Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis.

A green and effective approach for the synthesis of structurally diversed α-hydroxyphosphonates via hydrophosphonylation of aldehydes under solventless conditions and promoted by biosourced catalysts, called ecocatalysts "Eco-MgZnOx" is presented. Ecocatalysts were prepared from Zn-hyperaccumulating plant species Arabidopsis halleri, with simple and benign thermal treatment of leaves rich in Zn, and without any further chemical treatment. The elemental composition and structure of Eco-MgZnOx were characterized by MP-AES, XRPD, HRTEM, and STEM-EDX techniques. These analyses revealed a natural richness in two unusual and valuable mixed zinc-magnesium and iron-magnesium oxides. The ecocatalysts were employed in this study to demonstrate their potential use in hydrophosphonylation of aldehydes, leading to various α-hydroxyphosphonate derivatives, which are critical building blocks in the modern chemical industry. Computational chemistry was performed to help discriminate the role of some of the constituents of the mixed oxide ecocatalysts. High conversions, broad substrate scope, mild reaction conditions, and easy purification of the final products together with simplicity of the preparation of the ecocatalysts are the major advantages of the presented protocol. Additionally, Eco-MgZnOx-P could be recovered and reused for up to five times.

Trace Metal(oid) Accumulation in Edible Crops and Poplar Cuttings Grown on Dredged Sediment Enriched Soil.

The development of a biomonitor in the context of multiple-element contamination in urban environments was tested by comparing element transfer in edible crops and poplar ( Torr. × A. Henry cutlivar 'Skado'). A multielemental analysis was performed with various common edible crops (cucumber [ L.], pepper [ L.], cabbage [ L.], and lettuce [ L.]) and the Skado poplar cultivar grown on soils that received sediments dredged from water canals in the 1960s. Sediments were distributed unevenly on the soil, allowing us to sample two types of areas that were either weakly (Area 1) or highly (Area 2) contaminated, mainly by Cd, Pb, and Zn. We registered an accumulation of Cd and Zn in the edible parts of crops, with higher values recorded for leafy vegetables than for fruit vegetables. We did not detect any accumulation of Pb in the plant species studied. We calculated the fresh mass that must be consumed daily to reach tolerable daily intake (TDI) recommendations for each element and found evidence that Cd could be ingested in sufficient amounts to reach the TDI in this context. Poplar and pepper leaves accumulated more Cd and Zn than the edible parts of the study crops grown on both substrates, which suggests that poplar and pepper may be suitable species for biomonitoring element transfer to vegetation in this context.

Agronomic Practices for Improving Gentle Remediation of Trace Element-Contaminated Soils.

The last few decades have seen the rise of Gentle soil Remediation Options (GRO), which notably include in situ contaminant stabilization ("inactivation") and plant-based (generally termed "phytoremediation") options. For trace element (TE)-contaminated sites, GRO aim to either decrease their labile pool and/or total content in the soil, thereby reducing related pollutant linkages. Much research has been dedicated to the screening and selection of TE-tolerant plant species and genotypes for application in GRO. However, the number of field trials demonstrating successful GRO remains well below the number of studies carried out at a greenhouse level. The move from greenhouse to field conditions requires incorporating agronomical knowledge into the remediation process and the ecological restoration of ecosystem services. This review summarizes agronomic practices against their demonstrated or potential positive effect on GRO performance, including plant selection, soil management practices, crop rotation, short rotation coppice, intercropping/row cropping, planting methods and plant densities, harvest and fertilization management, pest and weed control and irrigation management. Potentially negative effects of GRO, e.g., the introduction of potentially invasive species, are also discussed. Lessons learnt from long-term European field case sites are given for aiding the choice of appropriate management practices and plant species.

Field evaluation of industrial non-food crops for phytomanaging a metal-contaminated dredged sediment.

