Search

The phytoextraction potential of Arabidopsis halleri (L.) O'Kane & Al Shehbaz and Salix viminalis L. to partially remove Zn and Cd in soil was investigated. In an urban field site, a very short rotation coppice of willows was implemented, and growth parameters were monitored for 3 years. A. halleri was cultivated in the same site with or without fertilizer to improve biomass yield and/or Zn and Cd aerial part concentrations. Effects of harvest and co-cultivation on these two parameters were measured. To determine if willows and A. halleri leaves were risky in case of consumption by a herbivorous invertebrate like the landsnail Cantareus aspersus, metal concentrations of snails fed with Zn- and Cd-enriched and low enriched leaves were compared. Willows and A. halleri grew well on the metal-contaminated soil (1.7 and 616 mg kg-1 Cd and Zn, respectively). The A. halleri Zn foliar concentration reached the Zn hyperaccumulation threshold (> 10,000 mg kg-1 DW) in the presence of NPK fertilizer and although the soil was alkaline (pH > 8.2). Cd concentration increased with harvest and fertilizer. Cd and Zn foliar concentrations of willows were far above baseline values. Laboratory snails exposure revealed that willow leaves ingestion caused a moderate increase of Cd, Pb, and Zn bioaccumulation in snails compared to the one caused by A. halleri ingestion. The soil and plant metal concentrations were reflected by field snail biomonitoring. This study confirmed the interest of selecting A. halleri and willows to partially remove Zn and Cd in the soil and emphasized their potential usefulness in greening urban contaminated area and producing raw materials for green chemistry while paying attention to the environmental pollutant transfer.

International audience; Biomethane is a renewable energy gas with great potential to contribute to the diversification and greening of the natural gas supply. Ideally, biomethane can directly be injected into the natural gas grid system. For grid injection, specifications such as those in EN 16723-1 shall be met. One of the impurities to be monitored is hydrogen chloride (HCl). To assess conformity with the specification for HCl, accurate and reliable test methods are required. Here, we report the development of three novel test methods, based on a variety of laser absorption spectroscopy techniques (Direct absorption spectroscopy-DAS and wavelength modulation spectroscopy-WMS) and ion-exchange chromatography, for the measurement of HCl in biomethane. Gas mixtures of HCl in biomethane were used to demonstrate the performance of the spectroscopic systems in the nmol mol−1 to low μmol mol−1 ranges, achieving uncertainties in the 4% range, k = 2. For ion-exchange chromatography analysis, HCl was first collected on an alkali-impregnated quartz fiber filter. The analysis was performed according to ISO 21438-2 and validated using synthetic biomethane spiked with HCl. The relative expanded uncertainties for the ion exchange chromatography HCl measurements are in the 10–37% range, k = 2. The results presented for the 3 test methods demonstrate that the respective methods can be used for HCl conformity assessment in biomethane.

International audience; Phytomanagement uses plants and soil conditioners to create value on contaminated land while minimizing environmental risk. This work was carried out on a metal(loid)-contaminated site and aimed at assessing the suitability of Salvia sclarea L. (sage) and Coriandrum sativum L. (coriander) combined with an arbuscular mycorrhizal fungus (AMF) inoculant to immobilize metal(loid)s and produce essential oils (EO). The effect of the inoculant on the transfer of metal(loid)s (ML, i.e., Cd, Cu, Pb, Zn, As, Ni, and Sb) to plants and the ML soil mobility were investigated. The ML concentrations in EO from both plant species and the valorization options for the distillation residues (soil conditioner, animal fodder, and anaerobic digestion) were studied. Sage was a suitable candidate for this value chain because it presents an excluder phenotype and the residues of oil extraction could be used as a soil conditioner. The metal concentrations in the sage EO were similar to those obtained from plants cultivated on an uncontaminated soil. These results indicate the suitability of sage harvested on the contaminated soil according to the ML fate in the whole value chain. Like the EO of sage, ML concentrations in the coriander EO did not differ from those in the commercial EO that were obtained from plants grown on uncontaminated soil. However, the use of distillation residues of coriander was limited by their relatively elevated Cd concentrations. The use of a mycorrhizal inoculum did not decrease the Cd mobility in soil for the coriander.

