Copper-uptake mediated by an ecofriendly zwitterionic ionic liquid: A new challenge for a cleaner bioeconomy.

This study aims to investigate the ability of an imidazolium biobased Zwitterionic Ionic Liquids (ZILs) in enhancing the phytoavailability of copper from garden (G) and vineyard (V) soils using the model plant ryegrass. Uncontaminated and artificially contaminated CuSO4 soils, unamended and ZIL-amended soil modalities were designed. The copper/ZIL molar ratio (1/4) introduced was rationally established based on molecular modeling and on the maximal copper concentration in artificially contaminated soil. Higher accumulation of copper in the shoots was detected for the uncontaminated and copper contaminated ZIL amended V soils (18.9 and 23.3 mg/kg, respectively) contrary to G soils together with a ZIL concentration of around 3% (W/W) detected by LC-MS analyses. These data evidenced a Cu-accumulation improvement of 38% and 66% compared to non-amended V soils (13.6 and 13.9 mg/kg respectively). ZIL would be mainly present under Cu(II)-ZIL4 complexes in the shoots. The impact on the chemical composition of shoot was also studied. The results show that depending on the soils modalitity, the presence of free copper and/or ZIL led to different chemical compositions in lignin and monomeric sugar contents. In the biorefinery context, performances of enzymatic hydrolysis of shoots were also related to the presence of both ZIL and copper under free or complex forms. Ecotoxicity assessment of the vineyard soil samples indicated that the quantity of copper and ZIL remaining in the soils had no significant toxicity. ZIL amendment in a copper-contaminated soil was demonstrated as being a promising way to promote the valorization of phytoremediation plants.

Potentials of Miscanthus x giganteus for phytostabilization of trace element-contaminated soils: Ex situ experiment.

Phytomanagement is proposed as a cost-effective and environmentally-friendly suggestion for sustainable use of large metal-contaminated areas. In the current work, the energy crop miscanthus (Miscanthus × giganteus) was grown in ex situ conditions on agricultural soils presenting a Cd, Pb and Zn contamination gradient. After 93 days of culture, shoot and root growth parameters were measured. Soils and plants were sampled as well to study the TE accumulation in miscanthus and the effects of this plant on TE mobility in soils. Results demonstrated that miscanthus growth depended more on the soils silt content rather than TE-contamination level. Moreover, soil organic carbon at T93 increased in the soils after miscanthus cultivation by 25.5-45.3%, whereas CaCl2-extractible TEs decreased due to complex rhizosphere processes driving plant mineral uptake, and organic carbon inputs into the rhizosphere. In the contaminated soils, miscanthus accumulated Cd, Pb and Zn mainly in roots (BCF in roots: Cd " Zn > Pb), while strongly reducing the transfer of these elements from soil to all organs and from roots to rhizomes, stems and leaves (average TFs: 0.01-0.06, 0.11-1.15 and 0.09-0.79 corresponding to Cd, Pb and Zn respectively). Therefore, miscanthus could be considered a TE-excluder, hence a potential candidate crop for coupling phytostabilization and biomass production on the studied Metaleurop TE-contaminated soils.

Miscanthus x giganteus culture on soils highly contaminated by metals: Modelling leaf decomposition impact on metal mobility and bioavailability in the soil-plant system.

Miscanthus x giganteus is suggested as a good candidate for phytostabilization of metal-polluted soils. Its late harvest in winter generates large amounts of leaf litter on the soil surface. However, little is known about the mobility and the bioavailability of metals following leaf decomposition and the consequences on the succeeding culture. Ex situ artificial aging for 1, 3, and 6 months was conducted with miscanthus leaf fragments incorporated into three agricultural soils displaying a gradient concentration in Cd (0.6, 3.1 and 7.9 mg kg-1), Pb (32.0, 194.6 and 468.6 mg kg-1), and Zn (48.4, 276.3 and 490.2 mg kg-1) to simulate the leaf litter input over 20 years of miscanthus culture. We investigated the impacts on physicochemical and biological soil parameters, CaCl2-extractable metal, and their subsequent ryegrass shoot concentrations, and hence on ryegrass health. The results showed that the amended soils possessed higher pH along with greater available phosphorous and soil organic carbon values. The respiratory activity and microbial biomass carbon in the amended soils increased mainly after 1 month of aging, and decreased afterwards. Despite the higher Pb- and Zn-CaCl2 extractability in the amended soils, the phytoavailability slightly increased only in the most contaminated soils. Moreover, leaf incorporation did not affect the ryegrass biomass, photosynthetic pigment contents, nor the antioxidative enzyme activities. Conclusively, leaf incorporation induced slight variations in soil physicochemical and biological parameters, as well as metal extractability, but not to an extent that might cause a considerable threat to the subsequent culture. Nevertheless, these results are preliminary data that require confirmation by long-term in-situ experimentations as they reflect the modelization of long-term impact of leaf decomposition on soil-plant system.