Phytomanagement is a concept fit for a bio-based circular economy that combines phytotechnologies and biomass production for non-food purposes. Here, ten annual and perennial industrial non-food crops (Sorghum Biomass 133, Sorghum Santa Fe red, Linum usitatissimum L., Eucalyptus sp., Salix Inger, Salix Tordis, Beta vulgaris L., Phacelia tanacetifolia Benth., Malva sylvestris L., and Chenopodium album L.) were studied under field conditions for phytomanaging a metal (Cd, Cu, Pb, and Zn)-contaminated dredged sediment in the North of France. The crops were selected according to their relevance to pedoclimatic and future climatic conditions, and one or more non-food end-products were proposed for each plant part collected, such as biogas, bioethanol, compost, natural dye, ecocatalyst, and fiber. Based on the soil-plant transfer of metals, eight out of the crops cultivated on field plots exhibited an excluder behavior (bioconcentration factor, BCF < 1), a trait suitable for phytostabilization. However, these crops did not change the metal mobilities in the dredged sediment. The BCF < 1 was not sufficient to characterize the excluder behavior of crops as this factor depended on the total dredged-sediment contaminant. Therefore, a BCF group ranking method was proposed accounting for metal phytotoxicity levels or yield decrease as a complemental way to discuss the crop behavior. The feasibility of the biomass-processing chains was discussed based on these results and according to a survey of available legislation in standard and scientific literature.

Coriander (Coriandrum sativum) Cultivation Combined with Arbuscular Mycorrhizal Fungi Inoculation and Steel Slag Application Influences Trace Elements-Polluted Soil Bacterial Functioning.

The cultivation of aromatic plants for the extraction of essential oils has been presented as an innovative and economically viable alternative for the remediation of areas polluted with trace elements (TE). Therefore, this study focuses on the contribution of the cultivation of coriander and the use of arbuscular mycorrhizal fungi (AMF) in combination with mineral amendments (steel slag) on the bacterial function of the rhizosphere, an aspect that is currently poorly understood and studied. The introduction of soil amendments, such as steel slag or mycorrhizal inoculum, had no significant effect on coriander growth. However, steel slag changed the structure of the bacterial community in the rhizosphere without affecting microbial function. In fact, Actinobacteria were significantly less abundant under slag-amended conditions, while the relative proportion of Gemmatimonadota increased. On the other hand, the planting of coriander affects the bacterial community structure and significantly increased the bacterial functional richness of the amended soil. Overall, these results show that planting coriander most affected the structure and functioning of bacterial communities in the TE-polluted soils and reversed the effects of mineral amendments on rhizosphere bacterial communities and their activities. This study highlights the potential of coriander, especially in combination with steel slag, for phytomanagement of TE-polluted soils, by improving soil quality and health.

Phytoextraction of Zn and Cd with Arabidopsis halleri: a focus on fertilization and biological amendment as a means of increasing biomass and Cd and Zn concentrations.

The current work aims to investigate the influence of fertilization (fertilizer) and fungal inoculation (Funneliformis mosseae and Serendipita indica (formerly Piriformospora indica), respectively arbuscular mycorrhizal (AMF) and endophytic fungi) on the phytoextraction potential of Arabidopsis halleri (L.) O'Kane & Al-Shehbaz (biomass yield and/or aboveground part Zn and Cd concentrations) over one life plant cycle. The mycorrhizal rates of A. halleri were measured in situ while the fungal inoculation experiments were carried out under controlled conditions. For the first time, it is demonstrated that the fertilizer used on A. halleri increased its biomass not only at the rosette stage but also at the flowering and fruiting stages. Fertilizer reduced the Zn concentration variability between developmental stages and increased the Cd concentration at fruiting stage. A. halleri roots did not show AMF colonization at any stage in our field conditions, neither in the absence nor in the presence of fertilizer, thus suggesting that A. halleri is not naturally mycorrhizal. Induced mycorrhization agreed with this result. However, S. indica has been shown to successfully colonize A. halleri roots under controlled conditions. This study confirms the benefit of using fertilizer to increase the phytoextraction potential of A. halleri. Overall, these results contribute to the future applicability of A. halleri in a phytomanagement strategy by giving information on its cultural itinerary.

Mycorrhizal inoculation effects on growth and the mycobiome of poplar on two phytomanaged sites after 7-year-short rotation coppicing.

