is poorly documented in this type of environment. Four soils were sampled presenting different levels of contamination. The range of As concentrations in the samples was 1937-72,820mg/kg. Concentrations of Zn, Cu and Pb reached 90,190mg/kg, 9113mg/kg and 5777mg/kg, respectively. The high clay content of the subsoil and large amounts of charcoal from the use of firewood during the burning process constitute an ample reservoir of metals and As-binding materials. However, SEM-EDS observations showed different forms of association for metals and As. In metal-rich grains, several phases were identified: crystalline phases, where arsenate secondary minerals were detected, and an amorphous phase rich in Fe, Zn, Cu, and As. The secondary arsenate minerals, identified by XRD, were adamite and olivenite (zinc and copper arsenates, respectively) and two pharmacosiderites. The amorphous material was the principal carrier of As and metals in the central part of the site. This singular mineral assemblage probably resulted from the heat treatment of arsenic-containing shells. Microbial characterization included total cell counts, respiration, and determination of As(III)-oxidizing activities. Results showed the presence of microorganisms actively contributing to metabolism of carbon and arsenic, even in the most polluted soil, thereby influencing the fate of bioavailable As on the site. However, the mobility of As correlated mainly with the availability of iron sinks.

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation.

Regional distribution of mercury in sediments of the main rivers of French Guiana (Amazonian basin).

Use of mercury (Hg) for gold-mining in French Guiana (up until 2006) as well as the presence of naturally high background levels in soils, has led to locally high concentrations in soils and sediments. The present study maps the levels of Hg concentrations in river sediments from five main rivers of French Guiana (Approuague River, Comté River, Mana River, Maroni River and Oyapock River) and their tributaries, covering more than 5 450 km of river with 1 211 sampling points. The maximum geological background Hg concentration, estimated from 241 non-gold-mined streams across French Guiana was 150 ng g(-1). Significant differences were measured between the five main rivers as well as between all gold-mining and pristine areas, giving representative data of the Hg increase due to past gold-mining activities. These results give a unique large scale vision of Hg contamination in river sediments of French Guiana and provide fundamental data on Hg distribution in pristine and gold-mined areas.

Environmental impacts of unmanaged solid waste at a former base metal mining and ore processing site (Kirki, Greece).

The Kirki project aimed to identify, among the mining waste abandoned at a mine and processing plant, the most critical potential pollution sources, the exposed milieus and the main pathways for contamination of a littoral area. This was accompanied by the definition of a monitoring network and remedial options. For this purpose, field analytical methods were extensively used to allow a more precise identification of the source, to draw relevant conceptual models and outline a monitoring network. Data interpretation was based on temporal series and on a geographical model. A classification method for mining waste was established, based on data on pollutant contents and emissions, and their long-term pollution potential. Mining waste present at the Kirki mine and plant sites comprises (A) extraction waste, mainly metal sulfide-rich rocks; (B) processing waste, mainly tailings, with iron and sulfides, sulfates or other species, plus residues of processing reagents; and (C) other waste, comprising leftover processing reagents and Pb-Zn concentrates. Critical toxic species include cadmium and cyanide. The stormy rainfall regime and hilly topography favour the flush release of large amounts of pollutants. The potential impacts and remedial options vary greatly. Type C waste may generate immediate and severe chemical hazards, and should be dealt with urgently by careful removal, as it is localised in a few spots. Type B waste has significant acid mine drainage potential and contains significant amounts of bioavailable heavy metals and metalloids, but they may also be released in solid form into the surface water through dam failure. The most urgent action is thus dams consolidation. Type A waste is by far the most bulky, and it cannot be economically removed. Unfortunately, it is also the most prone to acid mine drainage (seepage pH 1 to 2). This requires neutralisation to prevent acid water accelerating heavy metals and metalloids transfer. All waste management options require the implementation of a monitoring network for the design of a remediation plan, efficiency control, and later, community alert in case of accidental failure of mitigation/remediation measures. A network design strategy based on field measurements, laboratory validation and conceptual models is proposed.

Quantitative, chemical, and mineralogical characterization of flue gas desulfurization by-products.

The objective of this study was to demonstrate that simple fractionation and selective dissolution techniques can be used to provide detailed chemical and mineralogical analyses of flue gas desulfurization by-products. The material studied was a mine grout prepared as a 1:1 mixture (wt./wt.) of fly ash (FA) and filter cake (FC) with hydrated lime (50 g kg(-1)) added to improve handling. The hydrated lime was composed mostly of calcite (CaCO3), portlandite [Ca(OH)2], lime (CaO), and brucite [Mg(OH)2] (515, 321, 55, and 35 g kg(-1), respectively) and had low (<6 g kg(-1)) concentrations of most trace elements. The FC contained hannebachite (CaSO3 x 0.5H2O) (786 g kg(-1)) with smaller quantities (<10 g kg(-1)) of calcite, quartz (SiO2), brucite, and gypsum (CaSO4 x 2H2O). Except for B and Cu, trace element concentrations were comparable to those in the hydrated lime. The FA contained both magnetic (222 g kg(-1)) and nonmagnetic (778 g kg(-1)) fractions. The former was composed mostly of hematite (Fe2O3), magnetite (Fe3O4), and glass (272, 293, and 287 g kg(-1), respectively), whereas the latter was enriched in glass, quartz, and mullite (Al6Si2O13) (515, 243, and 140 g kg(-1), respectively). Etching with 1% HF showed that 60 to 100% of trace elements were concentrated in the glass, although some metals (Co, Cr, and Mn) were clearly enriched in the magnetic phase. The aged grout contained 147 g kg(-1) ettringite [Ca6Al2(SO4)3(OH)12 x 26H2O] in addition to 314 g kg(-1) hannebachite and 537 g kg(-1) insoluble phases (mullite, quartz, hematite, magnetite, and glass).