A sustainable approach to manage metal-contaminated soils: a preliminary greenhouse study for the possible production of metal-enriched ryegrass biomass for biosourced catalysts.

Two kitchen garden soils (A and B) sampled in contaminated areas were amended using phosphates in sustainable quantities in order to reduce the environmental availability of potentially toxic inorganic elements (PTEs) and to favour the availability of alkali, alkali earth and micronutrients. The environmental availability of PTEs was evaluated using a potential plant for revegetation of contaminated soils (ryegrass) and a mixture of low molecular weight organic acids. Despite the highest contamination level of B, the concentration of metals was highest in the ryegrass shoots grown on A for the two harvests. These results correlated well with those obtained using low molecular weight organic acids for Cd, Zn and Cu, whereas this mixture failed to represent the transfer of nutrients due to the presence of biological and physiological mechanisms. The statistical differences between the biomass of ryegrass obtained at the first and the second harvests were attributed to the decrease of available potassium, implicated in the growth and development of plants. Phosphates increased the ratios Zn/Cd, Zn/Pb and Zn/Cu up to 176 ± 48, 38 ± 6 and 80 ± 12, respectively, and made possible the reduction of the concentration of Cd and Pb in the shoots of ryegrass by 22% and 25%, respectively. The concentration of Zn in the shoots of ryegrass from the first and the second harvests grown on soil A were in the range 1050-2000 mg kg-1, making this plant a potential biomass to (i) produce biosourced catalysts for organic chemistry applications in a circular economy concept and (ii) limit human exposure to commercial Lewis acids. A preliminary application was identified.

Effects of Heavy Metals Artificial Contamination on Porcellio laevis (Latreille, 1804) (Crustacea: Isopoda: Oniscidea).

This study aimed at determining the competition of cadmium (Cd), lead (Pb), zinc (Zn) and copper (Cu) on their assimilation, on the food consumption and the growth of terrestrial isopod Porcellio laevis. Individuals were exposed to artificially contaminated litter of Quercus for 4 weeks and were weekly weighed. At the end of the experiment, the concentration of Cd, Pb, Zn and Cu in individuals were measured by atomic absorption spectrometry. Biological parameters such as growth, and bioaccumulation factor (BAF) were calculated and results from the various treatments were compared. Depending on metals, weight loss or gain were recorded for isopods during the four weeks of exposure. A weight loss was measured on individuals exposed to Cd-contaminated litter whereas a weight gain was highlighted for those exposed to the Zn-contaminated litter. BAF values revealed that P. laevis was macroconcentrator of Zn and Cu and deconcentrator of Cd and Pb.

Measure of environmental stress on Porcellio laevis Latreille, 1804 sampled near active Tunisian industrial areas.

This study aimed to observe the type of asymmetry exhibited by Porcellio laevis sampled from 15 sites belonging to Tunisian industrialized areas. Physicochemical parameters such as pH, organic matter and CaCO3 contents were measured in soils. Moreover, Cd, Pb, Zn, and Cu concentrations were determined in both soils and woodlice. Additionally, 10 metrical traits were measured to evaluate the type of asymmetry on individuals: the basis, the second and the third articles of the antenna, the first article of the flagellum of the antenna and the merus, the carpus, and the propodus of the sixth and the seventh pereopods. Among the 531 measured individuals, 432 exhibited fluctuating asymmetry (FA) while the remaining individuals exhibited antisymmetry or directional asymmetry. The data obtained were analyzed using a multivariate statistical analysis. Contrary to our hypothesis, the results showed that individuals from contaminated sites have a low FA level, whereas those from uncontaminated sites have a high FA level, particularly females but with some exceptions. Variations in FA level in the traits and populations studied and its usefulness as a stress indicator were discussed.