Aims: Afforestation of trace-element contaminated soils, notably with fast growing trees, has been demonstrated to be an attractive option for bioremediation due to the lower costs and dispersion of contaminants than conventional cleanup methods. Mycorrhizal fungi form symbiotic associations with plants, contributing to their tolerance towards toxic elements and actively participating to the biorestoration processes. The aim of this study was to deepen our understanding on the effects of mycorrhizal inoculation on plant development and fungal community at two trace-element contaminated sites (Pierrelaye and Fresnes-sur-Escaut, France) planted with poplar (Populus trichocarpa x Populus maximowiczii). Methods: The 2 sites were divided into 4 replicated field blocks with a final plant density of 2200 tree h-1. Half of the trees were inoculated with a commercial inoculum made of a mix of mycorrhizal species. The sites presented different physico-chemical characteristics (e.g., texture: sandy soil versus silty-loam soil and organic matter: 5.7% versus 3.4% for Pierrelaye and Fresnes-sur-Escaut, respectively) and various trace element contamination levels. Results: After 7 years of plantation, inoculation showed a significant positive effect on poplar biomass production at the two sites. Fungal composition study demonstrated a predominance of the phylum Ascomycota at both sites, with a dominance of Geopora Arenicola and Mortierella elongata, and a higher proportion of ectomycorrhizal and endophytic fungi (with the highest values observed in Fresnes-sur-Escaut: 45% and 28% for ECM and endophytic fungi, respectively), well known for their capacity to have positive effects on plant development in stressful conditions. Furthermore, Pierrelaye site showed higher frequency (%) of mycorrhizal tips for ectomycorrhizal fungi (ECM) and higher intensity (%) of mycorrhizal root cortex colonization for arbuscular mycorrhizal fungi (AMF) than Fresnes-sur-Escaut site, which translates in a higher level of diversity. Conclusions: Finally, this study demonstrated that this biofertilization approach could be recommended as an appropriate phytomanagement strategy, due to its capacity to significantly improve poplar productivity without any perturbations in soil mycobiomes.

Phytomanagement of a metal(loid)-contaminated agricultural site using aromatic and medicinal plants to produce essential oils: analysis of the metal(loid) fate in the value chain.

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.

In situ cultivation of aromatic plant species for the phytomanagement of an aged-trace element polluted soil: Plant biomass improvement options and techno-economic assessment of the essential oil production channel.

Due to the presence of trace element (TE) in agricultural soils, wide areas are unproper for food production and the clean-up of soil is not a feasible option. Considering the potential remediation options, the use of aromatic plants producing a high quantity of biomass and developing high-added value sectors such as essential oil (EO) production could be valuable regarding one of the phytomanagement objectives, i.e. the restoration of an economic activity. The purpose of this study was hence to evaluate in situ the suitability of two aromatic crops, clary sage and coriander, for the phytomanagement of aged TE-polluted soils, taking into account plants' growth, development and biomass production, essential oil (EO) content and quality as well as a techno-economic feasibility analysis of the channel. In situ experiments have been carried out on two agricultural plots of 1.5 ha, a TE-polluted one (Pb: 394 ppm - Zn: 443 ppm - Cd: 7.2 ppm) and an unpolluted one (Pb: 22 ppm - Zn: 48 ppm - Cd: 0.4 ppm). Our findings have shown the ability of coriander and sage to grow similarly on both unpolluted and TE-polluted soil and to produce significant amounts of biomass. The pesticide residue and TE analyses have demonstrated that the EO only contained trace amounts of the contaminants, below or close to the limit of quantification of the method used and similar to marketed products. Mycorrhizal inoculation has also shown promising results by increasing the colonization rates of both aromatic plants, but did not result in higher biomass or EO amounts. Our study brings new evidence towards the potential of clary sage to be used for the phytomanagement of TE-polluted areas, given its perennial vegetation cover, tolerance to TE and obtained EO yields.

Urban soil phytomanagement for Zn and Cd in situ removal, greening, and Zn-rich biomass production taking care of snail exposure.

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.

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation.

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix "Tordis" (Salix schwerinii × Salix viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

Assessing phytotoxicity of trace element-contaminated soils phytomanaged with gentle remediation options at ten European field trials.