The study of different possible biomass valorization routes is crucial in order to diversify phytomanagement options, allowing the landowner/stakeholder to choose the best option based on site characteristics and the benefits of local value chains. In the current study, field and laboratory experiments were conducted to assess the suitabilitity of Malva sylvestris L. for the phytoattenuation of a dredged sediment disposal site contaminated with trace elements (trace element (Cd, Cu, Pb, and Zn). The selected crop was Malva sylvestris, a flowering plant from which a colourant can be extracted to be used in dying of textiles as a way to valorize the produced biomass grown on this contaminated land. Under the conditions of the investigated site, the analysis of TE in the sediment and the biomass matrix showed no effect of M. sylvestris on the sediment TE contamination mobility with an excluder phenotype (Bioconcentration factor &lt, 1). Metal concentrations were found to be the highest in the leaves followed by in the stem and flower. The dye extract obtained from the flower part of M. sylvestris permitted the silk alum-pretreated fabric to be dyed yellow, and the TE concentration in the dyed textile fabrics respected the threshold values set by OEKO-Tex standard 100.

Phytotechnologies for the management of lands contaminated with potentially toxic elements (PTEs) are considered as gentle alternatives to conventional remediation techniques. During the last few years, phytotechnologies have progressively shifted to phytomanagement, a concept that includes the valorization of the plant biomass produced on the contaminated site. This study aimed at evaluating the mid-term effect of ecto- and endomycorrhizal inoculation on the reduction of PTE mobility in soils and foliar accumulation by two poplar clones, Skado ( Populus trichocarpa x P. maximowiczii ) and I-214 ( P. deltoides x P. nigra ), dedicated to bioenergy purposes. The effects of inoculation were investigated in two large scale trials of 1 ha each. Poplars grown on highly contaminated soils accumulated excessive Cd and Zn in leaves compared with those planted on less contaminated soils, and the I-214 clone generally accumulated less PTEs than the Skado clone. Interestingly, the filtering capacity of mycorrhizal fungi was significant for Zn, Cu, Pb and Cr in Skado leaves only at the most contaminated areas after two growing seasons. These foliar concentrations were not correlated with Ca(NO 3 ) 2 -extractable concentrations in soils, suggesting that mycorrhizal fungi limited PTE translocation from roots to leaves without impacting PTE mobility in soils. Therefore, the reduction of PTE accumulation in poplar leaves may be optimized by selecting appropriate combinations of cultivars and inocula at specific PTE levels and soil conditions. Because Cd and Zn may pose a risk after leaf abscission and wood harvest, further research is needed to efficiently reduce Cd and Zn concentrations in poplar tissues. Otherwise, the phytomanagement of metal contaminated sites with poplars should include options to safely manage both leaves and wood.

Torrefaction (290 °C) and pyrolysis (450 and 800 °C) trials were performed at pilot scale with a patented reactor on metal-enriched poplars from a contaminated soil managed by phytotechnologies and poplars cultivated on uncontaminated soil, for comparison. This study emphasized the influence of temperature on end-product yield, metal distribution in end-products and metal behavior. Results showed that the evolution of the end-product yield, i.e. biochar, bio-oil and gas fractions, was depending on temperature rather than other parameters such as the origin or metal content of the tested poplars. Torrefaction decreased the processed poplars weight, leading to metal-enriched torrefied biomass as a major end-product. At 450 and 800 °C, metal behavior was governed by temperature. Nevertheless, the different chlorine content of initial biomass was hypothesized to be an important factor that could modify the metal behavior by increasing metal volatilization at process temperatures. Amongst the studied metals, Zn and Pb were hypothesized to form volatile metal chlorides, therefore increased metal volatilization from Control poplar biomass could be explained by increased chlorine content of such biomass. At 450 °C, metals were recovered in biochar, then in bio-oil and finally in gases. At 800 °C, similar results were obtained for Cu, confirming that Cu was not easily volatilized. On the contrary, Zn, Pb and Cd were mostly recovered in gases, which became the second metal recovery compartment. According to metal concentrations, valorization options were discussed for end-products.