Do biochars influence the availability and human oral bioaccessibility of Cd, Pb, and Zn in a contaminated slightly alkaline soil?

Different remediation techniques have been used to restore metal-contaminated sites, including stabilizing metals by adding amendments to the soils. This study experimented three biochars, made from wood and miscanthus, cultivated on contaminated and uncontaminated soils, used as amendments at a 2% application rate on a metal-contaminated soil for 9 months in laboratory-controlled conditions. The objective was to evaluate whether biochars were able to decrease the availability and human oral bioaccessibility of metals in an alkaline soil. To meet this goal, the modifications of the soil's physicochemical parameters, metal distribution in soil, and human bioaccessibility were evaluated at different sampling times. The results showed that biochar application to the alkaline soil did not always decrease the soil metal availability, which challenges the value of using biochars in already slightly alkaline soils at a low application rate. However, differences in efficiency between the three biochars tested were highlighted. The biochar produced with miscanthus cultivated on uncontaminated soil led to higher soil metal bioaccessibility. Moreover, because of the absence of any increase in soil metal availability with the biochar produced from biomass cultivated on contaminated soil, the use of such biochars can be recommended for the remediation of contaminated soil.

Sustainability of an in situ aided phytostabilisation on highly contaminated soils using fly ashes: Effects on the vertical distribution of physicochemical parameters and trace elements.

Aided phytostabilisation using trees and fly ashes is a promising technique which has shown its effectiveness in the management of highly metal-contaminated soils. However, this success is generally established based on topsoil physicochemical analysis and short-term experiments. This paper focuses on the long-term effects of the afforestation and two fly ashes (silico-aluminous and sulfo-calcic called FA1 and FA2, respectively) by assessing the integrity of fly ashes 10 years after their incorporation into the soil as well as the vertical distribution of the physicochemical parameters and trace elements (TEs) in the amended soils (F1 and F2) in comparison with a non-amended soil (R). Ten years after the soil treatment, the particle size distribution analysis between fly ashes and their corresponding masses (fly ash + soil particles) showed a loss or an agglomeration of finer particles. This evolution matches with the appearance of gypsum (CaSO4 2H2O) in FA2m instead of anhydrite (CaSO4), which is the major compound of FA2. This finding corresponds well with the dissolution and the lixiviation of Ca, S and P included in FA2 along the F2 soil profile, generating an accumulation of these elements at 30 cm depth. However, no variation of TE contamination was found between 0 and 25 cm depth in F2 soil except for Cd. Conversely, Cd, Pb, Zn and Hg enrichment was observed at 25 cm depth in the F1 soil, whereas no enrichment was observed for As. The fly ashes studied, and notably FA2, were able to reduce Cd, Pb and Zn availability in soil and this capacity persists over the time despite their structural and chemical changes.

Determining the influence of the physicochemical parameters of urban soils on As availability using chemometric methods: A preliminary study.

An initial exploration was conducted using mathematical and statistical methods to obtain relevant information about the determination of the physicochemical parameters capable of controlling As uptake by ryegrass grown on contaminated topsoils. Concentrations of As in the soils were from 10 to 47mg/kg, mainly in the As(V) form (57%-73%). Concentrations of As in water extracts were very low (61-700µg/kg). It was suggested that As(III) was mainly in the uncharged species and As(V) in the charged species. Chemometric methods revealed that the values of the ratio As(III)/As(V) depended on the assimilated-phosphorus, the pseudo-total and water-extractable Fe contents and the soil pH. Arsenic concentrations measured in ryegrass shoots ranged from 119 to 1602µg/kg. Positive linear correlations were obtained between As in ryegrass shoots and water extractable-As. The transfer coefficient of As correlated well with the ratio assimilated-phosphorus/Fe-oxides. As(III) uptake by the shoot of ryegrass was controlled by the organic matter and Fe-oxide contents.

Elaboration, characteristics and advantages of biochars for the management of contaminated soils with a specific overview on Miscanthus biochars.

