International audience | The cocktail of pesticides sprayed to protect crops generates a miscellaneous and generalized contamination of water bodies. Sorption, especially on soils, regulates the spreading and persistence of these contaminants. Fine resolution sorption data and knowledge of its drivers are needed to manage this contamination. The aim of this study is to investigate the potential of Mid-Infrared spectroscopy (MIR) to predict and specify the adsorption and desorption of a diversity of pesticides. We constituted a set of 37 soils from French mainland and West Indies covering large ranges of texture, organic carbon, minerals and pH. We measured the adsorption and desorption coefficients of glyphosate, 2,4-dichlorophenoxyacetic acid (2,4-D) and difenoconazole and acquired MIR Lab spectra for these soils. We developed Partial Least Square Regression (PLSR) models for the prediction of the sorption coefficients from the MIR spectra. We further identified the most influencing spectral bands and related these to putative organic and mineral functional groups. The prediction performance of the PLSR models was generally high for the adsorption coefficients Kdads (0.4 < R 2 < 0.9 & RPIQ > 1.8). It was contrasted for the desorption coefficients and related to the magnitude of the desorption hysteresis. The most significant spectral bands in the PLSR differ according to the pesticides indicating contrasted interactions with mineral and organic functional groups. Glyphosate interacts primarily with polar mineral groups (OH) and difenoconazole with hydrophobic organic groups (CH2, C=C, COO-, CO , CO -C). 2,4-D has both positive and negative interactions with these groups. Finally, this work suggests that MIR combined with PLSR is a promising and cost-effective tool. It allows both the prediction of adsorption and desorption parameters and the specification of these mechanisms for a diversity of pesticides including polar active ingredients.

Corresponding author. fax: +49 381 498 2159. E-mail address: bernd.lennartz@uni-rostock.de (B. Lennartz). | International audience | This work was initiated to study the effects of climate induced soil water status variations which can reach extreme values under natural conditions on the sorption process of hydrophobic organic compounds. Based on the classical slurry batch methodology an approach is developed that allows the fast and careful complete drying of soil suspensions (microwave technique). Classical adsorption experiments were followed by three desorption steps with and without drying cycles. Drying and re-wetting enhanced the sorption-desorption hysteresis and Freundlich adsorption coefficients increased from 5.9 to 16 and 5.2 to 21 over three drying cycles for diuron and terbuthylazine respectively. Assuming the validity of a dual stage adsorption process, model evaluation suggests that drying is as a shrinking-like process leading to conformational changes of the dominant sorbent (soil organic matter) which restrict the intra-micro-particle diffusion. Rewetting only leads to a partial recovery of the diffusional pore space.

International audience | In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces. © 2005 Elsevier Ltd. All rights reserved.

The objective of this work was to evaluate the adsorption capacity of alkylated modified porous biochar prepared by esterification and etherification (PSAC-2) for low concentrate volatile organic compounds (VOCs, toluene and ethyl acetate) in high humidity environment by experiments and theoretical calculations. Results showed that PSAC-2 has a large specific surface area and weak surface polarity, at 80% relative humidity, its capacities for toluene and ethyl acetate adsorption could be maintained at 92% and 87% of the initial capacities (169.9 mg/g and 96.77 mg/g). The adsorption behaviors of toluene, ethyl acetate, and water vapor were studied by adsorption isotherms, and isosteric heat was obtained. The desorption activation energy was obtained by temperature programmed desorption experiment. The outcomes manifested that the PSAC-2 can achieve strong adsorption performance for weakly polar molecules. Through density functional theory (DFT) simulations, owing to the interaction of hydrogen bonds, oxygen-containing groups became a significant factor influencing the adsorption of VOCs in humid environments. These results could provide an important reference for VOCs control in a high humidity environment.