International audience; Nanosized titanium dioxide (TiO2) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO2. Total Ti levels were chosen to evaluate the presence and distribution of TiO2 nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO3) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO2 nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO2 dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 µg Ti/g tissue agreed well.

The classification of waste as hazardous could soon be assessed in Europe using largely the hazard properties of its constituents, according to the the Classification, Labelling and Packaging (CLP) regulation. Comprehensive knowledge of the component constituents of a given waste will therefore be necessary. An analytical protocol for determining waste composition is proposed, which includes using inductively coupled plasma (ICP) screening methods to identify major elements and gas chromatography/mass spectrometry (GC-MS) screening techniques to measure organic compounds. The method includes a gross or indicator measure of 'pools' of higher molecular weight organic substances that are taken to be less bioactive and less hazardous, and of unresolved 'mass' during the chromatography of volatile and semi-volatile compounds. The concentration of some elements and specific compounds that are linked to specific hazard properties and are subject to specific regulation (examples include: heavy metals, chromium(VI), cyanides, organo-halogens, and PCBs) are determined by classical quantitative analysis. To check the consistency of the analysis, the sum of the concentrations (including unresolved 'pools') should give a mass balance between 90% and 110%. Thirty-two laboratory samples comprising different industrial wastes (liquids and solids) were tested by two routine service laboratories, to give circa 7000 parameter results. Despite discrepancies in some parameters, a satisfactory sum of estimated or measured concentrations (analytical balance) of 90% was reached for 20 samples (63% of the overall total) during this first test exercise, with identified reasons for most of the unsatisfactory results. Regular use of this protocol (which is now included in the French legislation) has enabled service laboratories to reach a 90% mass balance for nearly all the solid samples tested, and most of liquid samples (difficulties were caused in some samples from polymers in solution and vegetable oil). The protocol is submitted to French and European normalization bodies (AFNOR and CEN) and further improvements are awaited.

A series of amphiboles along the magnesioriebeckite - square Na2Mg3Fe3+ 2Si8O22(OH)(2)- ferri-clinoholmquistite - circle Li2Mg3Fe3+ 2Si8O22(OH)2 - join, defined by the Li-B(B) Na-1 exchange vector, were hydrothermally synthesized at 700 degrees C, 0.4 GPa, NNO + 1 redox conditions. Powder XRD and SEM-EDAX showed a very high (> 90%) amphibole yield for all samples. X-ray patterns were indexed in the C2/m space group; refined cell-parameters show a linear decrease of alpha and beta as a function of chemistry. IR spectra in the OH-stretching region show four main and rather sharp bands; these are assigned to Mg and Fe2+ at M(1,3), and indicate that the obtained amphiboles depart from the nominal octahedral composition (Mg-M1,3(3)). The IR spectra also show that there is an increasing filling-up of the A-site for increasing Na in the system (increasing solid-solution toward, arfvedsonite). Mossbauer spectra show four well-defined quadrupole doublets which are assigned to Fe3+ at M2 and to Fe2+ at M1, M3 and M4, respectively. The Fe3+/Fe2+ content derived from fitted peak areas show variable Fe3+ concentration along the series. Mossbauer spectra also show a distinct alteration of Fe-57 hyperfine parameters with changing Na-Li at M4. The most evident variation is observed for the quadrupole splitting of Fe3+ at M2, which increases by approximate to 50% from ferri-clinoholmquistite to magnesio-riebeckite; this suggest that the M2 octahedron in ferri-clinoholmquistite is much closer to the ideal geometry than the M2 octahedron in magnesio-riebeckite. Mossbauer spectra show also a well-defined increase in the Fe2+ quadrupole splitting of the M1 and M3 octahedra, which is attributed to the Na-Li distribution at the B-sites.