Biochars are products that are rich in carbon obtained by pyrolysis processes that consist in introducing a biomass (such as wood or manure) in a closed container and heating it with little or no available air. This paper reports the impacts of pyrolysis parameters on biochar characteristics. A preliminary examination of the scientific literature revealed that the type of feedstock, the temperature, the heating rate and the gas flow were the major parameters influencing the biochar characteristics. This review highlights the multitude of biochars that can be made and shows the importance of characterizing them before their use in soils. Then we assess how the input of biochars in soils can affect soil parameters. A review of the literature showed modifications on: i) the physical properties of soils (i.e. the modification in soil structure and water retention), ii) the chemical properties of soils (i.e. the modification of pH, cation exchange capacity, nutrient availability, the organic matter content) and iii) the biological properties (i.e. the changes in microbial and faunal communities). All these modifications can lead to an increase in crop productivity, which confirms the value of biochars as a soil amendment. Moreover, biochars can also provide an advantage for soil remediation. Indeed, biochars efficiently reduce the bioavailability of organic and inorganic pollutants. In addition, this review focuses on a specific plant that can be used to produce biochars: Miscanthus, a non-wood rhizomatous C4 perennial grass. Miscanthus presents advantages for biochar production due to: i) its lignocellulosic content, ii) its silicon content, which can mitigate environmental stresses (notably for plants grown on contaminated sites) and iii) the greater surface area of the Miscanthus biochars compared to the biochars produced with other feedstock.

Use of an in vitro digestion method to estimate human bioaccessibility of Cd in vegetables grown in smelter-impacted soils: the influence of cooking.

Metal contamination of urban soils and homegrown vegetables has caused major concern. Some studies showed that cadmium (Cd) was among the most significant hazards in kitchen garden soils and prolonged exposure to this metal could cause deleterious health effects in humans. In general, most risk assessment procedures are based on total concentrations of metals in vegetables. The present study assesses human bioaccessibility of Cd in vegetables cultivated in smelter-impacted kitchen garden soils. Seven vegetables (radish, lettuce, French bean, carrot, leek, tomato, and potato) were considered. Using the UBM protocol (unified BARGE bioaccessibility method), the bioaccessibility of Cd was measured in raw/cooked vegetables. A considerable amount of Cd was mobilized from raw vegetables during the digestion process (on average 85% in the gastric phase and 69% in the gastrointestinal phase), which could be attributed to a high uptake of Cd during the growth of the vegetables. Most Cd is accumulated in the vacuoles of plant cells, except what is absorbed by the cell wall, allowing Cd to be released from plant tissues under moderate conditions. Cooking by the steaming process generally increased the bioaccessibility of Cd in French bean, carrot, and leek. For potato, few or no significant differences of Cd bioaccessibility were observed after the steaming process, while the frying process strongly decreased bioaccessibility in both phases. The estimation of metal bioaccessibility in vegetables is helpful for human health risk assessment.

Phytomanagement of a metal-contaminated agricultural soil with Sorghum bicolor, humic / fulvic acids and arbuscular mycorrhizal fungi near the former Pb/Zn metaleurop Nord smelter.

As many contaminated agricultural soils can no longer be used for food crops, lignocellulosic energy crops matter due to their ability to grow on such soils and to produce biomass for biosourced materials and biofuels, thereby reducing the pressure on the limited arable lands. Sorghum bicolor (L.) Moench, can potentially produce a high biomass suitable for producing bioethanol, renewable gasoline, diesel, and sustainable aircraft fuel, despite adverse environmental conditions (e.g. drought, contaminated soils). A 2-year field trial was carried out for the first time in the northern France for assessing sorghum growth on a Cd, Pb and Zn-contaminated agricultural soil amended with humic/fulvic acid, alone and paired with arbuscular mycorrhizal fungi. Sorghum produced on average (in t DW ha-1): 12.4 in year 1 despite experiencing a severe drought season and 15.3 in year 2. Humic/fulvic acids (Lonite 80SP®) and arbuscular mycorrhizal fungi did not significantly act as biostimulants regarding the shoot DW yield and metal uptake of sorghum. The annual shoot Cd, Pb and Zn removals averaged 0.14, 0.20 and 1.97 kg ha-1, respectively. Sorghum cultivation and its metal uptake induced a significant decrease in 0.01 M Ca(NO3)2-extractable soil Cd, Pb and Zn concentrations by 95%, 73% and 95%, respectively, in year 2. Soluble and exchangeable soil Cd, Pb and Zn would be progressively depleted in subsequent crops, which should result in lower pollutant linkages and enhanced ecosystem services. This evidenced sorghum as a relevant plant species for phytomanaging the large area (750 ha) with metal-contaminated soil near the former Pb/Zn Metaleurop Nord smelter, amidst ongoing climate change. The potential bioethanol yield of the harvested sorghum biomass was 5589 L ha-1. Thus sorghum would be a promising candidate for bioethanol production, even in this northern French region.