Arsenic (As) pollution remains a major threat to the quality of global soils and drinking water. The health effects of As pollution are often severe and have been largely reported across Asia and South America. This study investigated the possibility of using unmodified biochar derived from rice husk (RB) and aspen wood (WB) at 400 °C and 700 °C to enhance the precipitation of calcium/arsenic compounds for the removal of As(III) from solution. The approach was based on utilizing calcium to precipitate arsenic in solution and adding unmodified biochar to enhance the process. Using this approach, As(III) concentration in aqueous solution decreased by 58.1% when biochar was added, compared to 25.4% in the absence of biochar. Varying the pH from acidic to alkaline enabled an investigation into the pH dependent dynamics of the approach. Results indicated that significant precipitation was only possible at near neutral pH (i.e. pH = 6.5) where calcium arsenites (i.e. Ca(AsO₂)₂, and CaAsO₂OH•½H₂O) and arsenates (i.e. Ca₅(AsO₄)₃OH) were precipitated and deposited as aggregates in the pores of biochars. Arsenite was only slightly precipitated under acidic conditions (pH = 4.5) while no arsenite was precipitated under alkaline conditions (pH = 9.5). Arsenite desorption from wood biochar was lowest at pH 6.5 indicating that wood biochar was able to retain a large quantity of the precipitates formed at pH 6.5 compared to pH 4.5 and pH 9.5. Given that the removal of As(III) from solution is often challenging and that biochar modification invites additional cost, the study demonstrated that low cost unmodified biochar can be effective in enhancing the removal of As(III) from the environment through Ca–As precipitation.

Arsenic (As) is among the most dangerous metalloids and is harmful to human wellbeing. In this laboratory study, Al(III)-modified kapok fibres (Al-Kapok) were used to remove As(V) from water. The sorbent was characterised using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX). Batch experiments were performed to observe the performance of Al-Kapok in the removal of As(V) and to examine the effects of pH, temperature, adsorbent dose, and coexisting ions on the adsorption process. The surface of the sorbent changed after aluminium modification, and the results of the batch experiments showed that the adsorption of As(V) occurred mainly via endothermic-spontaneous chemisorption at the solution and solid interface of Al-Kapok. The As(V) removal efficiency was approximately 76%–84%, and it was slightly affected at pH levels below 8.0. Further study showed that the maximum adsorption capacity of Al-Kapok for As(V) was 118 μg/g at 30 °C and pH 6, and notable adverse effects were caused by the presence of SO42−and PO43−. It was also found that the boundary layer and film diffusion contributed more to As(V) adsorption. After five adsorption/desorption cycles, regeneration recovered approximately 92% of the adsorption capacity of Al-Kapok used. Overall, Al-Kapok appears to be a suitable adsorbent material for the purification of As-contaminated water.

This study investigates the behavior of Tl in the Ría de Huelva (SW Spain), one of the most metal polluted estuaries in the world. Dissolved Tl concentration displayed a general decrease across the estuary during the dry season (DS); from 5.0 to 0.34 μg/L in the Tinto and Odiel estuaries, respectively, to 0.02 μg/L in the channel where the rivers join. A slighter decrease was observed during the wet season (WS) (from 0.72 to 0.14 μg/L to 0.02 μg/L) due to the dilution effect of rainfalls in the watersheds. These values are 3 orders of magnitude higher than those reported in other estuaries worldwide. Different increases in Tl concentrations with salinity were observed in the upper reaches of the Tinto and Odiel estuaries, attributed to desorption processes from particulate matter. Chemical and mineralogical evidences of particulate matter, point at Fe minerals (i.e., jarosite) as main drivers of Tl particulate transport in the estuary. Unlike other estuaries worldwide, where a fast sorption process onto particulate matter commonly takes place, Tl is mainly desorbed from particulate matter in the Tinto and Odiel estuaries. Thus, Tl may be released back from jarositic particulate matter across the salinity gradient due to the increasing proportion of unreactive TlCl⁰ and K⁺ ions, which compete for adsorption sites with Tl⁺ at increasing salinities. A mixing model based on conservative elements revealed a 6-fold increase in Tl concentrations related to desorption processes. However, mining spills like that occurred in May 2017 may contribute to enhance dissolved and particulate Tl concentrations in the estuary as well as to magnify these desorption processes (up to around 1100% of Tl release), highlighting the impact of the mine spill on the remobilization of Tl from the suspended matter to the water column.