Gentle remediation options (GRO), i.e. in situ stabilisation, (aided) phytoextraction and (aided) phytostabilisation, were implemented at ten European sites contaminated with trace elements (TE) from various anthropogenic sources: mining, atmospheric fallout, landfill leachates, wood preservatives, dredged-sediments, and dumped wastes. To assess the performance of the GRO options, topsoil was collected from each field trial, potted, and cultivated with lettuce (Lactuca sativa L.) for 48days. Shoot dry weight (DW) yield, photosynthesis efficiency and major element and TE concentrations in the soil pore water and lettuce shoots were measured. GRO implementation had a limited effect on TE concentrations in the soil pore water, although use of multivariate Co-inertia Analysis revealed a clear amelioration effect in phytomanaged soils. Phytomanagement increased shoot DW yield at all industrial and mine sites, whereas in agricultural soils improvements were produced in one out of five sites. Photosynthesis efficiency was less sensitive than changes in shoot biomass and did not discriminate changes in soil conditions. Based on lettuce shoot DW yield, compost amendment followed by phytoextraction yielded better results than phytostabilisation; moreover shoot ionome data proved that, depending on initial soil conditions, recurrent compost application may be required to maintain crop production with common shoot nutrient concentrations.

Potential of Ranunculus acris L. for biomonitoring trace element contamination of riverbank soils: photosystem II activity and phenotypic responses for two soil series.

Foliar ionome, photosystem II activity, and leaf growth parameters of Ranunculus acris L., a potential biomonitor of trace element (TE) contamination and phytoavailability, were assessed using two riverbank soil series. R. acris was cultivated on two potted soil series obtained by mixing a TE (Cd, Cu, Pb, and Zn)-contaminated technosol with either an uncontaminated sandy riverbank soil (A) or a silty clay one slightly contaminated by TE (B). Trace elements concentrations in the soil-pore water and the leaves, leaf dry weight (DW) yield, total leaf area (TLA), specific leaf area (SLA), and photosystem II activity were measured for both soil series after a 50-day growth period. As soil contamination increased, changes in soluble TE concentrations depended on soil texture. Increase in total soil TE did not affect the leaf DW yield, the TLA, the SLA, and the photosystem II activity of R. acris over the 50-day exposure. The foliar ionome did not reflect the total and soluble TE concentrations in both soil series. Foliar ionome of R. acris was only effective to biomonitor total and soluble soil Na concentrations in both soil series and total and soluble soil Mo concentrations in the soil series B.

Trace element bioavailability, yield and seed quality of rapeseed (Brassica napus L.) modulated by biochar incorporation into a contaminated technosol.

BACKGROUND AND AIMS: Rapeseed (Brassica napus L.) is a Cd/Zn-accumulator whereas soil conditioners such as biochars may immobilize trace elements. These potentially complementary soil remediation options were trialed, singly and in combination, in a pot experiment with a metal(loid)-contaminated technosol. METHODS: The technosol [total content in mg kg(-1) Zn 6089, Cd 9.4, Cu 110, and Pb 956] was either amended (2% w/w) or not with a poultry manure-derived biochar. Rapeseed was cultivated for both soil treatments during 24 weeks up to harvest under controlled conditions. RESULTS: Biochar incorporation into the technosol promoted the As, Cd, Cu, Mo, Ni, Pb and Zn solubility. It decreased foliar B, Cu and Mo concentrations, and Mo concentration in stems, pericarps and seeds. But, it did not impact neither the biomass of aerial rapeseed parts (except a decrease for seeds), nor their C (except a decrease for stems), seed fatty acid, seed starch and soluble sugar contents, and antioxidant capacity in both leaves and seeds. Biochar amendment increased the phytoextraction by aerial plant parts for K, P, and S, reduced it for N, Ca, B, Mo, Ni and Se, whereas it remained steady for Mg, Zn, Fe, Mn, Cu, Cd and Co. CONCLUSIONS: The biochar incorporation into this technosol did not promote Cd, Cu and Zn phytoextraction by rapeseed and its potential oilseed production, but increased the solubility of several metal(loid)s. Here Zn and Cd concentrations in the soil pore water were decreased by rapeseed, showing the feasibility to strip available soil Zn and Cd in combination with seed production.