Plant testing with hemp and miscanthus to assess phytomanagement options including biostimulants and mycorrhizae on a metal-contaminated soil to provide biomass for sustainable biofuel production.

The need of biofuels from biomass, including sustainable aviation fuel, without using agricultural land dedicated to food crops, is in constant demand. Strategies to intensify biomass production using mycorrhizal fungi, biostimulants and their combinations could be solutions for improving the cultivation of lignocellulosic plants but still lack well-established validation on metal-contaminated soils. This study aimed to assess the yield of Miscanthus x giganteus J.M. Greef & Deuter and Cannabis sativa L. grown on a metal-contaminated agricultural soil (11 mg Cd, 536 mg Pb and 955 mg Zn kg-1) amended with biostimulants and/or arbuscular mycorrhizal fungi, and the shoot Cd, Pb and Zn uptake. A pot trial was carried out with soil collected from a field near a former Pb/Zn smelter in France and six treatments: control (C), protein hydrolysate (a mixture of peptides and amino acids, PH), humic/fulvic acids (HFA), arbuscular mycorrhizae fungi (AMF), PH combined with AMF (PHxAMF), and HFA combined with AMF (HFAxAMF). Metal concentrations in the soil pore water (SPW), pH and electrical conductivity were measured over time. Miscanthus and hemp shoots were harvested on day 90. Both PH and PHxAMF treatments increased SPW Cd, Pb, and Zn concentrations (e.g. by 26, 1.9, and 22.9 times for miscanthus and 9.7, 4.7, and 19.3 times for hemp in the PH and PHxAMF treatments as compared to the control one, respectively). This led to phytotoxicity and reduced shoot yield for miscanthus. Conversely, HFA and HFAxAMF treatments decreased SPW Cd and Zn concentrations, increasing shoot yields for hemp and miscanthus. Shoot Cd, Pb, and Zn uptakes peaked for PH and PHxAMF hemp plants (in µg plant-1, Cd: 310-334, Pb: 34-38, and Zn: 232-309 for PHxAMF and PH, respectively), while lowest values occurred for PH miscanthus plants mainly due to low shoot yield. Overall, this study suggested that humic/fulvic acids can be an effective biostimulant for increasing shoot biomass production in a metal-contaminated soil. These results warrant further investigations of the HFAxAMF in field trials.

Multivariate analysis of chemical and genetic diversity of wild Humulus lupulus L. (hop) collected in situ in northern France.

The hop plant (Humulus lupulus L.) has been exploited for a long time for both its brewing and medicinal uses, due in particular to its specific chemical composition. These last years, hop cultivation that was in decline has been experiencing a renewal for several reasons, such as a craze for strongly hopped aromatic beers. In this context, the present work aims at investigating the genetic and chemical diversity of fifty wild hops collected from different locations in Northern France. These wild hops were compared to ten commercial varieties and three heirloom varieties cultivated in the same sampled geographical area. Genetic analysis relying on genome fingerprinting using 11 microsatellite markers showed a high level of diversity. A total of 56 alleles were determined with an average of 10.9 alleles per locus and assessed a significant population structure (mean pairwise FST = 0.29). Phytochemical characterization of hops was based on volatile compound analysis by HS-SPME GC-MS, quantification of the main prenylated phenolic compounds by UHPLC-UV as well as untargeted metabolomics by UHPLC-HRMS and revealed a high level of chemical diversity among the assessed wild accessions. In particular, analysis of volatile compounds revealed the presence of some minor but original compounds, such as aromadendrene, allo-aromadendrene, isoledene, ß-guaiene, α-ylangene and ß-pinene in some wild accessions; while analysis of phenolic compounds showed high content of ß-acids in these wild accessions, up to 2.37% of colupulone. Genetic diversity of wild hops previously observed was hence supported by their chemical diversity. Sample soil analysis was also performed to get a pedological classification of these different collection sites. Results of the multivariate statistical analysis suggest that wild hops constitute a huge pool of chemical and genetic diversity of this species.