Pollution in soil by petroleum hydrocarbon has become a global environmental problem. The bioremediation of petroleum hydrocarbon-contaminated soil was enhanced with the combination of an isolated indigenous bacterial consortium and biosurfactant. The biodegradation efficiency of total petroleum hydrocarbon (TPH) was increased from 12.2% in the contaminated soil to 44.5% and 57.7% in isolated consortium and isolated consortium & 1.5 g sophorolipid (SL)/kg dry soil, respectively. The half-life of TPH degradation process was decreased from 32.5 d in the isolated consortium reactor to 20.4 d in the isolated consortium & 1.5 g SL/kg dry soil. The addition of biosurfactant into contaminated soils improved the TPH desorption from solid matrix to the aqueous solution and the subsequent solubilization, which ultimately improved the bioavailability of TPH in contaminated soils. Biosurfactant also served as carbon sources which contributed to the stimulation of cell growth and microbial activity and accelerated the biodegradation process via co-metabolism. The enzyme activities and quantities of functional genes were demonstrated to be incremented in SL reactors. The biosurfactant improved the TPH bioavailability, stimulated the microbial activities and participated in the co-metabolism. The combination of bioaugmentation and SL benefitted the bioremediation of petroleum hydrocarbon-contaminated soil.

Though many studies pertaining to soil bioremediation have been performed to study the microbial kinetics in shake flasks, the process efficiency in column tests is seldom. In the present study, soil columns tests were carried out to study the biodegradation of soil contaminated with a high concentration of diesel (≈19.5 g/kg) petroleum hydrocarbons expressed as C₁₀–C₅₀. Experiments were done with crude enzymatic cocktail produced by the hydrocarbonoclastic bacterium, Alcanivorax borkumensis. A. borkumensis was grown on a media with 3% (v/v) motor oil as the sole carbon and energy source. The effects of the enzyme concentration, treatment time and oxidant on the bioremediation efficiency of C₁₀–C₅₀ were investigated. A batch test was also carried out in parallel to investigate the stability of the enzymes and the effect of the biosurfactants on the desorption and the bioconversion of C₁₀–C₅₀. Batch tests indicated that the biosurfactants significantly affected the desorption and alkane hydroxylase and lipase enzymes, maintained their catalytic activity during the 20-day test, with a half-life of 7.44 days and 8.84 days, respectively. The crude enzyme cocktail, with 40 U/mL of lipase and 10 U/mL of alkane hydroxylase, showed the highest conversion of 57.36% after 12 weeks of treatment with a degradation rate of 0.0218 day⁻¹. The results show that the soil column tests can be used to optimize operating conditions for hydrocarbon degradation and to assess the performance of the overall bioremediation process.

Thermal desorption is widely adopted for the remediation of organic compounds, yet is generally considered a non-green-sustainable manner owing to its energy-intensive nature and potential to deteriorate soil reuse. Here, lube oil-contaminated soils were remediated at 200–500 °C in nitrogen atmosphere, upon which removal behaviors of lube oil and physicochemical properties of soils were explored. Illumina 16S ribosomal RNA (rRNA) and 18S rRNA amplicon sequencing were employed to determine the relative abundances and diversities of bacteria and fungi in soils, respectively. The results indicated that, after heating at 350 °C for 60 min, 93% of the lube oil was reduced, with the residual lube oil concentration lower than the Chinese risk intervention values (GB 36600–2018). The weakly-alkaline, multi-phosphorus and char-rich soils after indirect thermal desorption could provide a nutrient source and favorable habitat space for living organisms, and the decomposition of minerals in soils is more conducive to the survival of organisms. Microbial species in soils after heating at 350 °C became extinct, however, microbial species after 3 days of recolonization were enough to carry out DNA extraction when these soils were exposed to natural grass land. Though the microbial richness and diversity in heated soils after 3 days of recolonization were still little lower than those in contaminated soils, Firmicutes (29.41%) and Basidiomycota (9.33%) became dominant at phyla level, while Planomicrobium (16.37%), Massilia (10.09%), Jeotgalibaca (7.91%) and Psychrobacter (6.84%) were dominant at general level, whose ecological function was more conducive to nutrient cycling and ecological resiliency. Overall, this innovative research provides a new perspective: low temperature indirect thermal desorption may also achieve a sustainable remediation, due to its energy-saving (low temperature), favorable physicochemical properties and the rapid recolonization capacity of microbial communities in heated soils.