Fate of cadmium in the rhizosphere of Arabidopsis halleri grown in a contaminated dredged sediment.

In regions impacted by mining and smelting activities, dredged sediments are often contaminated with metals. Phytotechnologies could be used for their management, but more knowledge on the speciation of metals in the sediment and on their fate after colonization by plant roots is needed. This work was focused on a dredged sediment from the Scarpe river (North of France), contaminated with Zn and Cd. Zn, Cd hyperaccumulating plants Arabidopsis halleri from metallicolous and non-metallicolous origin were grown on the sediment for five months in a pot experiment. The nature and extent of the modifications in Cd speciation with or without plant were determined by electron microscopy, micro X-ray fluorescence and bulk and micro X-ray absorption spectroscopy. In addition, changes in Cd exchangeable and bioavailable pools were evaluated, and Cd content in leachates was measured. Finally, Cd plant uptake and plant growth parameters were monitored. In the original sediment, Cd was present as a mixed Zn, Cd, Fe sulfide. After five months, although pots still contained reduced sulfur, Cd-bearing sulfides were totally oxidized in vegetated pots, whereas a minor fraction (8%) was still present in non-vegetated ones. Secondary species included Cd bound to O-containing groups of organic matter and Cd phosphates. Cd exchangeability and bioavailability were relatively low and did not increase during changes in Cd speciation, suggesting that Cd released by sulfide oxidation was readily taken up with strong interactions with organic matter and phosphate ligands. Thus, the composition of the sediment, the oxic conditions and the rhizospheric activity (regardless of the plant origin) created favorable conditions for Cd stabilization. However, it should be kept in mind that returning to anoxic conditions may change Cd speciation, so the species formed cannot be considered as stable on the long term.

Do Arabidopsis halleri from nonmetallicolous populations accumulate zinc and cadmium more effectively than those from metallicolous populations?

• The ability of metallicolous and nonmetallicolous populations of Arabidopsis halleri to accumulate zinc (Zn), cadmium (Cd) and lead (Pb) is compared here in order to explore the extent and variability of this trait in wild A. halleri plants. • Aerial plant parts and the soil around the harvested plants were collected and analysed for metal concentrations or total and extractable metal concentrations, respectively, for 20 metallicolous and 13 nonmetallicolous populations. • Results show that metallicolous and nonmetallicolous populations have the same ability to accumulate Zn and Cd but that neither population type is able to accumulate Pb. Between populations within type, an homogenous accumulating response is observed for Zn, whereas the ability to accumulate Cd is variable. • Zn and Cd accumulation to very high concentrations is a constitutive property of the species. The Zn and Cd hyperaccumulator trait of A. halleri from contaminated sites was confirmed. Interestingly, nonmetallicolous plants are Zn and Cd hyperaccumulators. The possibility of using A. halleri in phytoremediation is discussed.

Selecting chemical and ecotoxicological test batteries for risk assessment of trace element-contaminated soils (phyto)managed by gentle remediation options (GRO).

During the past decades a number of field trials with gentle remediation options (GRO) have been established on trace element (TE) contaminated sites throughout Europe. Each research group selects different methods to assess the remediation success making it difficult to compare efficacy between various sites and treatments. This study aimed at selecting a minimum risk assessment battery combining chemical and ecotoxicological assays for assessing and comparing the effectiveness of GRO implemented in seven European case studies. Two test batteries were pre-selected; a chemical one for quantifying TE exposure in untreated soils and GRO-managed soils and a biological one for characterizing soil functionality and ecotoxicity. Soil samples from field studies representing one of the main GROs (phytoextraction in Belgium, Sweden, Germany and Switzerland, aided phytoextraction in France, and aided phytostabilization or in situ stabilization/phytoexclusion in Poland, France and Austria) were collected and assessed using the selected test batteries. The best correlations were obtained between NH4NO3-extractable, followed by NaNO3-extractable TE and the ecotoxicological responses. Biometrical parameters and biomarkers of dwarf beans were the most responsive indicators for the soil treatments and changes in soil TE exposures. Plant growth was inhibited at the higher extractable TE concentrations, while plant stress enzyme activities increased with the higher TE extractability. Based on these results, a minimum risk assessment battery to compare/biomonitor the sites phytomanaged by GROs might consist of the NH4NO3 extraction and the bean Plantox test including the stress enzyme activities.

