Tetracyclines are a class of antimicrobials frequently found in the environment, and have promoted the proliferation of antibiotic resistance. An unanswered research question is whether tetracycline sorbed to soils is still bioavailable to bacteria and exerts selective pressure on the bacterial community for the development of antibiotic resistance. In this study, bioreporter E. coli MC4100/pTGM strain was used to probe the bioavailability of tetracycline sorbed by smectite clay, a class of common soil minerals. Batch sorption experiments were conducted to prepare clay samples with a wide range of sorbed tetracycline concentration. The bioreporter was incubated with tetracycline-sorbed clay at different clay/solution ratios and water contents, as well as using dialysis tubings to prevent the direct contact between bacterial cells and clay particles. The expression of antibiotic resistance genes from the bioreporter was measured using a flow cytometer as a measurement of bioavailability/selective pressure. The direct contact of bioreporter cells to clay surfaces represented an important pathway facilitating bacterial access to clay-sorbed tetracycline. In clay-water suspensions, reducing solution volume rendered more bacteria to attach to clay surfaces enhancing the bioavailability of clay-sorbed tetracycline. The strong fluorescence emission from bioreporter cells on clay surfaces indicated that clay-sorbed tetracycline was still bioavailable to bacteria. The formation of biofilms on clay surfaces could increase bacterial access to clay-sorbed tetracycline. In addition, desorption of loosely sorbed tetracycline into bulk solution contributed to bacterial exposure and activation of the antibiotic resistance genes. Tetracycline sorbed by soil geosorbents could exert selective pressure on the surrounding microbial communities via bacterial exposure to tetracycline in solution from desorption and to the geosorbent-sorbed tetracycline as well.

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5–3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥0.5 M NaOH ≥3 M NaOH ≥3 M HCl for smectite, and 0.5 M HCl ≥3 M NaOH ≥0.5 M NaOH ≥3 M HCl ≥ unmodified for palygorskite. A14C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5–8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.

Carbon nanotubes are often modified to be stable in the aqueous phase by adding extensive hydrophilic surface functional groups. The stability of such CNTs in water with soil or sediment is one critical factor controlling their environmental fate. We conducted a series of experiments to quantitatively assess the association between water dispersed multi-walled carbon nanotubes (MWCNTs) and three soil minerals (kaolinite, smectite, or shale) in aqueous solution under different sodium concentrations. ¹⁴C-labeling was used in these experiments to unambiguously quantify MWCNTs. The results showed that increasing ionic strength strongly promoted the removal of MWCNTs from aqueous phase. The removal tendency is inversely correlated with the soil minerals’ surface potential and directly correlated with their hydrophobicity. This removal can be interpreted by the extended Derjaguin–Landau–Verwey–Overbeek (EDLVO) theory especially for kaolinite and smectite. Shale, which contains large and insoluble organic materials, sorbed MWCNTs the most strongly.

International audience | Siderophores are chelators with a high selectivity for Fe(III) and a good affinity for divalent metals, including Cd(II) and Ni(II). Inoculation with siderophore-producing bacteria (SPB) has thus been proposed as an alternative to chelator supply in phytoremediation. Accurate assessments of the potential of this association require a dissection of the interaction of siderophores with metals at the soil–root interface. This study focuses on pyoverdine (Pvd), the main siderophore produced by Pseudomonas aeruginosa. We first assessed the ability of Pvd to coordinate Ni(II). The stability constant of Pvd–Ni(II) (log K L′Ni = 10.9) was found to be higher than that of Pvd–Cd(II) (log K L′Cd = 8.2). We then investigated the effect of a direct supply of Pvd on the mobilization, speciation, and phytoavailability of Cd and Ni in hydroponics. When supplied at a concentration of 50 μM, Pvd selectively promoted Ni mobilization from smectite. It decreased plant Ni and Cd contents and the free ionic fractions of these two metals, consistent with the free ion activity model. Pvd had a more pronounced effect for Ni than for Cd, as predicted from its coordination properties. Inoculation with P. aeruginosa had a similar effect on Ni phytoavailability to the direct supply of Pvd.