Advantages and limits to copper phytoextraction in vineyards.

Copper (Cu) contamination of soils may alter the functioning and sustainability of vineyard ecosystems. Cultivating Cu-extracting plants in vineyard inter-rows, or phytoextraction, is one possible way currently under consideration in agroecology to reduce Cu contamination of vineyard topsoils. This option is rarely used, mainly because Cu phytoextraction yields are too low to significantly reduce contamination due to the relatively "low" phytoavailability of Cu in the soil (compared to other trace metals) and its preferential accumulation in the roots of most extracting plants. This article describes the main practices and associated constraints that could theoretically be used to maximize Cu phytoextraction at field scale, including the use of Cu-accumulating plants grown (i) with acidifying plants (e.g., leguminous plants), and/or (ii) in the presence of acidifying fertilizers (ammonium, elemental sulfur), or (iii) with soluble "biochelators" added to the soil such as natural humic substances or metabolites produced by rhizospheric bacteria such as siderophores, in the inter-rows. This discussion article also provides an overview of the possible ways to exploit Cu-enriched biomass, notably through ecocatalysis or biofortification of animal feed.

The phytoextraction power of Cichorium intybus L. on metal-contaminated soil: Focus on time- and cultivar-depending accumulation and distribution of cadmium, lead and zinc.

This study is focused on the evaluation of the accumulation of Cd, Pb and Zn in five cultivars of Cichorium intybus L. (chicory) which were produced on contaminated agricultural soil. Over a growth period of 211 days, the roots and leaves were collected in four stages and then analyzed by flame atomic absorption spectrometry to measure the concentration and distribution of the target metals in these two chicory organs considering the weather and the nature of the cultivar. For all cultivars, sharp decreases of Pb (from 165 mg kg-1 to 3 mg kg-1), Cd (from 11 mg kg-1 to 5 mg kg-1) and Zn concentrations (from 157 mg kg-1 to 40 mg kg-1) in the roots were highlighted over time. The data collected enabled the calculation of the variation of the bioconcentration factor, the biological absorption coefficient and the translocation factor for Cd, Pb and Zn. These parameters were then correlated with the distribution of the fresh biomass of leaves and roots and several indicators such as chlorophyll content, flavonols, anthocyanin and nitrogen balance index were measured. The study concludes with the discussion on the ability of chicory to clean up contaminated agricultural soil. The current investigation has shown: i) a translocation of Cd (and Zn to a lesser extent) from the roots to the leaves; ii) an increase in the level of anthocyanins with the increase of the metal trace elements concentration in the leaf, while the content of chlorophyll and the nitrogen balance index decrease, which could be linked to the phenomenon of senescence; iii) an ability of the chicory to reduce the bioavailable pool of the three metal trace elements studied, in particular for Cd.

Growth and metal accumulation in Porcellio scaber exposed to poplar litter from Cd-, Pb-, and Zn-contaminated sites.

This study aimed at determining, in the laboratory, the effects of poplar litter collected in woody habitats contaminated by heavy metals on growth and metal accumulation in the terrestrial isopod Porcellio scaber. Cd, Pb, and Zn pseudototal and CaCl(2)-extractable concentrations in litter types were determined using AAS. Juveniles were fed ad libitum, individually, for 28 days with four litter types presenting an increasing gradient of metal contamination. Individuals were weighed every week and metal body burdens were determined at the end of the experiment. From the first week until the end of the experiment, a decrease in P. scaber growth related to the increase of metal concentration in litter types was recorded. Significant correlations were observed between metal body burdens and metal concentrations in litter types. However, Cd accumulation in woodlice appeared to be related to the Cd/Zn concentration ratio in litter types. All these results showed the potential of weight gain in P. scaber as a suitable indicator for litter quality assessment with ecological relevance.