Metal immobilization and soil amendment efficiency at a contaminated sediment landfill site: a field study focusing on plants, springtails, and bacteria.

Metal immobilization may contribute to the environmental management strategy of dredged sediment landfill sites contaminated by metals. In a field experiment, amendment effects and efficiency were investigated, focusing on plants, springtails and bacteria colonisation, metal extractability and sediment ecotoxicity. Conversely to hydroxylapatite (HA, 3% DW), the addition of Thomas Basic Slag (TBS, 5% DW) to a 5-yr deposited sediment contaminated with Zn, Cd, Cu, Pb and As resulted in a decrease in the 0.01 M Ca(NO(3))(2)-extractable concentrations of Cd and Zn. Shoot Cd and Zn concentration in Calamagrostis epigejos, the dominant plant species, also decreased in the presence of TBS. The addition of TBS and HA reduced sediment ecotoxicity and improved the growth of the total bacterial population. Hydroxylapatite improved plant species richness and diversity and decreased antioxidant enzymes in C. Epigejos and Urtica dïoica. Collembolan communities did not differ in abundance and diversity between the different treatments.

Phytoremediation as a management option for contaminated sediments in tidal marshes, flood control areas and dredged sediment landfill sites.

BACKGROUND, AIM AND SCOPE: Polluted sediments in rivers may be transported by the river to the sea, spread over river banks and tidal marshes or managed, i.e. actively dredged and disposed of on land. Once sedimented on tidal marshes, alluvial areas or control flood areas, the polluted sediments enter semi-terrestrial ecosystems or agro-ecosystems and may pose a risk. Disposal of polluted dredged sediments on land may also lead to certain risks. Up to a few years ago, contaminated dredged sediments were placed in confined disposal facilities. The European policy encourages sediment valorisation and this will be a technological challenge for the near future. Currently, contaminated dredged sediments are often not valorisable due to their high content of contaminants and their consequent hazardous properties. In addition, it is generally admitted that treatment and re-use of heavily contaminated dredged sediments is not a cost-effective alternative to confined disposal. For contaminated sediments and associated disposal facilities used in the past, a realistic, low cost, safe, ecologically sound and sustainable management option is required. In this context, phytoremediation is proposed in the literature as a management option. The aim of this paper is to review the current knowledge on management, (phyto)remediation and associated risks in the particular case of sediments contaminated with organic and inorganic pollutants. MAIN FEATURES: This paper deals with the following features: (1) management and remediation of contaminated sediments and associated risk assessment; (2) management options for ecosystems on polluted sediments, based on phytoremediation of contaminated sediments with focus on phytoextraction, phytostabilisation and phytoremediation of organic pollutants and (3) microbial and mycorrhizal processes occurring in contaminated sediments during phytoremediation. RESULTS: In this review, an overview is given of phytoremediation as a management option for semi-terrestrial and terrestrial ecosystems affected by polluted sediments, and the processes affecting pollutant bioavailability in the sediments. Studies that combine contaminated sediment and phytoremediation are relatively recent and are increasing in number since few years. Several papers suggest including phytoremediation in a management scheme for contaminated dredged sediments and state that phytoremediation can contribute to the revaluation of land-disposed contaminated sediments. The status of sediments, i.e. reduced or oxidised, highly influences contaminant mobility, its (eco)toxicity and the success of phytoremediation. Studies are performed either on near-fresh sediment or on sediment-derived soil. Field studies show temporal negative effects on plant growth due to oxidation and subsequent ageing of contaminated sediments disposed on land. The review shows that a large variety of plants and trees are able to colonise or develop on contaminated dredged sediment in particular conditions or events (e.g. high level of organic matter, clay and moisture content, flooding, seasonal hydrological variations). Depending on the studies, trees, high-biomass crop species and graminaceous species could be used to degrade organic pollutants, to extract or to stabilise inorganic pollutants. Water content of sediment is a limiting factor for mycorrhizal development. In sediment, specific bacteria may enhance the mobilisation of inorganic contaminants whereas others may participate in their immobilisation. Bacteria are also able to degrade organic pollutants. Their actions may be increased in the presence of plants. DISCUSSION: Choice of plants is particularly crucial for phytoremediation success on contaminated sediments. Extremely few studies are long-term field-based studies. Short-term effects and resilience of ecosystems is observed in long-term studies, i.e. due to degradation and stabilisation of pollutants. Terrestrial ecosystems affected by polluted sediments range from riverine tidal marshes with several interacting processes and vegetation development mainly determined by hydrology, over alluvial soils affected by overbank sedimentation (including flood control areas), to dredged sediment disposal facilities where hydrology and vegetation might be affected or managed by human intervention. This gradient is also a gradient of systems with highly variable soil and hydrological conditions in a temporal scale (tidal marshes) versus systems with a distinct soil development over time (dredged sediment landfill sites). CONCLUSIONS: In some circumstances (e.g. to avoid flooding or to ensure navigation) dredging operations are necessary. Management and remediation of contaminated sediments are necessary to reduce the ecological risks and risks associated with food chain contamination and leaching. Besides disposal, classical remediation technologies for contaminated sediment also extract or destroy contaminants. These techniques imply the sediment structure deterioration and prohibitive costs. On the contrary, phytoremediation could be a low-cost option, particularly suited to in situ remediation of large sites and environmentally friendly. However, phytoremediation is rarely included in the management scheme of contaminated sediment and accepted as a viable option. PERSPECTIVES: Phytoremediation is still an emerging technology that has to prove its sustainability at field scale. Research needs to focus on optimisations to enhance applicability and to address the economic feasibility of phytoremediation.