The sediments were studied according to the granulometric characteristics, the geochemical analyses of the sediments (organic matter (OM), carbonate, and pH), the analyses of heavy metals (HM) characteristics, and their contamination status in the ecological system and the mineralogical analysis of the sediments at 8 sites spread over the Marchica lagoon (NE-Morocco). Our results showed that the opening of the new wide and deep pass affected the spatial distributions of the metals, which were closely related to fine fraction and sediment OM concentration. In the north and southeast lagoon zones presented low concentrations of the HM, fine particles (clay), OM, whereas the south and the center of the lagoon were heavily loaded with HM and OM, corresponding to the trapping zones by fine particles. The results of mineralogy analyses have revealed the predominance of non-clay minerals such as quartz and calcite, and for the clay fractions of sediments showed that they are formed of illite, kaolinite, smectite, and chlorite in highly variable proportions; illite was the most dominant clay in the north-western Marchica lagoon sediments. Therefore, the HMs are fixed by clay colloids having a high cation exchange capacity with smectite-chlorite-kaolinite assembly.

This work investigated the impact of a clay mineral on toxic waste. The Ivorian Anti-pollution Center discovered the toxic waste from Probo Koala boat on 21 August 2006. This boat had been used to refine oil named naphtha of cokéfaction by Trafigura firm in the sea. The process of refining consists of caustic sodium carbonate washing and produced toxic waste. These toxic wastes have been unloading in 13 zones of the Abidjan district: Akouédo, Abobo, Abobo Alépé road (Djibi village), civile prison road (MACA), industrial zone of Koumassi, Port-Bouët - Vridi CAP Logistic (Rue Saint-Sylvestre)… This situation caused a socio-political crisis and generated the death of many people. To solve this problem, one first part has been excavated and sent to France to be incinerated. A second part is used to be a biopile for bioremediation. After these two processes, the rest of toxic waste remained in the place where they have been unloaded. The analyses of these toxic wastes show that polycyclic aromatic hydrocarbons (PAHs), oxygenated polycyclic aromatic compounds (O-PACs), volatile aromatic compound (VAC), mercaptan and sulfur molecules, and also heavy metal and organometallic are the principal polluters of these contaminated soils. From a mineralogical viewpoint, the tropical climate soils of Ivory Coast in general and district of Abidjan in particular constituted of about 50% of kaolinite, 30 to 40% of smectite, and 10 to 20% of illite (OSTROM 1993). In this study, we want to show the impact of this local clay on toxic waste.

The sorption of three organic contaminants with different structure and polarity including non-polar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), and polar 1,2-dichlorobenzene (DCB) onto original kaolinite, smectite, vermiculite, and fulvic acid (FA)/humic acid (HA)–clay complexes were investigated, and possible sorption mechanisms were inferred from sorption isotherms and characteristics of humic substances (HS) and HS–mineral complexes. Results showed smectite and vermiculite had stronger sorption ability than kaolinite, and the adsorbed amount of DCB was much higher than that of PHEN and TeCB on each clay. Due to FA/HA-facilitated hydrophobic interaction, FA/HA–clay complexes except FA–vermiculite complex showed a stronger affinity for PHEN and TeCB than the original clays, particularly for HA–clay complexes. The non-linearity parameter values of n for all the Freundlich sorption isotherms of DCB were greater than 1, indicating that clays possessed some unique sites with strong affinity and capacity to sorb DCB from aqueous solutions. FA/HA did not significantly affect the sorption of polar DCB on clays, implying sorption of DCB on clays was probably due to polar interactions between the polar group of DCB and clays. Cation-π bonding between PHEN and iron cation was directly evidenced by X-ray photoelectron spectroscopy, and FA impeded the sorption of PHEN on vermiculite by occupation of iron cation sites. This study will benefit understanding behaviors of contaminants in the soil environments.