Assessing Cd, Pb, Zn human bioaccessibility in smelter-contaminated agricultural topsoils (northern France).

The extractability of Cd, Pb, and Zn was investigated in contaminated agricultural topsoils located in an area highly affected by the past atmospheric emissions of two smelters in northern France in order to assess their mobility and human bioaccessibility. The determination of Cd, Pb, and Zn bioaccessibility (Unified Barge Method, in vitro test) was made to evaluate the absolute trace element (TE) bioavailability. The results highlighted differences in bioaccessibility between Cd, Pb, and Zn (Cd > Pb > Zn). The mean values of the bioaccessible fractions of Cd, Pb, and Zn during the gastric phase were 82, 55, and 33%, respectively, of the pseudototal concentrations, whereas during the gastrointestinal phase, the bioaccessible fractions of metals decreased to 45, 20, and 10%, respectively. Stepwise multiple regression analysis showed that human bioaccessibility was affected by various physicochemical parameters (i.e., sand, carbonates, organic matter, assimilated P, free Al oxides, and pseudototal Fe contents). Sequential extractions were performed as an indication of the TE availability in these soils. Cadmium occurred in the more available fractions, Pb was mostly present as bound by oxides, and a significant contribution to the pseudototal Zn concentration was defined as the unavailable residual form related to the crystalline structures of minerals. The concepts of bioavailability and bioaccessibility are important for quantifying the risks associated with exposure to environmental pollutants and providing more realistic information for human health.

Wheat and ryegrass biomass ashes as effective sorbents for metallic and organic pollutants from contaminated water in lab-engineered cartridge filtration system.

Three plant biomasses (miscanthus, ryegrass and wheat) have been considered for the preparation of five different sorbents evaluated for their potential to sorb cadmium and lead and four emergent organic compounds (diclofenac, sulfamethoxazole, 17α-ethynylestradiol and triclosan) from artificially contaminated water. Lab-created cartridges were filled with each sorbent and all experiments were systematically compared to activated charcoal Norit®. Results from activated charcoal, wheat straw and acidified wheat straw were supported by the Langmuir and Freundlich models. Wheat straw ashes were an excellent metal extractor that exceeded the potential of well-known activated charcoal. Acidified sorbents (wheat and ryegrass) were very effective in eliminating the selected emerging organic contaminants displaying equipotent or superior activity compared to activated charcoal. These results open the way for further in natura studies by proposing new biosource materials as new effective tools in the fight against water pollution.

Ex situ evaluation of the effects of biochars on environmental and toxicological availabilities of metals and polycyclic aromatic hydrocarbons.

The present study experimented five biochars, one made from wood (400 °C, 12 h) and four made from miscanthus cultivated on contaminated soils (temperature 400/600 °C, duration 45/90 min). They were used as amendments at a 2% application rate on soil, cultivated or not cultivated with ryegrass, contaminated with (i) metals (Cd, Pb, and Zn), (ii) eight polycyclic aromatic hydrocarbons (PAHs), and (iii) a mix of metals and PAHs. The objectives were (i) to compare the effectiveness of the five biochars on soil parameters and pollutant availability and (ii) to determine the influence of soil multicontamination and ryegrass cultivation on biochar effectiveness. The results showed that biochar application did not necessarily lead to lower pollutant extractability and metal bioaccessibility. However, differences were highlighted between the biochars. The miscanthus biochars produced at 600 °C (BM600) showed higher effectiveness at decreasing metal extractability than the miscanthus biochars produced at 400 °C (BM400) due to its better sorption characteristics. In addition, ryegrass cultivation did not impact pollutant availability but modified metal bioaccessibility, especially for the soil amended with the BM600 and the woody biochar. Moreover, the presence of PAHs also negatively impacted the metal bioaccessibility in the soil amended with the BM600, and, on the contrary, positively impacted it in the soil amended with the BM400. Complementary studies are therefore necessary to understand the mechanisms involved, particularly in a context where soils requiring remediation operations are often multicontaminated and vegetated.