Assessment of successful experiments and limitations of phytotechnologies: contaminant uptake, detoxification and sequestration, and consequences for food safety.

PURPOSE: The term "phytotechnologies" refers to the application of science and engineering to provide solutions involving plants, including phytoremediation options using plants and associated microbes to remediate environmental compartments contaminated by trace elements (TE) and organic xenobiotics (OX). An extended knowledge of the uptake, translocation, storage, and detoxification mechanisms in plants, of the interactions with microorganisms, and of the use of "omic" technologies (functional genomics, proteomics, and metabolomics), combined with genetic analysis and plant improvement, is essential to understand the fate of contaminants in plants and food, nonfood and technical crops. The integration of physicochemical and biological understanding allows the optimization of these properties of plants, making phytotechnologies more economically and socially attractive, decreasing the level and transfer of contaminants along the food chain and augmenting the content of essential minerals in food crops. This review will disseminate experience gained between 2004 and 2009 by three working groups of COST Action 859 on the uptake, detoxification, and sequestration of pollutants by plants and consequences for food safety. Gaps between scientific approaches and lack of understanding are examined to suggest further research and to clarify the current state-of-the-art for potential end-users of such green options. CONCLUSION AND PERSPECTIVES: Phytotechnologies potentially offer efficient and environmentally friendly solutions for cleanup of contaminated soil and water, improvement of food safety, carbon sequestration, and development of renewable energy sources, all of which contribute to sustainable land use management. Information has been gained at more realistic exposure levels mainly on Cd, Zn, Ni, As, polycyclic aromatic hydrocarbons, and herbicides with less on other contaminants. A main goal is a better understanding, at the physiological, biochemical, and molecular levels, of mechanisms and their regulation related to uptake-exclusion, apoplastic barriers, xylem loading, efflux-influx of contaminants, root-to-shoot transfer, concentration and chemical speciation in xylem/phloem, storage, detoxification, and stress tolerance for plants and associated microbes exposed to contaminants (TE and OX). All remain insufficiently understood especially in the case of multiple-element and mixed-mode pollution. Research must extend from model species to plants of economic importance and include interactions between plants and microorganisms. It remains a major challenge to create, develop, and scale up phytotechnologies to market level and to successfully deploy these to ameliorate the environment and human health.