The present research evaluates the influence of modification of smectite clay (BC) on its adsorption capacity of anionic dyes from aqueous solutions. Thermal (BC 250), acidic (BC H₂SO₄), and alkaline (BC NaOH) modification of clay was carried out. The clays were characterized by X-ray powder diffraction, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy. Adsorption of dyes was investigated by batch experiments at room temperature (23 ± 2 °C), a wide range of initial dye concentrations (1–1000 mg/dm³), and an adsorbent dose of 50 g. All modifications increased the clay’s adsorption capacity for Reactive Red 198, in the order BC H₂SO₄ > BC NaOH > BC 250 > BC; it was 10.32, 5.06, 3.32, and 2.92 mg/g, respectively. Acid and thermal modification of the clay increased its adsorption capacity for Acid Red 18, in the series BC H₂SO₄ > BC 250 > BC > BC NaOH; it was 3.07, 2.66, 2.16, and 1.28 mg/g, respectively. The experimental data were analyzed by Freundlich, Langmuir, Dubinin–Radushkevich, and Sips isotherms, using nonlinear regression. The experimental data best fitted the Sips isotherm. Taking into account the structure of the adsorbent and adsorbates and the results obtained, it can be concluded that the dyes were probably bound through chemisorption, by forming hydrogen bonds between Si–OH and Al–OH groups in the clay and –NH, –NH₂, and –OH groups in the dyes. From the results obtained, it can be concluded that smectite clay is a promising material for dye adsorption.

The fine fraction of the Tagaran natural clay (TC) from the Kurdistan region of Iraq-Sulaimani was characterized and used to remove Cd ions from industrial swage. Using XRF, XRD, SEM, and FTIR, the dominant clay mineral of the Tagaran clay mineral was identified as saponite, with minor amounts of chlorite. The clay was examined for its efficiency to adsorb and remove (Cd²⁺) in the presence of other heavy metal contaminants from Sulaimani industrial zone sewage by a batch method. The effect of initial pH, equilibrium time, temperature, clay dosage, and Cd²⁺ concentration was studied. Results were evaluated using Langmuir, Freundlich, Temkin, and Redlich-Peterson isotherms. The kinetics could be best fitted to pseudo-second-order reaction kinetic model. In addition, the activation energy and the amount of calculated and experimentally determined heavy metal loads were consistent. The thermodynamic studies showed spontaneous endothermic adsorption. The trioctahedral smectite (saponite) showed a good efficiency for the adsorption of Cd²⁺ from the real sample (up to 100%) which at least partly can be explained by cation exchange. Tagaran clay is a candidate material for the production of an adsorber material for removing Cd²⁺ from aqueous solutions.

Explosive compounds, including known toxicants 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), are loaded to soils during military training. Their fate in soils is ultimately controlled by soil mineralogical and biogeochemical processes. We detonated pure mineral phases with Composition B, a mixture of TNT and RDX, and investigated the fate of detonation residues in aqueous slurries constructed from the detonated minerals. The pure minerals included Ottawa sand (quartz and calcite), microcline feldspar, phlogopite mica, muscovite mica, vermiculite clay, beidellite (a representative of the smectite clay group), and nontronite clay. Energy-dispersive X-ray spectrometry, X-ray diffraction, and gas adsorption surface area measurements were made of the pristine and detonated minerals. Batch slurries of detonated minerals and deionized water were sampled for 141 days and TNT, RDX, and TNT transformation products were measured from the aqueous samples and from the mineral substrates at day 141. Detonated samples generally exhibited lower gas adsorption surface areas than pristine ones, likely from residue coating, shock-induced compaction, sintering, and/or partial fusion. TNT and RDX exhibited analyte loss in almost all batch solutions over time but loss was greater in vermiculite, beidellite, and phlogopite than in muscovite and quartz. This suggests common phyllosilicate mineral substrates could be used on military training ranges to minimize off-site migration of explosive residues. We present a conceptual model to represent the physical and chemical processes that occurred in our aqueous batches over time.